JPH083321A - Composition for coloring vinylidene chloride-based resin - Google Patents

Abstract

PURPOSE:To obtain the subject composition capable of giving a good-quality colored product with a pigment dispersed homogeneously therein, assuring stable extrudability even in coloring at high deepness, and capable of maintaining film characteristics even in conducting film processing, comprising a vinylidene chloride-based copolymer resin having a specific weight-average molecular weight and a specified proportion of a pigment. CONSTITUTION:This composition comprises (A) a vinylidene chloride-based copolymef resin 5000-80000 in weight-average molecular weight determined by gel permeation chromatography and (B) <=90wt.%, based on the composition, of a pigment. It is recommended that the component A be prepared, for example, by the following process: a mixture of ion-exchanged water, a suspending agent and polymerization initiator is incorporated with 50-85wt.% of vinylidene chloride monomer and 15-50wt.% of a monomer to be copolymerized therewith followed by heating at 40-80 deg.C under vigorous agitation to carry out a polymerization for about 10-50h.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition used for coloring a vinylidene chloride resin.

[0002]

2. Description of the Related Art It has been conventionally known that a vinylidene chloride resin is mixed with a coloring agent to form a film, a fiber, a sheet or the like. These are mainly pigments directly used as colorants. However, the method of directly using the pigment as the colorant causes the pigments to aggregate in the mixing process and contaminate the inside of the mixer,
There is a problem that extrusion processability is deteriorated, and such a phenomenon is particularly remarkable when high-density coloring is performed.

As a means for solving these problems, a masterbatch method in which a pigment is kneaded in advance in a vinylidene chloride resin is generally considered. However, since general vinylidene chloride resins have poor thermal stability, deterioration of the resin progresses due to shearing heat generation and the like due to kneading. Therefore, it is almost impossible to obtain a masterbatch having good dispersibility. On the other hand, a method in which a resin having a good compatibility with a vinylidene chloride resin is used as a vehicle can be considered. These are generally called moisturizing colors, and the vehicle whose main component is polyethylene wax (Japanese Patent Publication No. 35-1368).
No. 1), a resin whose main component is a vinyl chloride resin (Japanese Patent Publication No. 59-37019), and a resin whose main component is an ethylene-vinyl acetate resin. Further, as a coloring agent for vinyl chloride resin, there is a coloring agent whose main component is an acrylic-styrene copolymer resin or a polyester resin (JP-A-4-366152). The moisturizing color is
A resin mixture in which a pigment is dispersed in a fine powder state is formed in a resin serving as a vehicle, and the resin mixture is formed into a flake form,
It is obtained by processing into powder and is known as a colorant that is easy to handle.

[0004]

However, polyethylene wax (Japanese Patent Publication No. 35-1) is used as a vehicle when it is used for coloring vinylidene chloride resin among the above-mentioned wet colors.
No. 3681), ethylene-vinyl acetate resin, and vinyl chloride resin (Japanese Patent Publication No. 59-37019), phase separation of the resin occurs in the extruder, and stable extrusion cannot be performed. . Acrylic-styrene copolymer resin and polyester resin (Japanese Patent Laid-Open No. 4-36615)
No. 2) and the like have a problem that when formed into a film, the gas barrier property, which is a characteristic of vinylidene chloride resin, is deteriorated. Further, there is a problem that a sealing failure occurs when the film is subjected to high frequency sealing.

According to the present invention, when used for coloring a vinylidene chloride resin, it is possible to obtain a high-quality colored product in which the pigment is uniformly dispersed, and stable extrudability is obtained even when a high-concentration coloring is applied. It is an object of the present invention to provide a vinylidene chloride-based resin coloring composition capable of ensuring the above-mentioned properties and sufficiently retaining film properties such as barrier properties and high-frequency sealing properties.

[0006]

Means for Solving the Problems The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems. That is, the present invention is a coloring composition containing a vinylidene chloride-based copolymer resin and a pigment, wherein the vinylidene chloride-based copolymer resin has a weight average molecular weight of at least 55,000 as determined by gel permeation chromatography. It is a vinylidene chloride-based resin coloring composition which is 80,000 or less and the content of the pigment is 90% by weight or less based on the coloring composition. The contents will be described below.

The vinylidene chloride resin copolymer used in the present invention means that the content of vinylidene chloride is 50 to 99% by weight, vinylidene chloride and a polymerizable monomer (for example, vinyl chloride and methyl acrylate). , Butyl acrylate, etc.) is preferred and the total content is 50 to 1% by weight.
(Total weight of monomers). Above all, from the viewpoint of maintaining thermal stability during kneading-extrusion, the content of vinylidene chloride is 70 to 90% by weight, and the total content of vinylidene chloride and a polymerizable monomer is 30 to 10% by weight. Polymers are preferred.

The present invention differs from the prior art in that the resin used in the vehicle is a vinylidene chloride copolymer resin having a specific molecular weight. The importance of this difference is that it is possible to provide a colorant in which the pigment is retained in a homogeneous dispersion state in the vinylidene chloride copolymer resin by suppressing the thermal decomposition that occurs during kneading, and used in the vehicle. Since the vinylidene chloride-based copolymer resin does not undergo thermal decomposition so much and has good compatibility with the vinylidene chloride-based resin, it is possible to sufficiently exhibit the properties as a colorant.

FIG. 1 is an experimental view showing the state of thermal decomposition of a vinylidene chloride resin during heating and kneading (see Reference Example 1 below). That is, the horizontal axis represents the kneading time (minutes), the vertical axis represents the degree of yellowing and browning of the resin due to thermal decomposition (b value), and the discoloration of the resin progressing with the kneading time (thermal decomposition).
It shows the relationship of degree. The black circles (●) in FIG. 1 indicate the case of ordinary (weight average molecular weight 110,000) vinylidene chloride resin, and the white circles (◯) indicate the case of vinylidene chloride copolymer resin having a molecular weight of 40,000. . Also shown in the figure
The value of is the resin temperature indicated by the kneaded target resin.

When attempting to disperse a high-concentration pigment in the resin by the kneading effect of the resin using a heating roller or the like,
Generally, a kneading time of at least 15 minutes, preferably about 30 minutes is required. When the resin using the vehicle undergoes thermal decomposition during kneading, the thermal stability of the colored polymer as a whole is not only deteriorated due to the fact that the thermally decomposed resin is mixed with the coloring polymer together with the coloring agent. The quality of the molded product also deteriorates due to the effect of its thermal decomposition products. On the other hand, when the degree of thermal decomposition of the vinylidene chloride-based resin (yellowing or browning of the resin) is indicated by the b value of the color difference meter, while the b value including the original yellowing of the resin itself is 15 or less, It is empirically known that thermal decomposition is slight.

Considering the result of FIG. 1 from the above viewpoint,
For the conventionally known vinylidene chloride resin (molecular weight: 110,000), the degree of thermal decomposition is limited within a kneading time of 10 minutes (b value = 15).
When the kneading time exceeds 20 minutes, the b value reaches 50 and the thermal decomposition progresses significantly to reach the browning region. Therefore,
It is impossible to disperse the pigment in the resin by utilizing the kneading effect in the conventionally known vinylidene chloride resin. On the other hand, the vinylidene chloride copolymer resin (molecular weight 40,000) falling within the scope of the present invention has a b value of less than 15 even if the kneading time is 30 minutes, and suppresses the degree of thermal decomposition to a low level. It is understood that it is done. This effect of suppressing thermal decomposition is considered to be due to the low molecular weight (melt viscosity) of the vinylidene chloride-based copolymer resin, and it is often the case that the resin temperature does not rise due to shearing heat generated during kneading. It is presumed that this has contributed to the extension of the kneading time up to this point.
The fact that the increase in the resin temperature shown in FIG. 1 is lower for the low molecular weight resin is one of the reasons for the existence of the above phenomenon.

On the basis of the above experimental results, the present invention utilizes the "effect of extending the kneading time until thermal decomposition" of the low molecular weight vinylidene chloride copolymer resin into the vehicle (resin) pigment. Of the vehicle (resin) is utilized to ensure the extrudability of the colored polymer and the quality of the obtained colored product. Further, since the vehicle itself used is a vinylidene chloride-based resin which is the same as the base resin of the colored polymer, the compatibility between the resins is enhanced.

It is important that the vinylidene chloride copolymer resin, which can be expected to have the above-mentioned effects, has a weight average molecular weight of 55,000 or more and 80,000 or less as determined by gel permeation chromatography. From the viewpoint of the above, the range of 10,000 or more and 60,000 or less is preferable. 0.5
When the molecular weight is less than 1, the shear stress is too small. On the contrary, when the molecular weight exceeds 80,000, the effect of extending the kneading time is too small and both are inconvenient for dispersing the pigment.
The number average molecular weight of the vinylidene chloride copolymer resin in the present invention is about 20,000 to 40,000.

The vinylidene chloride copolymer resin in the present invention can be manufactured by the following method. First, in a polymerization machine, ion-exchanged water and cellulose such as methylcellulose as a suspending agent are used.
Organic derivative such as diisopropyl peroxydicarbonate as a polymerization initiator, and vinylidene chloride monomer in an amount of 50 to 85% by weight and a monomer to be copolymerized in an amount of 15 to 50% by weight. Charge approximately the same amount (weight) as ion-exchanged water, add it, and stir the mixture vigorously. Then, while heating to a temperature of 40 to 80 ° C, about 10
Polymerize for ~ 50 hours. Further, if desired, after polymerization is completed, the mixture is transferred to a slurry-mix tank, and the obtained product is added with a plasticizer such as an aliphatic dibasic acid ester or a fatty acid ester, epoxidized vegetable oils, condensed phosphates, stearic acid. Additives such as heat stabilizers represented by alkyls may be added in an amount of 0.1 to 10% by weight based on the total amount of the resin. After that, it is filtered, washed with water, transferred to a dehydrator to be dehydrated to some extent, and then dried by a floor dryer until the water is completely removed. The vinylidene chloride-based copolymer resin thus obtained has a resin melt viscosity using a flow tester CFT-500 type manufactured by Shimadzu Corporation under a condition of a load of 40 kgf and a die size of 1 mmφ-2 mmL at a temperature of 180 ° C. Apparent melt viscosity by constant temperature test (unit: pois
When e) is measured, it is preferably in the range of 500 to 9000 poise.

As the pigment used in the present invention, known pigments conventionally used for coloring vinyl chloride resins can be used. For example, inorganic pigments represented by titanium oxide, carbon black, cobalt blue, magnesium oxide, zeolite, calcium carbonate, barium sulfate, talc, silicon dioxide, alumina, etc., azo-based, benzimidazolone-based, diarylide-based, quinacridone-based, dioxazine An organic pigment represented by a system, an isoindolinone system, a phthalocyanine system, or the like can be used.

In the present invention, it is important that the pigment concentration in the obtained coloring composition is 90% by weight or less. If the pigment content exceeds 90% by weight, the amount of resin is relatively insufficient and the kneading operation is difficult, and the effect of preventing aggregation by coating the pigment with resin cannot be expected. From the viewpoint of keeping the pigment homogeneously dispersed in the resin,
The amount of pigment based on the coloring composition is preferably 5 to 60% by weight. The pigment concentration can be lowered to, for example, 1 to 3% by weight, but the low pigment amount means that the amount of the colorant composition used is relatively increased when the colored polymer is prepared. The higher the target pigment concentration of the colored polymer, the higher the amount of the low molecular weight resin to occupy. Therefore, the quality of the colored molded product may be deteriorated due to the increase of the low molecular weight resin. In such a case, it is desirable to increase the amount of pigment in the colorant composition to 10% by weight or more.

The coloring composition of the present invention is used for coloring a conventionally known vinylidene chloride resin. Particularly, the vinylidene chloride content is 50 to 99% by weight, and the total content of vinylidene chloride and a polymerizable monomer (specifically, vinyl chloride, methyl acrylate, butyl acrylate, etc. is preferably 50 to 1% by weight). % Copolymer having a weight average molecular weight of 90,000 to 140,000 and is optimally used. In addition, a vinylidene chloride content of 70 to 90% by weight and a total content of vinylidene chloride and a polymerizable monomer of 30 to 10% by weight, which are considered to be preferable from the viewpoint of increasing thermal stability during extrusion, Also used for coalescing.

[0018]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The evaluation method used in the present invention is as follows. (1) Weight average molecular weight The weight average molecular weights of the vinylidene chloride copolymer resin and the vinylidene chloride resin in the present invention are determined by gel permeation chromatography using polystyrene as a standard. The equipment used is as follows.

Model: High Performance Liquid Chromatography (manufactured by Waters) Column: Microstyrasil (manufactured by Waters) Solvent: Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, for liquid chromatography) The measuring method is as follows. A sample to be measured dissolved in tetrahydrofuran at a concentration of 0.5% by weight was injected into a column kept at 20 ° C. together with a solvent, and the change in output current value of the differential refractometer after injection of the sample with time was recorded. Have them be drawn on the total chart.

Molecular weights of 3600, 35000, 1100
For each of the five types of monodisperse polystyrenes of 00, 650000, and 146000, the measurement with this measuring instrument was completed in advance, and this data was used as a calibration curve to calculate the basis of vinylidene chloride copolymer resin and vinylidene chloride resin. And That is, the gel permeation chromatography count number (the number of seconds starting from the time of sample injection as 0) until the peak value of the output current of the differential refractometer is exhibited by the monodisperse polystyrene having the existing molecular weight, and its molecular weight (one The relationship with (logarithm) is used as the coordinate point, and a graph connecting these five types of coordinate points is created and this is used as the inspection line for calculating the molecular weight.

The measurement and calculation are as follows. From the relationship chart between the gel permeation chromatography count number drawn on the target resin sample and the output current value of the differential refractometer, the gel permeation chromatography count number 900 to 1440 is divided into 20 count positions. The output current value (Pi) shown in 1 is obtained as the frequency of the molecular weight (according to the inspection line) Mi corresponding to the gel permeation chromatography count number, and is calculated as follows.

Weight Fraction of Molecular Weight Mi Wi = Pi / ΣPi Next, the weight average molecular weights of the vinylidene chloride copolymer resin and the vinylidene chloride resin in the present invention are the weight fractions Wi of the molecular weight Mi thus calculated. Calculation is performed as follows using the molecular weight Mi. Weight average molecular weight = Σ (Wi × Mi) The content of the copolymer having a molecular weight of 20,000 or less in the present invention is
Calculate as follows. The weight fractions Wi corresponding to each of the Mi having a molecular weight of 20,000 or less are summed, and 100 times the sum is
The content (% by weight) of the copolymer having a molecular weight of 20,000 or less is used. (2) Practical evaluation of coloring composition [Coloring of vinylidene chloride resin] Vinylidene chloride resin (vinylidene chloride / vinyl chloride = 85/15% by weight in powder form) is used as a plasticizer and dibutyl seba as a heat stabilizer. Cate 3%, acetyltributyl citrate 2.5%,
2% epoxidized linseed oil, lubricant, 0.15% erucic acid amide as a satin finish, and 0.1% silicon dioxide are added and mixed in advance to obtain a target pigment concentration. (Hereinafter referred to as a coloring agent), and a conical blender (actual mixing capacity: 200 kg)
After dry blending for 200 minutes, 200 kg of vinylidene chloride resin (hereinafter referred to as a colored polymer) was prepared. [Formation of Colored Polymer into Film] The above colored polymer was supplied to an extruder having a diameter of 40 mm and an L / D = 18, which was equipped with a circular extrusion die having a slit of 1.5 mm and a diameter of 150 mm at its tip, and the colored polymer was tubularized. Extruded. After supercooling this tubular body, it is biaxially stretched 4 times in the flow direction and 4 times in the width direction using an inflation biaxial stretching method to obtain a tubular film, and the tubular film is folded with a pinch roll to obtain a target thickness of 40 μm. A flat long double ply film having a folding width of about 1 m was prepared. [Evaluation Items and Evaluation Scale] Extrusion Molding Stability Evaluation In carrying out continuous extrusion molding of a film by the above method, particular attention was paid to uniform thickness. However, depending on the object to be extruded, the thickness cannot be adjusted from the beginning, and even if the initial thickness can be adjusted, the thickness unevenness increases with time and the adjustment becomes impossible. Therefore, here, the length of the extrusion time during which the thickness variation range could be adjusted to the range of 10 μm was used as an index of the stability of the extrusion molding.

Evaluation scale Time during which uniform adjustment is possible Evaluation symbol Remarks 20 hours or more ○ Stable continuous production is possible 5 hours or more but less than 20 hours △ Productivity is poor but continuous production is possible less than 5 hours × Continuous production is not possible Evaluation of Dispersibility With respect to the colored film obtained in [Formation of colored polymer film], the state of dispersion of the pigment in the film was observed with an optical microscope. The area of 100 cm ² was randomly observed at 10 points, and the number of pigment agglomerates having a particle size of 40 μm or more was examined and used as an evaluation scale.

Evaluation scale Number of pigment lumps with a size of 40 μm or more Evaluation code Remarks 0 pieces ○ Excellent as product value 1 or more and less than 10 △ Product value 5 or more × No product value Friction fastness test Above The colored film obtained in [Polymer film formation] was subjected to a friction fastness test using a friction tester type II described in JIS-L0823 standard. As conditions, soybean oil is applied on the film, film 10 cm
The space was rubbed 100 times with a white cotton cloth to test how much color was transferred to the white cotton cloth and used for evaluation.

Evaluation scale Degree of color transfer of white cotton cloth Evaluation symbol Remark Color transfer cannot be confirmed ○ Excellent as product value Slightly visible △ Product value is fair Color transfer is considerably × No product value Oxygen permeation Evaluation of the colored film obtained in [Formation of colored polymer into film] according to JIS-K7126 (Mocon method), a film having a thickness of 40 μm was measured and converted into a thickness of 1 μm (unit: cc · μm / m ² · day at 4
0 ° C. 90% RH).

Evaluation scale Oxygen permeability (cc) Evaluation symbol Remark Less than 30 ○ Excellent as commercial value 30 or more and less than 35 △ Commercial value 35 or more × No commercial value High frequency sealability evaluation by automatic filling and packaging machine The colored film obtained in [Formation of colored polymer film] was evaluated for high-frequency sealing property by an automatic filling and packaging machine. That is, FIG. 2 is a schematic view showing the main steps of the automatic filling and packaging machine used for evaluation of high-frequency sealing property. In FIG. 2, a flat strip-shaped long film F1 of a vinylidene chloride-based resin film drawn from the original fabric A is
While continuously passing through the folder 1, both side edges of the strip-shaped films are overlapped to form a tubular shape, and subsequently, the films are overlapped between the high frequency electrodes 2 (applying side) and 3 (ground side). Complete tubular film F with welded joints
It becomes 2. On the other hand, the object to be packed 4 quantified by the metering pump M is filled into the tubular film F2 from the tip of the nozzle 5 through the flow path passing through the inside of the folder 1. Further, the tubular film F2 delivered by the feed roller 6 is squeezed by the pair of squeezing rollers 7 to the object 5 to be packaged at a constant cycle, and a ligation planned portion F3 is formed in the squeezed portion. The to-be-ligated portion F3 is simultaneously ligated at two locations by a metal clip in the ligating device 8, and the two ligatures are cut off to become individual packages F4, which are carried out through the chute 9. The main condition at this time is that the current value of high frequency welding is 7
0mA, electrode surface pressure 450g, film running speed 3
The product length of the package (the length between the ligating metal clips at both ends) was set to 0 mm / min, and the content was kamaboko meat. (A) Bag breakage rate of the package About 4000 pieces of the obtained package F4, the gauge pressure inside the heating can was 3.0 kg / cm ² , and the temperature was 120 ° C., 2
After heat and pressure sterilization under the condition of 0 minutes, and after pressure cooling to a temperature of 80 ° C. while maintaining the pressure in the heating can, the pressure was released and the product was taken out from the heating can to obtain a final package. 1000 pieces were collected from the final package obtained, the number of bags broken from the sealed portion of the package was investigated, and the bag breakage rate was evaluated by the following formula.

Bag-breaking rate (%) = (Number of bag-breaking pieces / 1000) × 100 Evaluation scale Bag-breaking rate (%) Evaluation symbol Remark 0% ○ Excellent product value 0.2% or more and less than 0.5% △ There is commercial value 0.5% or more × no commercial value (b) Pinhole rate 1000 pieces were randomly sampled from the final package and immersed in a dilute solution of methylene blue for 1 day. At that time, the portion where the contents of the package are dyed blue is used as a pinhole (if the film has a pinhole, the methylene blue solution permeates into the package and the contents are dyed blue). The number of occurrences was investigated and the pinhole rate was evaluated by the following formula.

Pinhole rate (%) = (number of pinholes generated / 1000) × 100 Evaluation scale Pinhole rate (%) Evaluation symbol Remark 0% ○ Excellent product value 0.2% or more 0. Less than 5% △ There is a commercial value 0.5% or more × There is no commercial value Comprehensive evaluation Overall evaluation was performed according to the following criteria with respect to the above-mentioned evaluation items.

Evaluation scale Content evaluation symbol All of the evaluation results of the above 5 items are ○ ○ There is no × of the evaluation results of the above 5 items, but △ is present △ × of the evaluation results of the above 5 items Have x

[0030]

Example 1 and Comparative Example 1 A vinylidene chloride copolymer resin having a weight average molecular weight of 40,000 (vinylidene chloride / vinyl chloride copolymer = 85/15% by weight) was used as a vehicle, to which epoxidized linseed oil was added. Was added so as to be 5% by weight with respect to the colorant, and Pig. Yellow8
Pigment No. 3 (Hoechst, trade name PV Fast Ye
(low) was added so as to be 30% by weight with respect to the colorant, and premixing was performed for 3 minutes using a high speed mixer manufactured by Kawata. The pre-mixture was heated to a roller surface temperature of 150.
Biaxial heating roller adjusted to ℃ (roller diameter 200m
m, roller speed ratio 1: 3, 50 μm between rollers) about 1
The mixture was kneaded by passing it 5 times over 5 minutes. Immediately after the kneading is completed, the roller is rapidly cooled to obtain a sheet having a thickness of about 1 mm,
This product was crushed with a juicer mixer to such an extent that it could pass through a 24 mesh screen to obtain a colorant (colorant N
o. 1).

Further, the vinylidene chloride-based copolymer resin used for the vehicle has a weight average molecular weight of 50,000,
In addition to the above, the colorant Nos. 60, 80,000, 40,000, 90,000 and 110,000 were used. The same experiment as in 1 was repeated (colorant No. 2,
3, 4, 5, 6, 7, and 8). Using these colorants, a colored polymer was prepared by the method described above in [Coloring of vinylidene chloride resin]. In this case, the amount of the colorant added was 1% by weight based on the weight of the colored polymer. A colored film is prepared from this colored polymer by the above-mentioned [Formation of colored polymer film], stability of extrusion molding, evaluation of dispersibility of pigment, evaluation of dye fastness test, evaluation of oxygen permeability, automatic filling and packaging machine. The high frequency sealability was evaluated for each colorant. They are collectively shown in Table 1 and Table 2. Table 1 shows the contents of the colorants in Table 2.

[0032]

[Table 1]

[0033]

[Table 2]

From the results shown in Table 2, the vinylidene chloride copolymer resin used as the vehicle for the colorant composition has a weight average molecular weight of from 5,000 to 80,000, which is used as the colorant. In that case, stable extrusion molding is possible, and the resulting film has good physical properties (colorant N
o. 1, 2, 3, 4, 5). On the other hand, when the weight average molecular weight is less than 50,000 or more than 80,000, the dispersibility of the pigment is poor, and the high frequency sealing property of the automatic filling and packaging machine is also deteriorated by this, so that it is practical. It is found that there is no colorant (see colorants Nos. 6, 7, and 8).

[0035]

[Comparative Example 2] The resin used in the vehicle was polyethylene wax (Mitsui Petrochemical Co., Ltd., trade name Mitsui High Wax), ethylene-vinyl acetate resin (Sumitomo Chemical Co., Ltd., trade name Evertate vinyl acetate content 15%), ethylene-acetic acid. Vinyl resin (Sumitomo Chemical Co., Ltd., trade name Evatate,
The colorant No. is the same as that of the above-mentioned colorant No. except that the vinyl acetate content is 26%), the acrylic-styrene copolymer resin (manufactured by Mitsubishi Rayon Co., Ltd., product name Metablen) and the vinyl chloride resin (manufactured by Sekisui Chemical Co., Ltd.) The experiment of No. 1 was repeated (colorants Nos. 9, 10, 11, 12, and 13 were used respectively).

Using these coloring agents, a colored polymer was prepared by the above method [Coloring of vinylidene chloride resin].
In this case, the amount of the colorant composition added was 1% by weight based on the weight of the colored polymer. A colored film is prepared from this colored polymer by the above-mentioned [Formation of colored polymer film], stability of extrusion molding, evaluation of dispersibility of pigment, evaluation of dye fastness test, evaluation of oxygen permeability, automatic filling and packaging machine. The high frequency sealing property was evaluated for each colorant composition. They are collectively shown in Table 3 and Table 4. Table 3 shows the contents of the colorants in Table 4.

[0037]

[Table 3]

[0038]

[Table 4]

From the results shown in Table 4, when the resin of the vehicle is different from the vinylidene chloride resin which is the base of the coloring polymer, one of the evaluation items becomes a problem and the coloring agent for the vinylidene chloride resin becomes a problem. It turns out that the product value is not satisfactory.

[0040]

Example 2 and Comparative Example 3 In addition to changing the pigment used for the colorant and the pigment concentration relative to the colorant as shown in [Contents of the colorant] in Table 5, the colorant Nos. Experiment 1 was repeated (colorants No. 14, 15, 1
6, 17, 18). Using these colorant compositions, a colored polymer was prepared by the method of [Preparation of colored polymer for evaluation]. A colored film is prepared from this colored polymer by the above-mentioned [Formation of colored polymer film], stability of extrusion molding, evaluation of dispersibility of pigment, evaluation of dye fastness test, evaluation of oxygen permeability, automatic filling and packaging machine. The high frequency sealing property was evaluated for each colorant composition. They are collectively shown in Table 6.

[0041]

[Table 5]

[0042]

[Table 6]

According to the results shown in Table 6, when the pigment concentration with respect to the colorant is within 90% by weight, the stability of extrusion molding when used as the colorant, the dispersibility of the pigment, and the evaluation of the film physical properties are all evaluated. It can be seen that the evaluation items are good (see Coloring Nos. 14, 15, 16, 17). Compared to this,
When the pigment concentration exceeds 90% by weight with respect to the colorant, the dispersibility of the pigment is poor and it is difficult to use it as a colorant (see Colorant No. 18).

[0044]

Example 3 Colorant No. The amount of the colorant composition added in 1 was changed, the pigment concentration in the film was changed as shown in [Contents of colorant] in Table 7, and the colored polymer was prepared by the method of [Coloring of vinylidene chloride resin] above. Created. A colored film is prepared from this colored polymer by the above-mentioned [Formation of colored polymer film], stability of extrusion molding, evaluation of dispersibility of pigment, evaluation of dye fastness test, evaluation of oxygen permeability, automatic filling and packaging machine. The high frequency sealing property was evaluated for each colorant composition. They are collectively shown in Table 8.

[0045]

[Table 7]

[0046]

[Table 8]

From the results in Table 8, it can be seen that good results were obtained even with a pigment concentration of 10% by weight relative to the film, and it is possible to produce a film colored at a high concentration.

[0048]

Example 4 The colorant No. Using the colorant No. 1, a colored polymer was prepared by the method of [Coloring of vinylidene chloride resin] above. In this case, the addition amount was set to 1% by weight, 5% by weight and 10% by weight to obtain three kinds of colored polymers respectively. The colored polymer has a diameter of 0. 7mm extrusion port is 7
Two extruding dies arranged in a circle are supplied to an extruder having a diameter of 40 mm and L / D = 18 attached to the tip, and a molten filamentous body having a circular cross section is continuously extruded. This is divided into 8 yarns each, which is introduced into a cold water tank and heated with hot water whose temperature is adjusted to 30 ° C. to extend 4 times, and a target single yarn denier 120 (9 bundles, target total denier 1080 Multifilament)
It was extruded into a fiber (thread) by taking 8 pieces. The denier means the number of g of a yarn of 9000 m.

The stability of extrusion molding when using this colorant composition was evaluated by the length of extrusion time in which the denier variation range can be adjusted to a range of 20 denier. As a result, the stability was almost the same as in the case of extrusion molding of the uncolored polymer, and further, the result of observing the dispersion state of the pigment in the fiber with an optical microscope showed that there was no lump of the pigment, and the extrusion moldability and dispersion It was confirmed that there was no problem with sex. This result indicates that the colorant composition referred to in the present invention can be applied to other molded products of the film.

[0050]

Reference Example 1 This experiment is for an experiment in the state of thermal decomposition of vinylidene chloride resin shown in FIG. That is, two types of polymers, a vinylidene chloride / vinyl chloride copolymer (85/15% by weight) having a weight average molecular weight of 40,000 and 110,000 in the gel permeation chromatography method described in the present text, are added to epoxidized flaxseed. Oil was added in an amount of 2% by weight with respect to the weight of the colorant and mixed for 3 minutes by a high speed mixer manufactured by Kawata Co., Ltd. to prepare 3 kg of a polymer. Each of the prepared two kinds of polymer 500g,
Kneading is performed with a biaxial heating roller (roller diameter 200 mm, roller speed ratio 1: 3, roller gap 50 μm) adjusted to a roller surface temperature of 150 ° C., and 1 after starting kneading.
After 1 minute, a sheet with a thickness of about 1 mm (about 1 g of chips)
Was collected, and this color tone was measured by a color difference meter (Z-30 manufactured by Nippon Denshoku Co., Ltd.).
The b value was measured by the 0A reflection method). Then, the above measurement was repeated every 5 minutes from the start of kneading until the b value exceeded 50, and at the same time, the temperature of the resin being kneaded was measured by a contact type thermometer. Regarding the measurement results, the comparison between the two is summarized in FIG.

[0051]

INDUSTRIAL APPLICABILITY According to the present invention, when used for coloring a vinylidene chloride resin, it is possible to obtain a high-quality colored product in which the pigment is uniformly dispersed, and it is stable even when a high-concentration coloring is applied. It is possible to provide an excellent coloring composition which can ensure excellent extrudability and can sufficiently retain the characteristics of the film when processed into a film.

[Brief description of drawings]

FIG. 1 is an experimental view showing the state of thermal decomposition of vinylidene chloride resin during heating and kneading.

FIG. 2 is a schematic view showing main steps of a packaging machine.

[Brief description of reference numerals]

 1 Folder 2 High Frequency Electrode (Applying Side) 3 High Frequency Electrode (Ground Side) 4 Object to be Packaged 5 Nozzle 6 Feed Roller 7 Ironing Roller 8 Ligating Device 9 Shoot 10 Raw Fabrication Metering Pump F1 Flat Strip Long Film F2 Tube Film F3 ligation planned part F4 package

Claims (1)

[Claims] 1. A coloring composition comprising a vinylidene chloride-based copolymer resin and a pigment, wherein the vinylidene chloride-based copolymer resin has a weight average molecular weight of at least 55,000 as determined by gel permeation chromatography. 80,000 or less, and the content of the above pigment is 9 with respect to the coloring composition.
A vinylidene chloride-based resin coloring composition, which is 0% by weight or less.