TW203069B - - Google Patents

Description

Λ 6 Β6 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (1) Background of the invention The spherical fine particles of colored resin are used for paints, inks, plastics, plastics, rubber, etc. Agents, and matting agents, materials, cocoons and zebras used in electrostatic copiers and cosmetics. In detail, the invention has invented spherical fine particles of colored resin, which is a new type available in the industry and can be prepared by blending an amine-based resin cured product and an inorganic pigment, and there is a method for producing pellets. At present, spherical fine particles of various colored resins are used in plastics, paints, inks, cosmetics, etc., and have their own characteristics in various applications. Spherical fine particles of colored resin are made by blending dyes or pigments with resin. In this way, dyes and pigments are used in the form of a plaque mixed with resin, but not in their original form because of increased affinity for polymers such as paints, inks, plastics, male vinyl, rubber, etc. Moreover, when the fine particles are spherical, compared with the case where the particles are not in this shape, there is an advantage that the fluidity is improved in the molding process. In the case where the particles are used in coatings, fibers, etc., the surface is smooth and can be increased. advantage. Spherical fine particles of colored resin obtained by combining thermosetting resins such as phenol resins, chen resins, or thermoplastic resins such as acrylic resins, vinyl resins, and organic dyes or organic pigments are superior to transparency and character, but they are easy to use * Poor heat resistance, light resistance, solvent resistance, weather resistance, impermeability, etc. On the other hand, spherical fine particles of colored resins, in which inorganic pigments are used for coloring, are superior to those using dyes in terms of solvent resistance, light resistance, heat resistance, and permeability resistance, in terms of light resistance and heat resistance It is better than those using organic pigments. (Please read the precautions on the back before filling in this page) Binding, Ordering, Threads, and Paper Sizes Use the Chinese National Standard (CNS> A4 Specification (210x297 g *) -3 ~ Bei Gong, Central Bureau of Standards, Ministry of Economic Affairs Printed by the consumer cooperative Λ 6 _B6_ V. Description of the invention (2) It is known that colored resin fine particles prepared by coloring thermoplastic resin with pigments, for example, colored resin fine particles obtained by blending and crushing thermoplastic resins and pigments ( Japanese Official Patent Provisional Pub 1 i caton, showa 58-17169), colored resin spherical fine particles (Japanese Official Patent Gazette, showa 57-22324) obtained by adding a pigment to a reaction mixture such as suspension polymerization, and in Colored resin spherical fine particles obtained by coating pigments on the surface of thermoplastic resin fine particles after chemical or physical treatment (Japanese Official Patent Provisional Publication. Showa 63-10671) 〇 In addition, colored resin balls obtained by coloring thermosetting resins with pigments Shaped fine particles are known, for example, colored thermosetting resins made by adding pigments when synthesizing thermosetting resins such as phenol resins by addition polymerization and addition condensation reactions Spherical fine particles. The problem is the currently known colored resin spherical fine particles, among which the above-mentioned thermoplastic resins are used, heat resistance, solvent resistance, chemical resistance, etc., the adhesion between the resin particles and the pigment is poor, and the colored particles The surface smoothness is poor. Moreover, the problem is that currently known colored resin spherical fine particles, in which the above thermosetting resin is used, the particles are widely distributed, and the non-true spherical fine particles have the defect that the particles are brittle, and because of the need for certain applications Grading etc. becomes angry 0- expensive. SUMMARY OF THE INVENTION The present invention solves the above-mentioned defects and problems of the colored resin spherical fine particles obtained by the currently known technology, and its subject is to propose a colored resin spherical fine particles (please first Read the precautions on the back and then fill out this page) Binding · Order. Thread _ All paper sizes are used in B «Home Standard (CNS) A 4 specifications (210X297 public S :) -4-Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Printed 030 ^ 5 Λ 6 ___ Β6 Fifth, the description of the invention (3) and the colored resin spherical fine particles, of which the particles are spherical and have excellent heat resistance, solvent resistance, and chemical resistance. to make Spherical shape, durability and color rendering are fully satisfactory, and is conducive to industrialization. In order to solve the above-mentioned sassafras, the present invention proposes a method for preparing colored spherical resin particles, in which amine-based resin and inorganic pigment are blended and emulsified, The polycondensation reaction is carried out under emulsification conditions. Therefore, the amine-based resin cooked product and the inorganic pigment are blended together so that the ratio of the inorganic pigment to the total amount of the amine-based resin cooked product and the inorganic pigment is in the range of about 1 to 30 weight percent (hereinafter , ~% By weight 〃 referred to as "percentage" or% unless otherwise defined). Furthermore, the present invention proposes a method for producing the above-mentioned colored resin spherical fine particles, the special emblem of which is that the amine-based resin is the initial reaction product of formaldehyde and amine-based compounds, at least one of which is selected from the group consisting of beiizoguanamine and cyclohexane The amount of guanamine in the group of cyciohexanecarboguanamine and cyclohexenecarboguanamine is about 40% to about 100% by weight, and the inorganic pigment is black and has Processing of compounds with functional groups with reactive and / or affinity. Moreover, in order to solve the above-mentioned problems, the present invention proposes a spherical fine particle of colored resin, which comprises an amine-based resin cured product and an inorganic pigment in one body, and the ratio of the inorganic pigment to the amount of the amine-based resin cured product and the inorganic pigment It is in the range of about 1 to 30 weight percent, wherein the amine-based resin cured product is a reaction product of formaldehyde and an amine-based compound, at least one of which is selected from the group consisting of benzoguanamine and cyciohexanecarb-oguanamine , Cyclohexenecarboguana (cyclohexenecarboguana-(please read the precautions on the back before writing this page) 装-线-winter paper scales for easy use in China's sleepy family's (CNS) A 4 specifications (210x297 g *) -5-Beta Industrial Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs .-- " Manufacture Λ 6 __Β6_ V. Description of invention (4) Mine) The amount of guanamine is about 40 to about 100 weight percent, and the inorganic pigment It is a master black and is processed with a compound having a functional group reactive and / or compatible with the master black functional group. In the present invention, the ratio of the inorganic pigment to the total set of the amine-based resin cured product and the inorganic pigment is required to be about 1 to 30%. If the ratio of the inorganic pigment is below the range, the colored spherical resin particles have a problem of lack of coloring, and if the ratio is large, the inorganic pigment is not fixed to the amine-based resin, the particle shape is distorted, and the particle distribution is broadened Question. In addition, the use of amine-based resins provides colored resin spherical fine particles with excellent heat resistance, solvent resistance, and chemical resistance. The inorganic pigment and the amine-based resin cured product are blended into a plaque by the colored resin spherical fine particles prepared by the present invention, for example, the following. In this regard, the colored resin spherical fine particles are colored with inorganic pigments. The colored resin spherical fine particles of the present invention have a spherical shape, for example, a particle size ratio (major axis / secondary axis), which is determined by 200 copies of spherical fine particle images obtained by an electron microscope, and the fan size is about 1. ◦ to 1. 2 5 〇 The amine-based resin in the present invention is a resin obtained by polycondensation reaction of at least one or two or more amine-based compounds and formaldehyde, wherein the amine-based compound has two or more intramolecular amine groups and is selected from, for example, containing urea , Melamine, beuzoguanamine, cyclohexaneca-rboguanamine, cyclohexenecarbog-uanam i ne, etc. Moreover, the amino resin can be alcohol Convert to ether. As described below, if processed black is used ("CB "-the word is used to refer to" black "in this article), it is better to use an amine compound and formaldehyde polycondensation reaction (please read the back Please fill out this page again) Please use Chinese National Standards (CNS) Grade 4 specifications (210X297mm) for each paper size -6-Printed by Beigong Consumer Cooperation Co., Ltd., Central Standards Bureau, Ministry of Economic Affairs ^ 030C ^ Λ 6 _B6_ V. DESCRIPTION OF THE INVENTION (5) The initial reaction product (main condensation product) is an amine-based resin, wherein the amine-based resin is selected from at least one selected from benzoguanamine, cyclohexane carboguanamine, and chen The gua-namine of cyclohexene carboguanamine is about 40 to 100 percent, and the initial reaction product can be converted into ether. If the processed CB is used, the reason why this amino resin is better is that the resin has good affinity with the processed CB and the C B is uniformly dispersed. It is preferable to use an amine-based resin primary reaction product having a methanol mixing degree of 400% or less as the amine-based resin of the present invention. The methanol mixing degree of the primary reaction product shows the polycondensation ratio of the amine-based resin, which is to dissolve 2g of the primary reaction product in 5g of methanol, drop water into the resulting solution while maintaining 25¾, and determine the water weight required to obtain turbidity The value derived by multiplying the weight ratio with the initial reaction product by 100. The inorganic pigment used in the present invention is not particularly limited to types and shapes, for example, one or two or more selected from titanium oxide, iron oxide, vaporized zinc, barium sulfate, sulfuric acid 0, barium succinate, calcium strontium, and strontium acid Compounds such as magnesium, talc, clay, and black to improve colorability (improvement of resin dispersibility, etc.), if necessary, use a pulverizer such as ball mill to make the particle size 5 or less, 0.1 or Smaller is better. Using inorganic pigments, colored resin spherical fine particles will have hiding power. When using colored resin spherical fine particles as above, for example, it can be arranged not to show the color of the surface (or substrate) to be coated and the coloring can be no worse than other colors. In the present invention, the amount of inorganic pigments can be appropriately determined to be contained in the colored tree (please read the precautions on the back before filling the nest page). Thread · Winter paper standard Xiaoazhong #quasi (CNS) T4 specifications ( (210 father, 297 public herbs) -7-The Ministry of Economic Affairs, Central Standards Bureau, Beigong Consumer Cooperative printed isocrystal 10? DESCRIPTION OF THE INVENTION (6) The ratio of the inorganic mesh in the lipid spherical fine particles to the total amount of the amine-based resin cured product and the inorganic pigment is about 1 to%, preferably about 5 to 20%. To obtain this ratio, although it depends on the type of amine-based resin and inorganic pigment, the ratio of inorganic pigment used is, for example, about 0.9 to 27% relative to the total amount of amine-based resin and inorganic pigment. · The inorganic pigments used in the present invention can be surface-treated to improve the dispersibility of amine-based resins. In addition, at least any one of dyes and organic pigments can be used as an auxiliary. In particular, when CB is a compound (A) that has a functional group that is reactive and / or affinity with the functional group present on the surface of CB, it can obtain an excellent splitting property for the initial compound of amine compound and formaldehyde Black resin spherical fine particles, and its color is also excellent. When the above compound (A) has a reactive functional group that can easily react with a functional group present on the surface of the CB (for example, —0H, —C00H, —C = 0, etc.) and / or has affinity with the CB functional group In the case of functional groups, the compound (A) can be used without any restriction. The compound (A) may have one or more radicals such as, for example, aziridinyl, oxazolinyl, N-hydroxyalkylamido, epoxy, thiocyclic gas, isopentenyl, hydroxyl , Amine groups, imine groups, etc., monomers or polymerizable monomers, or if necessary, may be a compound obtained by polymerizing one or two or more polymerizable monomers according to a known method. Examples of the compound (A) are, for example, polyethyleneimine having an average molecular weight of about 300 to 100,000, polyethylene glycol glycidyl ether having an average molecular weight of about 70 to 100,000, and an average molecular weight of about 200 to 1 〇, ◦ ◦ (poly) alkanediol, its derivatives, etc. As for the example of polyethylene glycol glycidyl ether, for example, the paper standard shown in the general formula (I) is applicable to the Chinese National Standard (CNS) A 4 specifications (210 X 297 public). 1 8 _ (please first Hf Note to write this page again) Packing and ordering., 0300, 0300 A6 B6 Amendment ^ 1¾ said: Ming () R-0-(-CH2-CH2〇-)-n_CH2-CH-CH2 (1) Ο (at Here, R is a hydrogen atom or at least one group selected from an alkyl group having 1 to 2 ◦ atoms and a substituent; an aryl group; and an unsaturated aliphatic residue group, and η is an integer of 1 to 30) . To process CB with compound (Α), for example, perform the following steps. Using a kneader (grinding device), the CB and the compound (Α) are sufficiently kneaded and heated to a specific temperature, thereby improving the reactivity and affinity between the functional groups on the surface of the CB and the functional groups of the compound (Α). The preferred emulsifiers used in the present invention are such as protective colloids and, for example, polyvinyl alcohol, polyvinylpyrrolidine, carboxymethyl cellulose, alkali metal salts of polyacrylic acid, styrene-maleic acid copolymer Alkali gold salts, etc., of which, polyvinyl alcohol is particularly preferred. The emulsification using emulsifiers in the present invention can be carried out by directly adding emulsifiers to the system, which is then completed by blending a specific amount of inorganic pigments in the amine-based resin, or separately arranging an emulsifier aqueous solution, in which the amine-based resin and inorganic pigments are added The mixture, which is then agitated with a stirrer, for example, colloid mill, dispersion mill, homomixer, homogenizer, etc., to generate a strong shear force. The amine-based resin used in the above emulsification process is an initial reaction product with a methanol mixing degree (degree of polycondensation ratio) of 4 ◦ 0% or less, and the initial reaction product with a mixing ratio of 200% or less is better. The particle size varies with the methanol mixing ratio (please read the precautions on the back and then fill out this page). Installed. Ordered. Printed by the Ministry of Economic Affairs, Central Standards Bureau, Industrial and Consumer Cooperative. The paper size is applicable to the Chinese National Standard (CNS) A4 specifications (210 X 297 mm), 030 ^ -Amendment A6 B6 Printed by the Ministry of Economic Affairs, Central Standards Bureau, Negative Work Consumer Cooperative Fifth, Invention Note (8) becomes smaller and larger and becomes smaller as the degree of mixing becomes larger. If the degree of methanol mixing is greater than 400%, the hydrophilicity is too large to obtain monodisperse particles. In addition, although the degree of condensation of the primary reaction product of the amine-based resin can be controlled by the methanol mixing degree as described above, it can also be controlled by GPC (gel permeation chromatography), LC (liquid chromatography), and acetone mixing degree. In such a control method, from the viewpoint of operation and reproducibility, it is preferable to use acetone mixing degree control. The acetone mixing degree indicates the polycondensation degree of the amine-based resin, which is to dissolve 2g of the initial reaction product in 5g of acetone, keep the water dripping into the liquid at 2 5 * 0, determine the amount of water required to achieve white turbidity, and connect the water and the initial reaction product The weight ratio is multiplied by 100. The preferred acetone mixing degree of the initial reaction product is in the range of about 50 to 500% and more preferably in the range of about 100 to 300%. If the acetone mixing degree exceeds 500%, the particles are difficult to obtain, and if it is 50% or less, it is difficult to obtain spherical fine particles. The preferred amount of emulsifier added is more preferably in the range of about 1 to 30% and about 2 to 1% for the amine-based resin. The particle size becomes smaller as the amount of emulsifier added increases, and the diameter increases as the amount of emulsifier decreases. If the added amount is less than 1%, it is impossible to emulsify, and if it exceeds 30%, the fine particles obtained by aging are difficult to separate into single particles. The particle size becomes smaller as the stirring efficiency increases and becomes larger as the efficiency decreases. This is because the increase or decrease of the stirring efficiency used to obtain the emulsified state is related to the force of shearing the initial reaction product. In this way, by appropriately selecting the polycondensation degree, emulsifying amount, and stirring efficiency of the amine-based resin, colored resin spherical fine particles having a true spherical and narrow particle distribution and having the desired particle diameter of the present invention can be synthesized at will. In the present invention, the spherical colored resin spherical fine particles mean the particle size ratio (the main axis to the secondary axis of the 200 spherical fine particle images obtained by electronic display mirrors (please read the precautions on the back before writing Page) | Binding _ Order · This paper scale is applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm) -10-Λ 6 Β6

Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of Invention (9) It was decided to be in the range of about 1.0 to 1.1. The curing catalyst used in the present invention is a polycondensation catalyst of an amine-based resin, for example, one or two or more appropriately selected from inorganic pigments such as hydrochloric acid, sulfuric acid, phosphoric acid, etc .; carboxylic acids such as benzoic acid, phthalic acid, acetic acid, acetone, water Yang acid, etc .; ammonium salts such as ammonium chloride, ammonium phosphate, etc .; sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, dodecyl benzenesulfonic acid, etc. The above-mentioned curing medium is preferably used in the range of amine-based resin emulsified in an amine-based resin emulsified with inorganic pigments (but the pigment is not taken into account), which is approximately mature. Processed CB is about ◦. 01 to 5%), more preferably about 0.2 to 5% (if processed CB is used, it is about 0.2 to 2%). If the added amount of the curing catalyst is too large, the emulsified state is broken and aggregates are formed. If the added amount is too small, the curing is insufficient or it takes a long time. Maturation is like keeping the cooked product, for example, a temperature range of about 10 to 200 ^ 0 for 1 hour, and then maintaining it at a temperature range of about 4 ◦ to 20Ot under normal or high pressure. The termination of aging is when the cooked product is insoluble in propylene, methanol, and methyl alcohol. Ethyl ketone, dioxane, dimethyl formaldehyde amine, etc. When the aging is terminated, the colored resin spherical fine particles are separated according to a well-known method and various separation methods are freely adopted, for example, natural sedimentation and centrifugal sedimentation combined with decantation, filtration and separation. The separated colored resin spherical fine particles are available in paste and dispersed forms, dispersed in water and various organic solvents, for example, non-polar solvents such as toluene, xylene, etc .; polar solvents such as methyl ethyl, methanol, Ethanol, isopropanol, dimethylformamide, tetrahydrofuran, etc .; and mixed solvents of these solvents. Colored resin spherical fine particles, after separation step, according to well-known methods such as natural drying, drying under reduced pressure, and heat (please read the precautions on the back before filling the nest page) Use the Chinese B Family Standard (CNS) Grade A 4 specifications (210 father 297 public ridges) -11-Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ^ 03ϋυ9 Λ 6 __Β6 V. Description of the invention (10 dry by air drying. Because the desired heat resistance, water resistance, solvent resistance, etc. of the colored resin spherical fine particles are further improved by performing hot working at a temperature of 100 to 20 ° after the drying step, it is better to perform hot working if necessary. However, when the drying step is performed at an extremely high temperature, it is known that hot processing is performed simultaneously, so hot processing is not necessary in this case. Colored resin spherical fine particles, after drying, are crushed by force to destroy the aggregated state, which is applied The force is supplied by pulverizers such as ball mills, hammer mills, and jet mills to obtain colored resin fine particles, which are fine powders after drying. Moreover, colored resin spherical fine particles, after drying, can be dispersed in a solvent to obtain paste or Decentralized form. The colored resin spherical fine particles are carried out, for example, in the polycondensation reaction in an emulsified state, the average particle diameter is in the range of about 0.1 to 50 μm, but the average particle diameter may exceed this range. In addition, in the present invention, the polycondensation reaction Carrying out in an emulsified state means that the polycondensation reaction is carried out under the condition that the droplets are dispersed in the dispersion medium, and the reaction is not limited to emulsification polycondensation, but includes suspension polymerization, etc. The colored resin spherical fine particles and their preparation methods are currently known The superiority is described below. ① The colored resin spherical fine particles of the present invention are superior in various properties, and the original superior properties of the amine-based resin are, for example, heat resistance, solvent resistance, chemical resistance, and durability. * ② The colored resin spherical fine particles of the present invention have excellent affinity with plastics such as thermoplastic resins and thermosetting resins, natural rubber, synthetic rubber, printing inks, and coating excipients. ③ Because the colored resin spherical fine particles of the present invention Good coloring and authenticity (please read the precautions on the back and then fill out this page). Packing · All paper sizes can be used in China National Standard (CNS) A 4 specifications (210X297) "-12 -丨 ϋ3ϋ 〔*. Λ 6 Β6 Beigong Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs. V. Invention description (1J spherical shape and narrow particle distribution, so the fluidity during processing when used in combination with molding resins becomes better, Moreover, the operation efficiency is improved. Furthermore, the colored resin spherical fine particles with different colors and different particle diameters can be blended with each other at random, which can be used for various coloring different from the current method of using pigments. ④ The production method of the colored resin spherical fine particles of the present invention can be produced Really spherical, narrow particle distribution, showing uniform dispersion of inorganic pigments, and excellent coloring, without compromising the various superior properties originally possessed by amine-based resins, such as heat resistance, solvent resistance, chemical resistance, and durability Resin spherical fine particles ⑤ The colored resin spherical fine particles of the present invention can be produced by controlling the particle diameter of the colored resin spherical fine particles in the range of about 0.1 to 50wm by an industrially advantageous method. Description of preferred examples Hereinafter, Examples and Comparative Examples are shown, but the present invention is not limited to the following examples. In Table 1, the synthesis conditions of Examples 1 to 6 and Comparative Examples 1 to 4 are listed. Example 1 In a bottle equipped with a stirrer, a reflux condenser, and a thermometer, 150 g (0.8 m〇i2) of benzene was placed Guanguanamine (benzoguanamine) 162g 37% concentration of formaldehyde water (2.0 〇m〇P aldehyde), and 0.65g 10% aqueous solution of sodium metabosate, the mixture was reacted under stirring at 94-95C temperature for 5 hours, as a result of methanol mixing 60% and (please read the precautions on the back before filling in this page) 4 paper scales are easy to use Chinese Η home rubbing standards (CNS> A 4 specifications (210x297 mm) -13--r, Bu A6 B6 Central Ministry of Economic Affairs Printed by Beigong Consumer Cooperative of the Bureau of Standards V. Description of the invention (12) The initial reaction product of C_250% mixing degree. To this initial reaction product is added 20 g of gasification agent (TA — 10 0, Fuji Titanium Industry Co., Ltd. .Made) and the mixture was reacted for 30 minutes with stirring, so as to obtain the initial reaction product dyed white by vaporized titanium. Individually, 1 g. 5 g Kuraray poval 205 (partial hydrolysis product of polyethylene glycol, Manufactured by Kuraray Co., Ltd.) The aqueous solution prepared by dissolving in 145 g of water is warmed to 9 ° L: Then, use The mixer (Model M, manufactured by Tokushu Kilca Kogyo Co., Ltd.) was stirred at 6000 rpm. The Kurar ay poval aqueous solution under stirring was added with the above white primary reaction product to obtain a white emulsion. Cooled at 40 t: For this emulsion, add 4 . 5 g of dodecane benzene sulfonic acid, the mixture is slowly heated and entangled under stirring at 50, 70 and 80 ° C for 2 hours each, so as to obtain polycondensation under emulsification conditions A solution of colored resin spherical fine particles suspended by reaction aging. When this suspension is observed with an optical microscope (600x magnification), it can be seen that the solution includes spherical fine particles with a diameter of about 4wm. The colored resin fine particles are filtered It was separated from the suspension, rinsed with water, dried at 100 ℃ for 1 hour, and then treated at 15 〇t: heat for 3 hours, and pulverized in a mortar to obtain a bright white colored resin spherical fine powder. Observation of 200 fine-grained electron microscope images obtained by scanning electron microscope (S-570, manufactured by Hitachi S-eisalcu-Sho), the colored resin spherical fine particles with 1.05 Particle size ratio (major axis / secondary axis) It is known that almost all vaporized titanium is dispersed into colored resin spherical fine particles. When measuring the particle size of the colored resin spherical fine particles with a Coulter counter (TA-2 type, the paper size is applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm) One 14 One {Please read the precautions on the back and then write this page) G3_ Λ 6 _B6_ V. Description of the invention (13

Coulter Co., Ltd.), found that the average particle diameter is 4.2 5 and the particle distribution is extremely narrow. In addition, the colorability, heat resistance, dispersibility, and water resistance of such colored resin spherical fine particles are studied as follows. It was found that such colored resin spherical fine particles are white spherical fine particles excellent in colorability, heat resistance, dispersibility, and water resistance. The results are shown in Table 2. Using a color difference meter, the color of the color between the pigment used and the fine particles of the obtained colored resin is compared and evaluated by the following criteria. Round 〇: The color difference between the inorganic inorganic pigment and the colored resin fine particles is 1% or less. Triangle △: The color difference between the inorganic inorganic pigment and colored resin fine particles exceeds 10% and less than 20%. Cross X: The color difference between the inorganic pigment itself and the colored resin fine particles is 20% or more. According to JIS K-5 1 0 1 (16), the heat resistance was studied by the deformation formed at 18 ° C for 2 hours and evaluated according to the following criteria. Round ○: The particle size ratio is determined after the heat resistance test and the difference from the untreated comparison is less than 10%. The Ministry of Economic Affairs Central Standards Bureau M Industry Consumer Cooperative. Ten systems (please read the precautions on the back before filling in this page) Cross X: The particle size ratio is determined after the heat resistance test and the difference from the untreated comparison is 10% or more Big. «Τ Dispersion according to JIS Κ-5101 (7) By fully kneading 2〇g printing paint and 5g colored resin fine particles, and then using a grinding rule to produce a groove corresponding to three times the average particle size of the powder, and inspect the groove The groove marks are evaluated. The dispersion is rated according to the following criteria. Successful inspection: less than 3 lines in groove marks. For various paper sizes, the Chinese National Standard "CNS" Grade 4 (210x297 gong) is used -15-

Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Λ 6 _Β_6 5. Description of the invention (14 test failure: there are 3 lines or more in the groove marks. According to JIS 1 < — 5101 (12), about 0.58 colored resin sphere The fine particles are placed in a glass test tube, add lOmp water, heat to 9 510, let cool, and pick the color to study the water resistance, and evaluate according to the following standards. Colorless and transparent: because the pigment has not come off from the colored spherical resin particles , So water resistance is good. Slightly white turbidity: Because the pigment is removed from colored resin spherical fine particles, water resistance and silicon are poor. Slightly black: Because the pigment is removed from colored resin spherical fine particles, the water resistance is poor. Fen Shi Example 2 — 4 and fch Comparative Example 1—3 Repeat the method of Example 1, except that the resin and pigment concentration, emulsifying amount, and stirring rate become the conditions described in Table 1, thereby obtaining colored resin spherical fine particles. The results are not shown in Table 2. Example 5 φ · The method of Example 1 was repeated, except that 20 g of Fe304 (spiral type, manufactured by Mitsubishi Metal Corporation) was used instead of oxychin, and colored resin spherical fine particles were obtained. Colored resin spherical fine particles with an average of 5.1 1 wm Path (

Coulter counter value) and spherical fine particles of black resin, same as in Example 1 (please read the precautions on the back and then fill out this page) Binding-Ordering-All paper sizes are easy to use a «家 橾 准 (CNS) A 4 specifications (210x297 male dragon) -16-030C3 Λ 6 Β 6 5. Description of the invention (In the case, it shows a true spherical shape and has good coloring, heat resistance, dispersibility, and water resistance. The results are shown in Table 2. Fen Example 6 In a bottle equipped with a stirrer, a reflux condenser, and a thermometer, put 1 I2g (0.6m〇5) benzoguanamine (benzoguanamine) 25g melamine (◦. 2moi2) 145g 37% concentration of formaldehyde water (1.8moi2 formaldehyde), and 0.65g of a 10% aqueous solution of sodium sulfonate, the mixture was reacted for 6 hours at 94-951C with stirring, so as to obtain the initial reaction product with a methanol mixing degree of 35% and acetone mixing degree of 150%. To the initial reaction product, 15 g of Soy Black (MA600, manufactured by Mitsubishi kasei Corporation) was added and the mixture was stirred for 3 ◦ minutes, so that the initial reaction product was obtained by dyeing black with sulfone black. As a rule, 7.5 g of Kuraraypoval 205 (polyethylene The part of dilute alcohol is based on the consumption of employees of the Central Standardization Bureau of the Ministry of Economic Affairs. The printed product (manufactured by Kuraray Co., Ltd.) was dissolved in an aqueous solution of 140 g of water to a temperature of 90¾, and then, using a homomixer (manufactured by M-type Tokushu Kika Kogyo Co., Ltd.) at 600 0 0 r pm Stirring. Add the above black primary reaction product to the black Kuraray poval aqueous solution under stirring to obtain a black emulsion. Cool to 40t: add 4.lg dodecylbenzene sulfonic acid to this emulsion, and slowly warm the mixture under stirring The tandem is heated at 50, 70 and 90 ° C for 2 hours each, so as to obtain a solution of colored resin spherical fine particles suspended by polycondensation reaction under emulsification conditions. This suspension is subjected to an optical microscope (6 0 0x magnification) solution can be seen during observation-17-(please read the precautions on the back before filling in this page) Each paper size is free to use China National Standard (CNS) A4 specifications (210x297 mm) Printed by the Bureau ’s Consumer Cooperative Society ^ Λ 6 _Β6_ V. Description of the invention (10 includes spherical fine particles with a diameter of about 6 Zim. Colored resin-like fine particles are separated from the suspension by filtration, rinsed with water, and dried at 1001C for 1 hour. Then heat treatment at 150¾ for 5 hours to The grinding bowl is slightly crushed, so that bright black colored resin spherical fine powder is obtained. When observing the colored resin fine particles obtained by scanning electron microscope, it has a particle size ratio of 1.06 (major axis / secondary axis) and, because No black black has been found that has not been converted into particles, so it is known that almost all sulfonic black is dispersed into colored fine spherical resin particles. When the particle diameter of this colored resin spherical fine particles (TA-2 type, manufactured by Coulter Co., Ltd.) was measured with a Coulter counter, it was found that the average particle diameter was 5.87 Wm and the particle distribution was extremely narrow. In addition, such colored resin spherical fine particles are excellent in color rendering, heat resistance, dispersibility, and water resistance. Results 7F in Table 2. hh Comparative Example 4 Place 2 g acrylic acid, 240 g methyl methacrylate, 29 g divinylbenzene, 50 g styrene resin, lg azobisisobutylene in a bottle equipped with a stirrer, reflux condenser, and thermometer , And 25g Shuo black (MA 600, manufactured by Mitsubishi kasei Corporation) and the mixture was thoroughly stirred and mixed uniformly, thereby obtaining a black solution. Individually, ginseng dissolves 17 g of Kuraray poval 205 (partially hydrolyzed product of polyvinyl alcohol, manufactured by Kuraray Co., Ltd.) in 600 g of water and uses a homomixer (M type, Tokushu Kika) under a nitrogen atmosphere. Kogyo Co., Ltd.) stirred at 6000 rpm. Add the above black solution to the Kuraray p-ova 1 aqueous solution under stirring and warm the resulting mixture to (please read the precautions on the back before filling out this page). (CNS) A4 specifications (210x297 g *) -18-Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Λ 6 __ Β6 V. Description of invention (17 8Ot and placed at this temperature for 30 minutes. Then, the mixture was moved into the four necks In the bottle, the polymerization reaction was stirred and heated under 8 Ot: nitrogen atmosphere for 5 hours, so as to obtain a suspension of black heat-cured resin. When the suspension was observed with an optical microscope (600 times magnification), it was found that the solution included Spherical fine particles with a particle size of about 6 wm. The matured resin is filtered and separated from the suspension, rinsed with water, dried at 100Ό, and crushed in a mortar, so as to obtain black matured resin spherical fine particles. When the spherical particles of the matured resin obtained by observation were observed, the particle size ratio (major axis / secondary axis) was 1.1 and it was found that the black particles were converted into particles. When the particle size of the resin spherical fine particles was measured with a Coulter counter, it was found The average particle size is 6. 23wm The particles are widely distributed. In addition, the resin spherical fine particles have poor color rendering, dispersibility, and water resistance. The results are shown in Table 2 and Table 1. The synthesis conditions for Examples 1 to 6 and Comparative Examples 1 to 4 are shown. (Please Please read the precautions on the back and fill in this page.) The specifications of the National Sample Standard (CNS) A 4 (210x297 g *) -19-ο 3 ο G 6Λπ in the use of various papers 1 The conditions for printing and synthesis of employees ’cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs (蛀 1) Tree species and« degree (*)) Concentration (1 weight) Emulsified mist (% Λ) ttmixed degree (rpa) Emulsified chrysanthemum (rp ·) Zero_ «Combined degree (") B "" Qu Qu degree ⑷ Xiao Shiyong 1 K base street ridge 91.3 8-7 4.8 6000 good 60 250 Actual confession 2 R base tree mulberry 79 · 2 20.8 4.8 6000 good 60 2S0 real streamer 3 R base cabinet 91.1 3 8-7 10.6 6000 good 60 250 real travel example 4 according to Qi goods 93.1 3 8-7 2.8 2000 good 60 250 real key holding 5 R base «Κ91.3 8.7 4.8 6000 eood 60 250 actual supply of 6 κ base «luan 92.7 7.3 3-8 6000 β〇ο < 1- 35 150 comparative support 1 e base« Κ63 · 6 36.4 4-8 6000 e〇〇d 60 250 comparative support 2 Press the base tree »99.3 0-7 4. 8 6000 good 60 2S0 Compare with 3 K-based resin 91.3 8.7 0.9 2000 ft〇a «* hat bad 60 250 Compare with 4 propylene based" Remaining 92 · 8 7-2 5.0 6000 t {〇od — — (fi X) « »Soup: t-tree BS / (» 科 霣 + 树》 重)】 X 100 Pigment degree: [bright weight / (pigment words + tree ΚΜ >) Χ100 emulsifying dose: [emulsion pain weight / (emulsion Μ 簠+ Shu Huanzhong)] Χ100 This paper standard is used in the SS home «quasi (CNS) A 4 specifications (2) 0x297 public ¢) Read the precautions before filling ο / fvv ϋ 6 6 ΛΠ V. Description of the invention (丨 〇 Table 2 (dress 1/2) colored ankle chopper kjin l) 9Λ) n »tb (suspicion) (/ iin) m & k m & t points tttt JIS K-5101 (7) wtmm K- S10102) HIMtilS K-S101 (16) wmi 〇11-0 4.25 1-05 o wmsj o wmz 73-7 26.3 4-S3 lU o mm m & mo mm3 89-0 11-0 1-QS 1.18 o mas ) m & mo Ming-0 11-0 40.23 1.04 o 'mm & j 〇mms 89.0 11.0 5.U 1-07 o mm »m & m 〇mme 90-9 9-1 5.87 1.06 o m & m 〇 (please Read the precautions on the back before writing this page) Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 1) Post: [flamitas / (lanthanum is suspected to be + Pengzhong)] χιοο ai ^ bfc * cswEffi /] χχ〇〇 The size of this paper uses China's "Home Standard (CN5) A 4 specifications (210x297 Gongluo) fj 〇3〇 ^ V. Description of Invention (w) Table 2 (玢 2/2)

The physical properties of the colored cabinet κ 镳 grass (column η tree • ripening ratio is higher than the average grain complex ttStb with peach content JIS «water β JIS Xie JtS («) («) (um) (main axis / secondary axis> ; K-5XOI (7) Κ-510ΚΙ2) K-5101 U6) Comparison A 1 54.0 46.0 8.32 1.32 Failed light a er er 〇tb compared to Μ 2 99-1 0.9 4.10 1.04 X planting success ft color mingming. Comparing Μ 3 89.0 U.0 72.15 1.36 △ Oak and wood failure ft Domina 〇 Comparison side 4 92.8 7.2 6.23 1-22 Δ. Gun brewing lost light color X (please read the precautions on the back before filling this page) Printed by the Central Standards Bureau of the Ministry of Industry and Consumer Cooperatives

(Note 1) Tree · MMbft ratio: [«Teng ripening" 霣 / (tree mule ripening _ weight + «material weight)] X100 kiln material ratio: [" Branch weight / («Bronze weight + A material weight)]] xiOO The standard of this paper is the 8 national quasi (CNS) A 4 specifications (210X297 gong) ^ 〇3〇υ ·: η buckle. Ml B 丨 A6 B6 5. Description of the invention (21) As shown in Table 2, implement The colored resin spherical fine particles of Examples 1 to 6 have a spherical shape and are superior in all coloring properties, dispersibility, water resistance, and heat resistance. However, in Comparative Example 1, since the pigment ratio is high, the dispersibility and water resistance are poor. In Comparative Example 2, since the pigment ratio is low, the colorability is poor. In Comparative Example 3, spherical fine particles were not obtained. This is because the polycondensation reaction did not proceed under emulsification conditions. In Comparative Example 4, since the cured amine-based resin was not used, the colorability, dispersibility, water resistance, and heat resistance were inferior. Next, the present invention shows examples and comparative examples using processed black as an inorganic pigment, but the present invention is not limited to the following examples. 1 | First, an example of processing black is shown. Participant Example 1 In a Labo Plasto mill (manufactured by Toyoseiki Seisaku-Sho, Ltd.), 100 parts by weight of MA-6 0 0 (manufactured by Mitsubishi Kasei Corporation) was placed as CB, and 200 parts by weight of E ρ 〇 min SP-3 0 0 (manufactured by N i ρ ρ ο n S hokubai Co., Led.,) It is a polyethyleneimine with a molecular weight of 30, ◦00, and the mixture is at 10◦ ~ Central Bureau of Standards, Ministry of Economic Affairs S Printed by the Industrial and Commercial Cooperative Society for 2000 t: the temperature is stirred and kneaded for 20 minutes, and then cooled to a processed black, this is called CB (1). Reference Example 2 Repeat the steps of Reference Example 1 except for 10 ◦ parts by weight of Denacol EX-171 (manufactured by Nagase Chemicals Co., Ltd.), which is lauryl alcohol polyethylene glycol glycidyl ether with a molecular weight of 902. To replace 200 -23-(please read the note $ item first and then this page) This paper size is applicable to China National Standard (CNS) A 4 specifications (210 X 297 mm) Λ 6 Β 6 Central Bureau of Standards 3 Industrial & Consumer Cooperative,-" System V. Description of invention (Except for more than 2 parts by weight of polyvinylamine, obtained processed sulphur black. This is called CB (2). Reference example 3 Repeat the steps of reference example 1, Except for 100 parts by weight of PEG 1000 (Kanto Chemicals Co., Inc.), which is polyethylene glycol with an average molecular weight of 1,000, it is used to replace 200 parts by weight of polyethyleneimine. Processed black. This is called CB (3). Table 3 lists the synthesis conditions of Examples 7-17 and Comparative Examples 5 and 6. Example 7 is equipped with a stirrer, reflux condenser, and thermometer. Put 187g (1.0m〇J?) Benzoguanamine (benzoguanamine), 25g melamine (0.2moin 243g 37% concentration of formaldehyde water (3.0mo) 2 formaldehyde) in the four-necked bottle, 0. 95gl0% aqueous solution of sodium masterbatch, the mixture was reacted at a temperature of 94-951C under stirring for 3.5 hours, from which the initial reaction product of methanol mixing degree 60% and acetone mixing degree 2 50% was obtained. 67.1 g of CB (2) from Reference Example 2 was added and the mixture was stirred for 30 minutes, thereby obtaining the initial reaction product of blackening by CB. Individually, 15.9 g of K-uraray poval 205 (polyvinyl alcohol Part of the hydrolysate (1 (11 ^ -ray Co., Ltd.)) dissolved in 1 8 3 g of water solution was prepared to 9〇t temperature, then, using a homomixer (M-type Tokushu Kika Kogyo ( Please read the precautions on the back before filling in this page) Clothing and paper scales are easy to use China National Standard (CNS) A 4 specifications (210x297 public burial) -24-Λ 6 Β6 Printed by the Consumer Cooperative, member of the Central Standards Bureau of the Ministry of Economic Affairs Ⅴ 3. Description of the invention (manufactured by 23 Co., Ltd.) at 600 rpm jS. The Kura-ray poval aqueous solution under search is added with the above black primary reaction product to obtain a black emulsion. Cooled at 40t: this emulsion is added 4. 62 g of dodecane benzene sulfonic acid, the mixture is slowly heated and ore is mixed under stirring at 5 0, 70 and 9 01C For 2 hours, there was in the emulsification conditions of the reaction solution was aged condensing spherical particles of a black resin suspension polymerization. When this suspension was observed with an optical microscope (600 times magnification), it was seen that the solution included spherical fine particles with a particle size of about 5 / im. The black resin-like fine particles are separated from the suspension by filtration, rinsed with water, dried at 100t: 1 hour, then heat-treated at 150 1C for 5 hours, and crushed slightly with a mortar to obtain black colored resin spherical fine particle powder . When observing 200 obtained colored resin spherical fine particles with a scanning electron microscope, the particle size ratio is 1.05 (major axis / secondary axis) and because no black particles that have not been converted into particles are found, almost all are known Sulphur black is dispersed into black resin spherical fine particles. When the particle diameter of the black resin spherical fine particles was measured with a Coulter counter, the average particle diameter was found to be 5.05 wm and the particle distribution was extremely narrow. In addition, when the resin fine particles of this colored resin were studied for coloring, dispersibility, water resistance, etc. as described above, they were found to be black resin spherical fine particles excellent in all physical properties. Article Fenshi Example 8 _ 1 0 The method of Example 7 was repeated, except that CB (1) and CB (3) and the unprocessed CB (MA-600 above) obtained from Reference Examples 1 and 3 were used to replace under the conditions of Table 3. In addition to CB (2), black resin fine particles are obtained. (Please read the precautions on the back and then fill in this page) Each paper size is used in the National B Standard «quasi (CNS) A 4 specifications (210X297 public *) -25-Λ 6 _B6 V. Description of the invention (24 The results are shown in the table 5. Endeavour Example 1 1 1 1 6 and hh repeat the method of Example 7 compared to Examples 5 and 6, except that the CB addition amount, emulsifying amount, methanol mixing degree, and propanol mixing degree are shown in Tables 3 and 4. The fine particles of black resin are obtained. The trappings are shown in Tables 5 and 6. Example 1 7 Repeat the method of Example 7, except that benzoguanamine is replaced by cyclohexanecarboguanamine. In addition, black resin fine particles were obtained. The results are not shown in Table 6. In addition, the following are evaluation criteria for the colorability of the colored resin spherical fine particles obtained in Examples 7-17 and Comparative Examples 5 and 6. Round 〇: The color difference between the inorganic pigment itself and the colored resin fine particles is 5% or less. The consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs Du Xiu (please read the precautions on the back before filling in this page) Triangle △: inorganic pigment itself The color difference between the fine particles of colored resin is more than 5% and less than 10%. Prepared to cross X: inorganic pigment itself The color difference with the colored resin fine particles is 10% or more. In Tables 3 and 4, the synthesis conditions of Examples 7 to 17 and Comparative Examples 5 and 6 are shown. For each paper size, the Chinese National Standard (CNS) is used A4 specifications (210x297 g *) -26-^ .1 ο 3 ο Ministry of Economic Affairs Central Standards Bureau Beigongxiao # Cooperative printing 31 V. Description of invention (νό Table 3 Synthetic conditions (荘 1 > tree «type and soup degree Yanke «Class and Leakage (« 霣) emulsified metal (i% M)) A _ rent combination degree (%) propyl Mn Ni degree (%) actual signal supply 7 R base 9 9 CBC2) Χ0.0 5-0 60 250 Actual travel for 8 K base tree K90.0 CB (1) 10.0 5-0 60 250 Example 9 Amino base »90.0 CB (3) 10.0 so 60 250 Actual example 10 Amino base 90.0 Unprocessed CB 10.0 5.0 60 250 Example 11 Mengji Shuteng 90.0 CB (2) 10.0 5.0 75 350 Gong Shiyong 12 Wrestling Base Tree »90 · 0 CB (2) 10.0 5.0 35 150 Example 13 Amino Tree Hall 90.0 CB (2) 10.〇2.5 60 250 (Note U tree porridge concentration: [Xie 鱳 霣 / (pigment Μ + 湳 霣 >) xloo 鳗 Material concentration: [鳳 料 £ ✓ (銷 科 重 + tree 豳 霣 >) χι〇〇Emulsion surface : C emulsification "8 weights / (emulsion stroke weight +« 風 霣 >] xioo (please read first Note the back of the nest reloading the page) · installed under this offer degrees side due to the quasi Nakajima (⑽ A feud ⑵ use. χ_) _ 卞 ο ϋ G 6 ΛΠ V. Description of the invention (i) Table 4 Synthesis conditions (Note 1) Types of resins and cosmetics types and concentrations of emulsified noodles_Mixed degree acetone mixed (, heavy) («Heavy } (*) Degree (*) Example 14 Amino resin 90.0 CB (2) 10-0 uo 60 250 Example 15 Amino resin 95.0 CB (2) 5.0 5-0 60 250 Example 16 Amino resin 80.0 CB (2) 20.0 5.0 60 250 Example 17 Amino resin 90.0 CB (2) 10.0 5.0 60 250 Comparative Example 5 Amino resin 62 · 0 CB (2) 38.〇5-0 60 250 Comparative Example 6 Amino resin 99.5 CB {2) 0-5 5-0 60 250 (Please read the precautions on the back before filling in this page) Packed. Printed by the employee cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (Note υ resin * degree: [resin weight / ( Tremor weight + resin weight)] xioo pigment * degree: [pigment weight / (pigment weight + resin weight)] > < 10 square emulsification volume: [emulsion * weight / (emulsion weight + resin weight)] xioo The 5fc scale of the original paper is used in the national standard (CNS) A 4 specifications (210x297 gong) · > Γ 030 ^ ¾ Λ 6 Β 6 V. Description of the invention (4) Table 5 The properties of colored pait grains (Note 1) Tree》 Salting ratio 0 material ratio Average & filming ratio and coloring property score «Property JIS Water resistance JIS Water resistance JIS (% Λ) (% Λ) (κ m) (Main shaft / time Μ) K'5101 (7) K-S10XC12) K -5101 (16) Supplied by Zhan 7 87.3 12-7 5.05 1.04 〇TT paid successfully and mingled. Instance of real travel β 87.3 12.7 4.85 1.04 〇 Successful inspection and transparent color 〇 Real travel 9 9-3 12-7 5.15 1.06 〇Successful inspection of Dooming 〇Gong Zhanbai 10〇67.3 12-7 4.70 1.06 Δ Contribute successfully to look up of Taoming 〇Bao Shi Example 11 87.3 12.7 2.10 1.04 〇Successful inspection of the machine Dou Ming 〇 Administration 12 87.3 12.7 10.04 1.05 〇Easy inspection and transparent color ○ Real travel example 13 87.3 12.7 40.22 1.06 〇Issuance inspection successful and transparent color (please read the notes on the back before filling in this page) {装-线 线. Ministry of Economic Affairs Bureau of Standards ΚΚ 工 消 # Printed by the cooperative (Note 1) Shuhuan Maturation "ratio: C tree B matured weight / (tree mule weight + Gu Kezhong >) xioo« Material ratio: [《科 重 / (树 鼸抯 化 铕 霣 + 欢 意 意]] This paper standard is used in the S National Standard (CNS) A 4 specifications (210X297 male dragon) ίν · ϋ 3 ο 12 66 ΛΒ Employee of the Central Standards Bureau of the Ministry of Economic Affairs消 #Cooperative printed five. Description of the invention (vp Table 6 "Sex (Cholesterol 1 > The ratio of the tree to the goose and the average grain size of the tree tree of the colored tree is higher than the average grain size of the tree" compared to the coloring point JIS Momo to JIS Jazz Familiar with JIS (% Λ) (m) (spindle / time_> K-S101 ⑺ K-510K12) K-5101 (16) For Xiaolv 14 87.3 12-7 0.85 1.05 〇 Eaves measurement succeeded鰌 for 15 93.7 6-3 4.95 X.03 〇tt moose success _ Sedao Ming 〇 Baozhu Yong 74.7 25.3 7.31 1.07 〇 check ft success color channel "〇 Xiao drawing support Γ7 87.3 12.7 4.97 1-05 〇 Moose success Shovel color is transparent 〇Comparative example 5 51.9 48.1 8.13 1.22 〇MM lost light black 〇Comparative for 6 99-4 0.6 5.01 1-04 X successful check-up complexion transparent 0 (please read the precautions on the back before writing this page ) (Note 1) Tree mule * chemical ratio: [tree «* chemical« weight / (plant ** chemical 《weight + * material weight)] X100 tree material ratio: [heap weight / (tree maturing »weight + ( Material weight)] The 5fc scale of this paper is used in a ® home standard (CMS) A 4 specifications (210x297 mm). The Central Standards Bureau of the Ministry of Economic Affairs Staff Consumer Cooperative System Λ 6 ____ Β_6 V. Description of invention (23 as shown in Tables 5 and 6) Show The colored resin fine particles in Examples 7 and 17 are black resin spherical fine particles excellent in colorability, dispersibility, water resistance, and heat resistance, and the CB_processed product has superior color rendering properties than the CB_unprocessed product. In Comparative Example 5, since the CB content exceeds the range of about 1 to 30%, the average particle size and particle size ratio become large and the dispersibility is low. In Comparative Example 6, since the CB content is less than about 1 to 30%, the coloring property is poor. Example 1 ft black resin spherical fine particles, 10 g, which was obtained in Example 7, 4 s calcium stearate, 1 000 g polypropylene cylindrical particles (K — 10 1 4 manufactured by Chisso Corporation) Mix with a high-speed mixer, and then do not mold it into plates with a thickness of 2 mm, 4 mm, and 6 mm each using an injection molding machine (model SG25, manufactured by Sumitomo Heavy Industries, Ltd., at a temperature of 25 01 C). All the resulting plates have a smooth surface, gloss, and uniform black with no color irregularities, and are superior in chemical resistance, solvent resistance, and water resistance. Fen Shi Example 1 9 black resin spherical fine particles, 10g, which is obtained in Example 7, 4 rash g stearic acid 0, 1 000g polyethylene cylindrical particles (J-40, Nippon Petrochemicals Co., Ltd. (Made) mixed with a high-speed mixer, and then individually molded into 2mm, 4mm, and 6mm plates with an injection molding machine (model SG 25, manufactured by Sumitomo Heavy Industries, Ltd., at 2 OOP temperature). All the resulting plates are provided (please read the precautions on the back before filling the nest page). All paper sizes are free to use China National Standard (CNS) A 4 specifications (210x297 g *) _ 30-Μ I.) 'Λ 6 Β6 Ministry of Economic Affairs, Central Standards Bureau, β-consumer cooperation, Du Wu system V. Description of the invention (2 piano smooth surface, gloss, and uniform black with no color irregularities, and its chemical resistance, solvent resistance, water resistance, etc. Dou Han Example 2 0 Black resin spherical fine particles, 10 g, which is obtained in Example 7, 4 g calcium stearate, 1 000 g polystyrene columnar particles (X Η 8 0 3, Asahi Chemical (Industry Co., Ltd.) mixed with a high-speed mixer, and then, do not use an injection molding machine (SG25 type, Sumit 〇m ο H eavy Industries, L td., At 2 2 ◦ Χϋ temperature) Molded into 2mm, 4mm and 6mm thick plates. All the obtained plates have a smooth surface, gloss, and uniform black with no color irregularities, and their chemical resistance, solvent resistance, and water resistance It is superior. Example 2 1 Black resin spherical fine particles, which are obtained in Example 7, and more than propylene [Trademark "Arotane 207 ", non-volatile component 50%, manufactured by Nippon Shokubai Co., Ltd., combined and dispersed therein so that the fine particle content is 30% (= [black resin spherical fine particles / (Black resin spherical fine-grain decapropylene polyol)] XI 〇〇). Even without the use of strong dispersing devices such as sand milling, the dispersion is still superior. The resulting liquid I and polyfunctional isocyanate [trademark, ' Sumidur ", manufactured by Sumitomo Bayer Urethane Co., Ltd.] combined and mixed thoroughly so that the weight ratio is 9 (liquid I) to 1 (isocyanate). The resulting dispersion is diluted with diluent (including toluene and ethyl acetate 1: 1) The mixture) is diluted to obtain the viscosity of the gas spray, which is obtained (please read the precautions on the back and then fill out this page) to install < order each paper size to use Chinese sleepy home «quasi (CNS) A 4 specifications ( 210x297 public love) -31-Λ 6 Β 6

Printed by Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (to the coating composition. This coating composition is sprayed on the polystyrene board using air and forcedly dried at 60¾ for 30 minutes. The surface of the obtained test piece is completely matt Randomness and almost no sand-like feeling under the touch. Moreover, this plate is excellent in alkali resistance, acid resistance, solvent resistance, and water resistance. Example 2 2 Black resin spherical fine particles, which are examples 7 obtained, combined with acrylic resin [trademark "Aroset 5227々, non-volatile component 45%, manufactured by Nippon Shokubai Co., Ltd.] and dispersed therein so that the fine particle content is 30% (= [black Resin spherical fine particles / (black resin spherical fine particles) acrylic resin)] X100). Even if a strong dispersion device such as sanding is not used, the dispersion is still superior. The resulting dispersion is diluted with a diluent (including a 1: 1 mixture of toluene and ethyl acetate) to obtain a sprayable viscosity, thereby obtaining a coating composition. This coating composition was applied to a polystyrene board using a gas barrier and forced to dry at 60C for 3 ◦ minutes. The surface of the obtained test piece had no gloss randomness at all, and there was almost no sand feeling when touched. Moreover, the plate is superior in alkali resistance, acid resistance, solvent resistance, and water resistance. Example 2 3 Black resin spherical fine particles, 40 g, which is obtained in Example 7 and lithographically printed with 1 40 s The blend of excipients used in the ink was kneaded without the use of a dispersant, but three sticks were used. The black resin spherical fine particles are sufficiently dispersed in the excipient. Add 4 s ink solvent to the dispersion slurry obtained at 100 g (please read the precautions on the back before filling in this page). Packing-line < each paper size is free to use China National Standard (CNS) A4 specifications (210X297 *) One 32 — Λ 6 Β6 rr, .ν

5. Description of the invention (3J, ◦. 2g 6% cobalt desiccant, and 1.5g 6% magnesium desiccant and knead the resulting mixture to obtain a black ink, which is converted into a uniform slurry. The printed matter, which is flattened with black ink Printed by printers, the blackness is superior. (Please read the precautions on the back before writing this page) Binding · Order-China National Standards (CNS) A4 for all paper sizes made by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Specification (210x297mm) -33-

Claims (1)

丨 1: > 5 Supplements 丨 A7 B7 C7 D7 Printed by Beigong Consumer Cooperative of the Bureau of Standards of the Ministry of Justice VI. Patent Application Annex II: Patent Application No. 80107229 Chinese Application Patent Scope Amendment 1982 Monthly Amendment 1. A method for preparing spherical fine particles of colored resin, including blending and emulsifying amine-based resin and inorganic pigment, and performing polycondensation reaction under emulsification conditions, and blending the amine-based resin cooked product and inorganic pigment into one The ratio of the inorganic pigment to the total amount of the amine-based resin cured product and the inorganic pigment is 1 to 30% by weight, wherein the amine-based resin is the initial reaction product of formaldehyde and the amine-based compound, at least one of which is selected from benguamin (Benzoguanamine) The amount of guanam in the cyclohexane carboguanamine, cyclohexene carboguanamine is 40 to 100 weight percent, and the inorganic pigment is black, which It is processed with a compound having a functional group that is reactive and / or compatible with the master black functional group, and the amount of the emulsifier relative to the amine-based resin is 1 to 30% by weight. 2. The method for producing colored resin spherical fine particles as claimed in item 1 of the patent scope, wherein the compound having a functional group having reactivity and / or affinity with the master black functional group is at least one selected from the general formula (1) Of the polyethylene glycol glycidyl ether compounds and their derivatives shown, R-0-(-CH2-CH2〇-)-n-CH2-CH-CH (1) {Please read the precautions on the back first Fill in this page) 0 "Paper" scale speed using China's a standard (CNS) A4 specifications (210x297 mm) 1 Printed A7 B7 small body ci by the Beigong quasi-bureau quasi-bureau co-operative of Yiyang Department ^ _D7 ___ VI. Application for patent model Group. (Here, R is a hydrogen atom or at least one group selected from an alkyl group having 1 to 20 large atoms and may have a substituent; an aryl group; and a group in an unsaturated aliphatic residue, and η is 1 to An integer of 30). 3. A spherical fine particle of colored resin, which contains an amine-based resin cured product and inorganic pigment in one body, and the ratio of inorganic pigment to the total amount of amine-based resin cured product and inorganic pigment is 1 to 30 weight Percentage range, where the amine-based resin cured product is the reaction product of formaldehyde and amine-based compounds, at least one of which is selected from benzoguanamine, cyclohexane carboguanamine, and cyclohexane carboguanamine (C-yclohexenecarboguanamine) The amount of guanamine (guanam i ne) is 40 to 100 weight percent, and the inorganic pigment is black, and it is reactive and / or affinity with a functional group with sulfonate black Functional compound processing. 4. For example, the colored resin spherical fine particles of item 3 of the scope of patent application, in which the ratio of inorganic pigments to the total amount of amine-based resin cured products and inorganic pigments is 5 to 2 0 96 weights. 5. If the colored resin spherical fine particles of item 3 of the patent application range, the average particle size is in the range of 0.1 to 50ym. 6. If the colored resin spherical fine particles of items 3, 4 or 5 of the patent application range, the particle size ratio (major axis to secondary axis) is in the range of 1.0 to 1.1. (Please read the precautions on the back before filling the nest page) _Filled • Ordered. This paper size is applicable to China National Standards (CNS) A 4 specifications (210x297 g; ft ·) -2-