KR101977321B1 - Process for producing highly heat-resistant orange type inorganic pigment for Polyamide, and highly heat resistant orange type inorganic pigment for Polyamide produced by this process - Google Patents

Abstract

The present invention relates to a method of producing a highly heat-resistant orange type inorganic pigment for polyamide which is produced by firing a mixture of inorganic material powder including titanium dioxide (TiO_2), zinc peroxide (ZnO_2) and a stannic oxide (SnO_2), and a highly heat-resistant orange type inorganic pigment for polyamide produced thereby. According to the present invention, the highly heat-resistant orange type inorganic pigment is an environmentally friendly inorganic pigment which has excellent compatibility with a polyamide resin used as an orange colored material for automobile components such as a battery pack, a high voltage cable and peripheral parts thereof having a highly heat-resistant and high rigidity material applied thereto, and which has excellent heat resistance not to be carbonized or discolored during processing of the resin at high temperatures. Unlike an existing method of producing an orange type inorganic pigment, the method of the present invention has an effect of obtaining a high productivity by firing a mixture of the inorganic material powders and producing the orange type inorganic pigment such that the orange type inorganic pigment can be produced by a simple method.

Description

TECHNICAL FIELD [0001] The present invention relates to a process for producing a highly heat-resistant orange inorganic pigment for polyamide and an orange-based inorganic pigment produced by the process, this process}

The present invention relates to an orange-based inorganic pigment produced by firing a mixture of titanium dioxide (TiO ₂ ), zinc oxide (ZnO ₂ ) and inorganic tin oxide (SnO ₂ ), and a high heat- It is excellent in compatibility with polyamide resin used as orange automobile parts material such as battery pack, high voltage cable and its peripheral parts, Resistant orange inorganic pigment for polyamide and an orange-based inorganic pigment produced by the method.

In recent years, interest in eco-friendly vehicles and hybrid vehicles has been increasing rapidly due to environmental regulations in the world's automobile market. In the case of a hybrid vehicle using both power sources of gasoline and electricity, , Which is a next-generation automobile with fuel economy higher than that of conventional vehicles and dramatically reducing emissions of harmful gases.

In the case of hybrid vehicles, unlike conventional automobile parts, newly applied parts include battery packs, high-voltage cables, and their peripheral components. High heat-resistant and high-rigidity materials are used for fire prevention and shock protection. In addition, there is a standard for expressing the risk visually, and it is classified into a general voltage cable which distinguishes colors according to parts and a high voltage cable of orange color.

Conventional general-purpose plastics usually have a processing temperature of less than 200 ° C. Therefore, in order to realize orange color from general-purpose plastics, it is possible to use existing organic pigments such as moribundate orange and permanent nut orange. However, Since the cable is installed in the engine room and is directly or indirectly affected by the heat of the engine, it is difficult to apply the general-purpose plastic and the use of the high-heat-resistant plastic is required.

In order for plastics to have high heat resistance, general-purpose plastics such as polypropylene (PP) have limitations, so polyamide (PA), an engineering plastic, is utilized. Since the above-mentioned polyamide (PA) material has a processing temperature in the vicinity of 250 to 300 ° C, there is a limit to the implementation of an orange color as a conventional pigment, that is, it is difficult to realize a desired color due to damage of the pigment during processing.

In order to prevent the occurrence of fire and to protect the impact, a polyamide material having high heat resistance and high rigidity should be used. In order to apply the orange inorganic pigment thereto, a red color series pigment should be used However, red color pigments are currently products of lead compound, molybdate orange or cadmium compound, and are subject to many restrictions on human health and environmental regulations, In Engineering Plastics, a part of Solvent Dye is applied as a coloring agent in the red color series. However, the purchase price is too high, and due to the nature of Solvent Dye, the hiding power is low, (Migration) phenomenon occurs and there is a problem that usage is restricted.

Therefore, a variety of researches and developments have been made to develop high-heat-resistant red color pigments in domestic and foreign companies. However, due to lack of technology and application, red color red series excellent in compatibility with polyamide (PA) Have not been developed until now.

On the other hand, referring to the prior art documents for inorganic pigments embodying orange-based colors, a pigment based on Pigment Orange (CI) Pigment Orange 82, in particular titanium oxide containing tungsten oxide, zinc oxide, There has been proposed an invention relating to a mixed metal oxide pigment based on tin oxide and optionally silica, other metal oxides and / or metal sulfides, a method for producing the same, and use thereof as a colorant in various applications. In Patent Document 2, titanium tetrachloride, Tin and zinc chloride were dissolved in a concentrated hydrochloric acid aqueous solution at room temperature to prepare a solution prepared so that the molar ratio of titanium to tin and zinc was 2: 1: 1 and the pH was adjusted to 0.5. The solution was added to an aqueous solution of sodium carbonate under nitrogen, , Stannic oxide, and zinc oxide are precipitated together, and the resulting mixture is dried and fired. People are proposed.

However, the patent document 1 proposes a technique for providing an inorganic pigment exhibiting a desired color such as high saturation, high opacity and / or red coloration in combination with excellent performance properties such as weatherability, There has been proposed a technique relating to a colored inorganic complex of titanium, tin and zinc oxide used for producing a pigment capable of imparting a color of red, yellow or green to plastics, paints, glass or ceramics, There is a problem that it is not properly verified to be applied to a polyamide (PA) material having a temperature of ~ 300 ° C.

Therefore, the applicant of the present invention has completed the present invention by developing a high heat resistant orange inorganic pigment that can be applied to polyamide (PA) having a high processing temperature as described above.

Korean Patent Publication No. 10-2016-0014632 (published on Feb. 11, 2016) Inorganic red pigment U.S. Patent No. 4,063,956 (registered on December 20, 1977) Colored inorganic complexes for use as pigments and compositions containing them

The present invention relates to an orange-based inorganic pigment produced by firing a mixture of titanium dioxide (TiO ₂ ), zinc oxide (ZnO ₂ ) and inorganic tin oxide (SnO ₂ ), and a high heat- It is excellent in compatibility with polyamide resin used as orange automobile parts material such as battery pack, high voltage cable and its peripheral parts, Resistant orange inorganic pigment for a polyamide, which is an environmentally friendly inorganic pigment which does not contain an organic pigment, and an orange-based inorganic pigment produced by this method.

Accordingly, the present invention has solved the problems such as deterioration of hiding power and occurrence of migration phenomenon due to use of a high-priced solvent dye product as a coloring agent.

Unlike the conventional method of producing an orange-based inorganic pigment, the present invention fires a mixture of inorganic material powders of titanium dioxide (TiO ₂ ), zinc peroxide (ZnO ₂ ) and tin oxide (SnO ₂ ) Based inorganic pigment for polyamide, which is capable of producing an orange-based inorganic pigment by a simple method, and to provide an orange-based inorganic pigment which is produced by the method To be a different task.

The present invention relates to a process for producing a composite material, which comprises a combination step (P100) of combining a titanium dioxide (T), zinc peroxide (S) and an inorganic material powder of tin (Z) (P200) for preparing a mixture by uniformly mixing the inorganic material powders in the combination, a firing step (P300) for preparing the fired product by heating the mixture prepared in the step and heating the mixture, A pulverizing step (P400) of pulverizing the calcined product to produce a powder slurry; a drying step (P500) of heating the powder slurry to remove moisture contained in the powder slurry prepared in the step And a re-pulverization step (P600) of pulverizing the powder dried in the above step and pulverizing the pulverized powder uniformly to a size of the fine particles. The method of manufacturing the solving means of the problem.

The combining step (P100) is carried out by combining the titanium dioxide (T), zinc peroxide (S) and zinc oxide (Z) so that the composition ratio (based on the weight ratio) is 100:50 to 60:50 to 60, After step P500, a coloring step (P510) for color modification is added by adding a coloring agent (C) to the dried powder to prepare an orange-based inorganic pigment of desired color.

It is another object of the present invention to provide a highly heat-resistant orange inorganic pigment for polyamide which is produced by the above-described method.

The present invention is excellent in compatibility with a polyamide resin used as an orange automobile parts material such as a battery pack to which a high heat resistance and high rigidity material is applied, a high voltage cable and peripheral parts thereof, Based inorganic pigment which is excellent in heat resistance at the time of processing and which is not carbonized and is not discolored is different from the conventional method of producing an orange-based inorganic pigment by firing a mixture of an inorganic material powder to produce an orange- It is possible to produce an orange-based inorganic pigment, so that the productivity is high.

1 is a process block diagram showing a process for producing a highly heat resistant orange inorganic pigment for polyamide according to a preferred embodiment of the present invention,
2 is a process block diagram showing a process for producing a highly heat resistant orange inorganic pigment for polyamide according to another preferred embodiment of the present invention,
3 is a photograph of a highly heat resistant orange inorganic pigment for polyamide according to an embodiment of the present invention,
FIG. 4 is a photograph of an orange dye and an organic pigment of a comparative example contrasted with the embodiment of the present invention,
FIG. 5 shows a test apparatus for bleeding test of a highly heat resistant orange inorganic pigment for polyamide according to an embodiment of the present invention,
6 is a photograph showing a result of a bleeding test of an orange inorganic pigment according to an embodiment of the present invention,
7 is a photograph showing a result of a bleeding test of an orange dye and an organic pigment of a comparative example in contrast to the example of the present invention,
8 is a photograph showing a result of a migration test of a highly heat resistant orange inorganic pigment for polyamide according to an embodiment of the present invention.
9 is a photograph showing a result of a migration test of an orange dye and an organic pigment in a comparative example in contrast to the example of the present invention,
10 is a photograph showing a result of a heat resistance stagnation test and a dendriticity test of a highly heat resistant orange inorganic pigment for polyamide according to an embodiment of the present invention,
11 is a photograph showing the result of the heat resistance stagnation test and the dendritic compatibility test of the orange dyes and the organic pigments of the comparative examples as contrasted with the examples of the present invention,
12 is a view showing a result of a color difference change test of a processed polyamide resin according to an embodiment of the present invention,
13 is a view showing the result of the color difference change test of the processed polyamide resin of the comparative example in contrast with the example of the present invention,
14 is a photograph showing prototypes of automotive parts processed by using a polyamide resin obtained by mixing and processing a high heat resistant orange inorganic pigment for polyamide according to an embodiment of the present invention.

Hereinafter, a method for producing a highly heat-resistant orange inorganic pigment for polyamide and an orange-based inorganic pigment produced by the method according to a preferred embodiment of the present invention are described in detail with reference to the accompanying drawings. In the drawings, the drawings and the detailed description of the present invention are omitted or simplified in order to facilitate understanding of the construction and operation of the orange phosphorus inorganic pigment field.

The highly heat-resistant orange inorganic pigment for polyamide according to the preferred embodiment of the present invention is a combination of titanium dioxide (T), zinc peroxide (S) and inorganic tin (Z) A mixing step (P200) of adding a mixture prepared in the above step to a mixer and uniformly mixing the inorganic material powders in the combination to produce a mixture; A calcination step (P300) of adding the mixture prepared in the above step to a calcination furnace and heating the mixture to produce a calcined product; a pulverizing step (P400) of pulverizing the calcined product to obtain a powder slurry; A drying step (P500) of heating the powder slurry to remove moisture contained in the powder slurry prepared in the step (P500), and pulverizing the dried powder in the step After the grinding step (P600) ;, it characterized in that the manufacturing is highly heat-resistant polyamide-based inorganic orange pigment (P) for.

Hereinafter, the manufacturing process of the highly heat resistant orange inorganic pigment for polyamide according to the present invention will be described in detail in each step as follows.

In the present invention, the combining step (P100) is a step of combining titanium dioxide (T), zinc peroxide (S) and tin oxide (Z) so that the composition ratio (based on the weight ratio) is 100:50 to 60:50 to 60 .

In the present invention, titanium dioxide (TiO ₂ ), which is an inorganic oxide used as a raw material for producing a high heat-resistant orange inorganic pigment, is also called titanium dioxide or titanium dioxide. It is a white powder with a tasteless odor and excellent hiding power, Since it has insulating properties, it becomes a white pigment and has a characteristic of forming a titanium dioxide film by easily reacting with oxygen when exposed to air because of its great oxidizing power.

And zinc oxide (ZnO ₂ ) is a tin oxide which is a raw material of metal oxide ceramics. It contains rutile structure. It has an appearance of noxious white odorless powder and is mixed with other metal oxides and used as a pigment. It is also used as a catalyst application agent in the production of organic acids and acid anhydrides by oxidation of aromatic compounds, soluble in reflux, insoluble in water, and has a high surface area and a semi-magnetic property. The composition ratio of zinc peroxide (ZnO ₂₎ in the invention is preferably titanium dioxide (TiO ₂₎ zinc peroxide based on 100 parts by weight of (ZnO ₂₎ 50 ~ 60 parts by weight.

When the composition ratio of zinc oxide (ZnO ₂ ) is less than 50 parts by weight, coloring power is deteriorated and it may be discolored to light orange color. When it exceeds 60 parts by weight, dark red color color) may be discolored.

In addition, 2-tin oxide (SnO ₂ ) is a white powder present as a mineral called tin stones in nature. It is reduced by hydrogen at high temperatures to become metal tin, and the polyamide resin is discolored by light and heat .

When the composition ratio of the tin oxide (SnO ₂ ) is less than 50 parts by weight, the reaction condition and the active power are inhibited and the color may be greenish. If the composition is more than 60 parts by weight There is a fear that the color becomes yellowish and bright in the yellow color.

In the present invention, the mixing step (P200) Mixing the mixture prepared in the combining step (P100) into a mixer and uniformly mixing the inorganic material powders in the mixture using an agitator to prepare a mixture, wherein the mixing method is the same as the conventional powder mixing method Mix by method.

In the firing step P300 of the present invention, a mixture of titanium dioxide (T), zinc peroxide (S) and tin (Z) oxide is injected into a firing furnace and fired. A nitrogen (N) min, the temperature of the sintering furnace is set to 850 캜, the temperature is raised for 4 to 6 hours, and then maintained at 850 캜 for 2 to 3 hours, followed by natural cooling.

If the firing conditions in the firing step P300 are less than the firing conditions defined above, the metal compounds of titanium dioxide (T), zinc peroxide (S) and oxidizing agent 2 tin (Z) There is a fear that it is not sufficiently fused. If the firing condition is out of the range defined above, there is a fear that an excessive use of energy may cause uneconomical problems.

In the present invention, the pulverization step (P400) is a step of pulverizing the fired product produced in the firing step (P300) to prepare a powder slurry. The pulverization step (P400) is a step of pulverizing the fired product produced in the firing step (P300) by using water as a solvent using Bead MILL or JAR MILL It is preferable to pulverize the powder in water at a speed of 180 to 220 rpm for 1 to 3 minutes.

In the present invention, the drying step (P500) comprises heating the powder slurry to remove moisture contained in the powder slurry produced in the pulverization step (P400), wherein the powder slurry is heated to 150 to 250 At And then dried for 2 to 4 hours.

In the re-pulverization step (P600) of the present invention, the powder dried in the drying step (P500) is dried in the form of agglomerated powder agglomerates. Therefore, in order to pulverize the agglomerated agglomerated powder agglomerates into fine particles, And pulverizing the dried powder with a pin mill to homogeneously pulverize the powder into fine particles.

The size of the pulverized particles is usually 1 to 1.5 占 퐉, and can be appropriately adjusted without being limited to the range of the numerical values defined above.

In the present invention, the coloring step (P510) is a step of color modification by adding a coloring agent (C) to the dried powder after the drying step (P500) to produce an orange-based inorganic pigment of desired color.

The coloring agent (C) used in the present invention may be a orange, orange, red or white pigment in order to obtain a desired color. In addition to the pigments defined above, other coloring agents may be used depending on the color desired, or the amount of the coloring agent added may be appropriately adjusted.

Meanwhile, the polyamide which is a synthetic resin material for applying the high heat-resistant orange inorganic pigment (P) according to the present invention is a high-functional resin which is one kind of engineering plastics, and is a synthetic resin having an amide bond connected to -CONH- It is a polymer material. A typical example of the polyamide resin is nylon, which is a trade name of DuPont, USA. The material is rich in self-lubricating property, has a small coefficient of friction, and is excellent in abrasion resistance, and has excellent impact resistance and heat resistance. Nylon 6 and nylon 66 are widely used for automobiles. However, nylon 66, which has less hygroscopicity than nylon 6 and has a high tensile strength, is increasing in use mainly in automobiles, and is used in door handles, switch parts, gears, And so on.

Polyamide which is a synthetic resin material for applying the high heat-resistant orange inorganic pigment (P) according to the present invention is specifically exemplified by polyamide 6, polyamide 11, polyamide 12, polyamide 46, polyamide 66 , Polyamide 610, polyamide 612, polyamide 613, polyamide 614, polyamide 615, polyamide 616, polyamide 910, polyamide 912, polyamide 913, polyamide 914, polyamide 915, polyamide 936, poly Amide 1010, polyamide 1012, polyamide 1013, polyamide 1014, polyamide 1210, polyamide 1212, polyamide 1213 or polyamide 1214, and the like.

It is most preferable to use a polyamide 6 or a polyamide 66 as a polyamide which is a synthetic resin material for applying the high heat-resistant orange inorganic pigment (P) according to the present invention. In some cases, polyamide 6 or poly Amide 66 is preferably used in combination.

An example of a conventional method of producing an orange-based color polyamide resin component using the orange-based inorganic pigment (P) according to the present invention is as follows.

0.3 to 0.5 wt% of an antioxidant, 0.5 to 0.7 wt% of a compatibilizer, 0.3 to 0.5 wt% of a lubricant, 0.3 to 0.5 wt% of a flow improver, 85 to 90 wt% of a polyamide resin, 0.3 to 0.5% by weight of a liquid additive, and 0.5 to 0.7% by weight of a pigment are mixed to produce a polyamide resin component by injection molding or extrusion molding.

In the present invention, an example of a method of manufacturing a polyamide resin component by the above composition ratio is described. However, the present invention is not necessarily limited to the range of the above-described composition ratio, The composition ratio can be appropriately adjusted.

Accordingly, the high heat-resistant orange inorganic pigment for polyamide produced by the above-described method is an orange automobile parts material such as a battery pack to which a high heat resistance and high rigidity material is applied, a high voltage cable and its peripheral parts As an environmentally friendly inorganic pigment which is excellent in compatibility with a polyamide resin to be used and excellent in heat resistance at the time of processing a resin and is not carbonized and does not discolor, unlike conventional orange-based inorganic pigment production methods, Based inorganic pigment is produced by firing a mixture of an inorganic material powder and an orange-based inorganic pigment by a simple method, and productivity is high.

Hereinafter, the high heat-resistant orange inorganic pigment for polyamide according to the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to the following examples.

1. Preparation of high heat-resistant orange inorganic pigments for polyamides

(Example 1)

The combination of the titanium dioxide (T), the zinc peroxide (S) and the tin oxide (Z) in a composition ratio of 100: 50: 50 was introduced into a mixer, (N) gas was supplied into the calcining furnace at a rate of 1 L / min while setting the temperature of the calcining furnace at 850 ° C., the temperature was raised for 4 hours, and the mixture was maintained at 850 ° C. for 2 hours The naturally cooled fired product was put into a pulverizer and water was pulverized with a bead mill at 180 rpm for 1 minute using a bead mill to remove water contained in the powder slurry at 150 ° C. for 4 minutes To 93 parts by weight of the powder obtained by the time drying, 5 parts by weight of a coloring additive (Yellow 6508W of Colorant Korea) as a colorant (C) and 5 parts by weight of a white pigment (White 6628 of Colorant Korea) were added, With Powder a modified pinmil (Pin MILL) to re-pulverized so that the particle size of 1 ~ 1.5 ㎛ prepare a polyamide with high thermal orange-based inorganic pigment (P) for.

(Example 2)

The combination of the titanium dioxide (T), the zinc peroxide (S) and the tin oxide (Z) so that the composition ratio (based on the weight ratio) was 100: 60: 60 was introduced into a mixer, (N 2) gas was supplied at a rate of 1 L / min into the firing furnace, the temperature was raised to 850 ° C., the temperature was raised for 6 hours, and the mixture was maintained at 850 ° C. for 3 hours The naturally cooled calcined material was charged into a pulverizer, and water was pulverized with a bead mill at a speed of 220 rpm for 3 minutes using a bead mill. To remove water contained in the powder slurry, 62.5 parts by weight of a color orange (Orange STZ-1811, manufactured by Colorant Korea) as a colorant (C) was added to 37.5 parts by weight of a time-dried powder, and the powder was subjected to color modification with an orange- And then re-pulverized to a size of 1 to 1.5 mu m to prepare a highly heat-resistant orange inorganic pigment (P) for polyamide.

(Example 3)

The combination of titanium dioxide (T), zinc peroxide (S) and zinc oxide (Z) in such a manner that the composition ratio (based on the weight ratio) of the titanium oxide (T) 3 parts by weight of toning red (Red W12U, manufactured by Colorant Korea) as a coloring agent (C) was added to 97 parts by weight of a powder dried at 250 ° C for 2 hours to prepare a pin- To obtain a high heat resistant orange inorganic pigment (P) for polyamide.

(Example 4)

The combination of the titanium dioxide (T), the zinc peroxide (S) and the tin oxide (Z) so that the composition ratio (based on the weight ratio) was 100: 60: 50 was put into a mixer and processed 2 parts by weight of toning red (Red W12U, manufactured by Colorant Korea) as a coloring agent (C) was added to 98 parts by weight of a powder dried at 250 ° C for 3 hours to obtain a pin mill, To obtain a high heat resistant orange inorganic pigment (P) for polyamide.

(Comparative Example 1) to (Comparative Example 4)

In Comparative Examples 1 to 4, Orange Y (S company dye), Orange G (S company dye), Orange L (S company dye) and Orange 6 (S company organic pigment) were used.

FIG. 3 is a photograph of a pigment of an embodiment of a highly heat-resistant orange inorganic pigment for polyamide according to an embodiment of the present invention, and FIG. 4 is a cross- Orange Y, Orange G, Orange L, and Orange 6 from the left side are photographs of the dyes and pigments used in the comparative examples in contrast to the high heat resistant orange inorganic pigments.

2. Preparation of orange colored polyamide resin

Using the orange-based inorganic pigments (P) of Examples 1 to 4 prepared in 1 above and the dyes and organic pigments of Comparative Examples 1 to 4, additives were added as shown in Table 1 below, An orange-colored polyamide resin was prepared under the processing conditions shown in [Table 2].

division Content (% by weight) Remarks PA66 RV 87.8 Base Resin Impact Resistant 10 Reinforcing agent Antioxidant 0.3 additive Compatibilizer 0.5 additive Lubricant 0.3 additive Flow improver 0.3 additive Liquid additive 0.3 additive Pigment 0.5 - Sum 100

division Screw RPM Shear ℃ Processing conditions 450 to 500 40 to 50 280 ± 1

3. Evaluation of high heat-resistant orange inorganic pigments and polyamide resins for polyamides

The dyes and organic pigments of Examples 1 to 4 and Comparative Examples 1 and 4, which were the high heat-resistant orange inorganic pigments for polyamide prepared according to the above-mentioned method 1, The test results for the specific gravity and melting point (Tm) for the samples are shown in Table 3 below.

Item unit standard Test Methods Example Comparative Example One 2 3 4 One 2 3 4 importance - 4.8 ↓ ASTM D6683 4.62 4.42 4.56 4.24 1.52 1.53 1.55 1.50 Melting point
(Tm) ℃ 320 ↑ ASTM D3418 320 ↑ 320 ↑ 320 ↑ 320 ↑ 300 ↑ 300 ↑ 300 ↑ 300 ↑

According to the contents of the above Table 3, the specific gravity and melting point of the high heat-resistant orange inorganic pigments of Examples 1 to 4 and the dyes and organic pigments of Comparative Examples 1 to 4 were specified. As a result, It was confirmed that the specific gravity of the high heat-resistant orange inorganic pigment of Example 4 was 4.8 or less, which is the basic goal of the present invention, while the dyes and organic pigments of Comparative Examples 1 to 4 were all 1.5 to 1.55 in specific gravity.

As a result of the melting point (Tm) test, the high heat-resistant orange inorganic pigments of Examples 1 to 4 were measured at 350 DEG C under a nitrogen atmosphere. As a result, the melting point did not appear, However, the dyes and organic pigments of Comparative Examples 1 to 4 did not show a melting point at 300 ° C, and it was confirmed that carbonization was started all over 320 ° C.

Therefore, the heat-resistant orange inorganic pigments of Examples 1 to 4 according to the present invention have a higher melting point (Tm) than the dyes and organic pigments of Comparative Examples 1 to 4, Can be easily carried out.

On the other hand, the flowability (MI), tensile strength (TS), flexural modulus (FM) of the nylon 66, which is the polyamide resin of Examples 1 to 4 and Comparative Examples 1 to 4, , Impact strength (IMP), specific gravity, compatibility test (Bleeding Test and Migration Test), specimen condition and color difference change are shown in Table 4 below.

Item unit standard Test Methods Example Comparative Example One 2 3 4 One 2 3 4 liquidity
(MI) g / 10 min 15 ↑ ASTM D1238 28.8 28.5 29.3 28.5 22.6 23.3 22.1 24.7 Seal
burglar
(TS) MPa 47 ↑ ASTM D3418 58 60 59 57 52 51 53 54 curve
Modulus of elasticity
(FM) MPa 1,550 ↑ ASTM D790 2,011 2,067 2,192 2,213 1,725 1,795 1,757 1,848 Shock
burglar
(IMP) J / m 133 ↑ ASTM D256 222 231 238 232 198 201 195 204 Compatibility B ¹⁾ - Good Visual judgment ○ ○ ○ ○ ○ ○ ○ ○ M ²⁾ - Good Visual judgment ○ ○ ○ ○ ○ ○ ○ ○ Psalter
condition - Good Visual judgment ○ ○ ○ ○ × × × △ Color difference
change ΔL 1.3 ↓ Color difference meter 1.2 1.1 1.2 1.2 2.7 2.5 2.3 2.7  Note 1) and 2)?: Good,?: Normal, Bad

The test items for the fluidity (MI), tensile strength (TS), flexural modulus (FM) and impact strength (IMP) of the above Table 4 were tested according to the method described in [Table 4] Respectively.

1) Bleeding test is done by ① after shaking for one hour in a paint shaker after precisely weighed according to the specimen condition in [Table 5] ② after covering the shaken colored resin with concealing (3) in a film applicator and air-dried for 1 hour, and (3) coated with 5 ml of a white paint at about 2/3 point on a dried cover paper and checked for bleeding .

Raw material name Example Comparative Example One 2 3 4 One 2 3 4 Acrylic resin (transparent) (g) 50 50 50 50 50 50 50 50 Glass beads (g) 50 50 50 50 50 50 50 50 Pigment or dye (g) 10 10 10 10 0.2 0.2 0.2 3

The migration test is performed by ① setting the temperature of the equipment equipped with 2 rolls before the experiment and stabilizing the temperature for about 1 hour (Roll set temperature: Roll 1: 105 ℃, Roll 2: 95 ℃) ② Put the LDPE prepared in accordance with the specimen conditions in Table 6 below into the heated roll to completely dissolve the resin. ③ Remove the resin with the spatula by putting the pigment in it and dispersing it for 5 minutes. 5), and the test pieces are aged in a dry oven at 80 DEG C for 12 hours, and then visually checked for migration.

Raw material name Example Comparative Example One 2 3 4 One 2 3 4 L.D.P.E (g) 50 50 50 50 50 50 50 50 Pigment or dye (g) 0.2 0.2 0.2 0.2 0.06 0.06 0.06 0.1

According to the contents of the above Table 4, nylon 66, which is a polyamide resin of Examples 1 to 4, has higher flowability (melt mass flow index) than nylon 66 which is a polyamide resin of Comparative Examples 1 to 4 Mechanical properties such as flowability (MI), tensile strength (TS), flexural modulus (FM) and impact strength (IMP) were all excellent.

In order to evaluate the compatibility of the acrylic resin and the linear low density polyethylene (LDPE) resin with the samples of Examples 1 to 4 and Comparative Examples 1 to 4, a bleeding test and a migration test Migration Test). As a result, all of the results shown in FIGS. 6 to 9 were satisfactory.

6, which is a drawing attached to the specification of the present invention, is a photograph showing a result of a bleeding test of an orange inorganic pigment according to an embodiment of the present invention, and FIG. 7 is a photograph (Bleeding Test) of the orange dyes and the organic pigments of Comparative Examples. And FIG. 8 is a photograph showing a result of a migration test of a highly heat-resistant orange inorganic pigment for polyamide according to an embodiment of the present invention. FIG. 9 is a photograph showing the results of a migration test This is a photograph of the result of migration test of organic pigments.

As a result of examining the state of the specimen to confirm the heat resistance stagnation test and discoloration, nylon 66, which is the polyamide resin of Examples 1 to 4, showed the thermal stability of the high heat resistant orange inorganic pigment The nylon 66, which is a polyamide resin of Comparative Examples 1 to 4, was excellent in compatibility between the resin and the pigment and not discolored, It was confirmed that the specimen of one part had a poor compatibility between the resin and the pigment and that there was a part that did not show a proper color or that it was discolored.

10, which is a drawing attached to the specification of the present invention, is a photograph showing a result of a heat resistance stagnation test and a dendriticity test of a highly heat resistant orange inorganic pigment for polyamide according to an embodiment of the present invention, The results of the heat resistance stagnation test and the dendritic compatibility test of the orange dyes and the organic pigments of the comparative examples, which are compared with those of the examples, are shown.

As a result of measurement of the color difference change using a spectroscopic colorimetric system (KONIKA MINOLTA, CM-3600D model), nylon 66 as a polyamide resin of Examples 1 to 4 was evaluated as a polyamide resin of Comparative Examples 1 to 4 It was confirmed that the color difference was less than that of the nylon 66.

12, which is a drawing attached to the specification of the present invention, is a view showing a result of a color difference change test of the processed polyamide resin according to Example 1 of the present invention, The drawing shows the result of the test.

The results of heavy metal detection tests on nylon 66, a polyamide resin of Examples 1 to 4, are shown in Table 7 below.

heavy metal standard
(mg / kg) exam
Way Example (mg / kg) One 2 3 4 Cadmium (Cd) 1 ↓ KS C IEC
62321 Not detected ¹⁾ Not detected Not detected Not detected Lead (Pb) 10 ↓ Not detected Not detected Not detected Not detected Mercury (Hg) 0.1 ↓ Not detected Not detected Not detected Not detected Chromium VI (Cr) 0.1 ↓ Not detected Not detected Not detected Not detected  Note 1) In the above, 'not detected' means below the detection limit.

According to the contents of the above Table 7, nylon 66, which is a polyamide resin of Examples 1 to 4, is environmentally friendly in which cadmium (Cd), lead (Pb), mercury (Hg) and chromium (Cr) It can be confirmed that it is a part material.

Therefore, the high-temperature-resistant orange inorganic pigment according to the present invention is applied to polyamides to provide an environment-friendly automobile having a bright orange color which is excellent in mechanical properties and does not discolor due to heat There is a characteristic that parts material can be manufactured.

As described above, the method for producing the highly heat-resistant orange inorganic pigment for polyamide according to the preferred embodiment of the present invention and the orange-based inorganic pigment produced by the method have been described. However, It will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit of the invention.

T: Titanium dioxide S: Zinc peroxide
Z: oxidizing agent 2 tin C: coloring agent
P: orange-based inorganic pigment

Claims (7)

A combination step of preparing a combination by combining the inorganic powder of titanium dioxide (T), zinc peroxide (S) and zinc oxide (Z) so that the composition ratio (by weight ratio) of 100:50 to 60:50 to 60 P100); and
A mixing step (P200) of putting the combination prepared in the above step into a mixer and uniformly mixing the inorganic material powders in the combination to prepare a mixture;
The mixture prepared in the above step was put into a firing furnace, and nitrogen (N) gas was supplied into the firing furnace at a rate of 1 L / min while setting the temperature of the firing furnace at 850 캜, raising the temperature for 4 to 6 hours, (P300) in which the mixture is kept for 3 hours and then cooled naturally to produce a fired product;
The fired product prepared in the above step is pulverized with water at a speed of 180 to 220 rpm for 1 to 3 minutes using Bead MILL or JAR MILL as a solvent to obtain a powder slurry (P400); and
To remove the moisture contained in the powder slurry prepared in the above step, the powder slurry was heated at 150 to 250 DEG C A drying step (P500) for heating for 2 to 4 hours;
A re-pulverization step (P600) of pulverizing the powder dried in the above step to uniformly pulverize the pulverized powder to a size of fine particles;
Based inorganic pigment for polyamide. ≪ RTI ID = 0.0 > 11. < / RTI >
delete delete delete delete The method according to claim 1,
(P510) for color modification by adding a coloring agent (C) to the dried powder to prepare an orange-based inorganic pigment having a desired color after the drying step (P500) A method for producing an orange-based inorganic pigment.
A combination of titanium dioxide (T), zinc peroxide (S), and tin (Z) oxide in an amount of 100:50 to 60:50 to 60 in terms of a composition ratio (weight ratio basis) 6. The high heat-resistant orange inorganic pigment for polyamide according to claim 1, which is produced by the method according to any one of claims 1 to 6.

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