KR950005306B1 - Method for producing spherical fine particles of colored resin - Google Patents

Abstract

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Description

Preparation method of colored resin spherical fine particles and colored resin spherical fine particles

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to colored resin spherical fine particles used in paints, inks, plastics, fibers, rubbers, colorants, chlorine agents, fillers, toners, electrostatic copiers, carriers, and cosmetics. More specifically, the present invention relates to novel industrially useful colored resin spherical fine particles incorporating an amino resin cured product and an inorganic pigment and a method for producing the same.

Conventionally, various types of stain-resin spherical fine particles have been used in plastics, paints, inks, cosmetics, and the like, and are characteristically used in their respective applications. Such colored resin spherical fine particles are made by integrating a dye or pigment with a resin. The use of such dyes and pigments in combination with the resins without the use of dyes and pigments as such is due to the fact that affinity with polymers such as paints, inks, plastics, fibers, and rubbers can be improved. In addition, when the fine particles are spherical, there is an advantage in that the molding fluidity is improved as compared with the case where the fine particles are not spherical, and when used in paints and fibers, the surface is smooth and the filling amount can be increased.

The colored resin spherical fine particles obtained by combining a thermosetting resin such as a phenol resin and an epoxy resin or a thermoplastic resin such as an acrylic resin or a vinyl resin with an organic dye or an organic pigment are excellent in clarity and coloring power, but have excellent heat resistance, light resistance, solvent resistance, It tends to be inferior in weather resistance and tricolor resistance. On the other hand, colored resin spherical fine particles using inorganic pigments for coloring are superior to organic pigments in terms of solvent resistance, light resistance, heat resistance, and tricolor resistance, and are superior to organic pigments in terms of light resistance and heat resistance.

As the colored resin fine particles in which the thermoplastic resin is colored with the pigment, for example, the colored resin fine particles (Japanese Patent Laid-Open No. 58-17169) obtained by mixing and pulverizing the thermoplastic resin and the pigment may be used during the reaction such as suspension polymerization. Colored spherical spherical fine particles obtained by adding (Patent No. 57-22324) and colored resin spherical fine particles obtained by coating a pigment after chemical or physical treatment on the surface of thermoplastic resin fine particles (Japanese Patent Laid-Open No. 63-10671). Publications) are known.

Moreover, as a colored resin spherical fine particle which colored the thermosetting resin with the pigment, the pigment | dye of the thermosetting resin obtained by adding a pigment when synthesize | combining thermosetting resins, such as a phenol resin and an epoxy resin, by polyaddition reaction and an addition condensation reaction, Particulates are known.

Conventional colored resin spherical fine particles using the thermoplastic resin have a problem of poor heat resistance, solvent resistance, chemical resistance, etc., poor adhesion between the resin fine particles and the pigment, and poor smoothness of the colored particle surface. In addition, the conventional colored resin spherical fine particles using the above-mentioned thermosetting resin have a wider particle size distribution, so that the particle shape is not a spherical fine particle, but the particles have weak defects, and such classification is necessary depending on the use. There is an expensive problem in terms of price.

The present invention solves the problems of the colored resin spherical fine particles obtained by the above-described prior art, which is spherical fine particles excellent in heat resistance, solvent resistance, and chemical resistance, may be spherical, and further satisfactory in durability and coloring power, An object of the present invention is to provide a method for producing industrially advantageous colored resin spherical fine particles and such colored resin spherical fine particles.

In order to solve the above problems, the present invention mixes and emulsifies an amino resin and an inorganic pigment, and performs a polycondensation reaction in an emulsified state so that the ratio of the inorganic pigment to the total amount of the cured amino resin and the inorganic pigment is 1-30% by weight ( Hereinafter, unless otherwise specified, [%] is [% by weight] to provide a method for producing colored resin spherical fine particles in which an inorganic pigment is integrated into a cured amino resin.

In the present invention, the amino resin is at least one guanamine selected from the group consisting of benzoguanamine, cyclohexanecarboguanamine, and cyclohexenecarboguanamine. An initial reaction product of an amino compound and formaldehyde, which occupies 40-100% by weight, and the inorganic pigment is treated with a compound having carbon black and a functional group having a functional group having a reactivity and / or affinity for the carbon black functional group. Provided is a method for producing resin spherical fine particles.

Furthermore, in order to solve the said subject, the present invention is colored resin spherical fine particles in which the cured amino resin and the inorganic pigment are integrated, and the ratio of the inorganic pigment to the total amount of the cured amino resin and the inorganic pigment is 1-30% by weight, The cured amino resin is a reaction product of formaldehyde with an amino compound having 40-100% by weight of at least one guanamine selected from the group consisting of benzoguanamine, cyclohexanecarboguanamine and cyclohexene carboguamine. Provided are colored resin spherical fine particles, in which an inorganic pigment is carbon black and is treated with a compound having a functional group having a reactivity and / or affinity with a functional group of the carbon black.

In the present invention, the ratio of the inorganic pigment to the total amount of the cured amino resin and the inorganic pigment is required to be 1-30%. If the ratio of the inorganic pigment is less than this range, there is a problem that the colorability of the colored resin spherical fine particles is insufficient, and if the ratio is large, the entire amount of the inorganic pigment cannot be fixed to the amino resin, the particles become distorted, and the particle distribution becomes wider. have. In addition, there is an advantage that the colored resin spherical fine particles excellent in heat resistance, solvent resistance, and chemical resistance can be produced by using the amino resin.

The colored resin spherical microparticles | fine-particles of this invention are manufactured as mentioned later, for example, and an inorganic pigment and an amino resin hardened | cured material are integrated. As a result, the spherical fine particles are colored with an inorganic pigment.

The spherical shape in the colored resin spherical fine particles of the present invention means, for example, that the particle diameter ratio (long diameter / short diameter) obtained on an electron microscope photograph of 200 colored colored spherical fine particles is in the range of 1.0-1.25.

In the present invention, the amino resin is, for example, urea, melamine, benzoguanamine, cyclohexanecarboguamine, cyclohexenecarboguamine, norbornanecarboguanamine (norbornanecarboguanamine) or novo having two or more amino groups in the molecule. It may be a resin obtained by a reaction for decondensing formaldehyde and one or more amino compounds selected from the group consisting of enecarboguanamine (norbornenecarboguanamine), and the amino resin may be etherified by alcohol. At least carbon selected from the group consisting of benzoguanamine, cyclohexane carboguanamine and cyclohexene carboguamine as amino resins when using carbon black treated as described below (hereinafter referred to as [carbon black] as [CB]) It is preferable to use the initial reaction product (preliminary condensation product) which polycondensed the amino compound and formaldehyde which one type guanamine occupies 40-100%, and may be etherified. It is preferable to use such an amino resin in the case of using the treated CB because of its good affinity with the treated CB and the uniform dispersion of the CB.

As the amino resin used in the present invention, an amino resin initial reaction product having methane miscibility of 400% or less is preferable.

Methanol miscibility of the initial reaction product indicates the degree of polycondensation of the amino resin, and 2 g of the initial reaction product is dissolved in 5 g of methanol and stored at 25 ° C. to add water dropping to create a turbidity. The weight of the water and the initial reaction product The weight ratio is multiplied by 100.

The inorganic pigment used for this invention does not specifically limit a kind and a shape. For example, one or two or more selected from titanium oxide, iron oxide, zinc oxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, talc, clay, carbon black, etc. are used, and colorability is improved (dispersibility is improved in resin. In order to meet the necessity for such a material), it is preferable that the particle size is 5 탆 or less by treatment with a mill such as a ball mill, and more preferably 0.1 탆 or less. By using inorganic pigments, colored resin spherical fine particles may be concealable. When such colored resin spherical fine particles are used, for example, it is possible to color the cloth (or lower limb) so that the color of the cloth (or lower limb) does not come out or is inferior to other colors.

In the present invention, the amount of the inorganic pigment may be appropriately set so that the inorganic pigment contained in the colored resin spherical fine particles is 1-30%, preferably 5-20%, based on the total amount of the cured amino resin and the inorganic pigment. . This ratio may vary depending on the type of amino resin and the type of inorganic pigment, but is used in an amount of 0.9 to 27% of the inorganic pigment for the total amount of the amino resin and the inorganic pigment.

The inorganic pigment used in this invention may be surface-treated in order to improve the dispersibility to amino resin.

Alternatively, at least one of the dye and the organic pigment may be used as an auxiliary. In particular, if the CB is treated with a compound (A) having a functional group having a reactivity and / or affinity with a functional group present on the surface of the CB, the dispersibility of the initial reaction product of the amino compound and formaldehyde is good, and the colorability is excellent. Black resin spherical fine particles can be obtained.

The compound (A) is a compound having a functional group having a reactive functional group and / or an affinity which can easily react with a functional group (for example, -OH, -COOH, -C = 0, etc.) present on the surface of the CB. Can be used without specific limitations. Compound (A) is, for example, a monomer having at least one aziridine group, oxazoline group, N-hydroxyalkyl amido group, epoxy group, thioepoxy group, isocyanate group, hydroxyl group, amino group, imino group, or the like. A polymerizable monomer may be sufficient, and 1 or 2 or more polymerizable monomers may be polymerized according to a well-known procedure as needed. Specific examples of the compound (A) are polyethyleneimine having an average molecular weight of 300-100,000, polyethylene glycol glycidyl ether having an average molecular weight of 70-100,000, (poly) alkylene glycols having an average molecular weight of 200-10,000, and derivatives thereof.

And as a specific example of the electrical polyethylene glycol glycidyl ether, there is a compound of the following general formula (1).

(Where R is a hydrogen atom or at least one group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aryl group and an unsaturated aliphatic residue which may have a substituent, and n is an integer of 1-30.)

The emulsifier used in the present invention is preferably an emulsifier to make a protective colloid, and examples thereof include polyvinyl alcohol, polyvinyl pitolidon, carboxymethyl cellulose, alkali metal salts of polyacrylic acid, alkali metal salts of styrene-maleic acid copolymer, and the like. Among these, polyvinyl alcohol is particularly suitable. In the present invention, the emulsifier using an emulsifier may be added directly to the mixed system by adding a predetermined amount of an inorganic pigment into the amino resin, or an aqueous emulsifier is prepared separately, and a mixture of the amino resin and the inorganic pigment is added to the liquid. It can be carried out by stirring with a powerful shearing stirrer, for example a colloid mill, a dispersing mill, a homomixer, a homogenizer or the like.

The amino resin used in the above emulsification is preferably an initial reaction product of 400% or less of methanol miscibility (degree of degree of polycondensation), and more preferably an initial reaction product of 200% or less. As the methanol miscibility becomes smaller, the particle diameter becomes larger, and as the methanol miscibility increases, the particle diameter becomes smaller. When methanol miscibility exceeds 400%, affinity becomes too large and it is difficult to obtain monodisperse particle | grains. The degree of condensation of the initial reaction product of the amino resin can be controlled even by methanol miscibility as described above, but can also be managed by gel permeation chromatography (GPC), liquid chromatography (LC), acetone miscibility, and the like. Among these, it is good to manage with acetone miscibility from a viewpoint of operability, reproducibility, etc. Acetone miscibility refers to the degree of polycondensation of amino resins. It is a value obtained by multiplying the weight ratio of the initial reaction product by 100 to the weight of water required to dissolve 2 g of the initial reaction product in 5 g of acetone and to preserve water at 25 ° C. Acetone miscibility of the initial reaction product is preferably 50-500%, more preferably 100-300%. If the acetone miscibility exceeds 500%, it is difficult to obtain particles, and if it is less than 50%, it is difficult to become spherical fine particles.

The amount of the emulsifier added is preferably 1-30%, more preferably 2-10%, based on the amino resin.

The larger the amount of the emulsifier used, the smaller the particle size, and the smaller the amount used, the larger the particle size. If the added amount of the emulsifier is less than 1%, emulsification is impossible. If it exceeds 30%, there is a problem that it becomes difficult to separate the fine particles obtained by curing into single particles. In addition, the particle diameter becomes smaller as the stirring efficiency is increased, and the particle diameter becomes larger as the stirring efficiency is lowered. This is because the up and down of the stirring efficiency for the emulsification is related to the magnitude of the shearing force of the initial reaction product.

As such, the polycondensation ratio of the amino resin, the amount of the emulsifier, and the stirring efficiency can be appropriately synthesized with spherical and narrow particle size distribution and colored resin spherical fine particles having a target particle diameter. In the present invention, that the spherical fine particles of the colored resin has a spherical shape means that the particle diameter ratio (longer diameter / shorter diameter) obtained on the electron micrograph of 200 of the colored resin spherical fine particles has a range of 1.0-1.1.

Curing catalyzers used in the present invention are polycondensation catalysts of amino resins. For example, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid: carboxylic acids such as benzoic acid, phthalic acid, acetic acid, propionic acid and salicylic acid: ammonium salts such as ammonium chloride and ammonium phosphate: sulfonic acids such as benzene sulfonic acid and paratoluene sulfonic acid. Or two or more can be selected suitably, and can be used. The electrocuring catalyst is preferably 0.01-10% (0.05% when using CB treated), more preferably, based on the solid content of the uncured amino resin emulsion colored with inorganic pigments (except pigments). 0.2-5% (0.2-2% with treated CB). If the amount of the curing catalyst is excessively large, the emulsion state is broken down and aggregates are formed. If the amount of the curing catalyst is too small, the curing is insufficient, and it is not preferable such that a long time is required for curing.

Curing is carried out, for example, at a temperature in the range of 10-200 ° C. for at least 1 hour, and then at a temperature in the range of 40-200 ° C. under normal pressure or pressure, and the cured product is acetone, methanol, methyl ethyl ketone, dioxane, dimethyl. When it becomes insoluble by formamide etc., it is set as hardening end.

After completion of the curing reaction, the colored resin spherical fine particles can be separated according to a known method. For example, various separation methods such as natural sedimentation, centrifugal sedimentation, decantation, separation by filtration, and the like. You can freely choose. Further, the colored resin spherical fine particles obtained by separation are water and various organic solvents, for example, nonpolar solvents such as toluene and xylene: polar solvents such as methyl ethyl ketone, methanol, ethanol, isopropyl alcohol, dimethyl formamide and tetrahydrofuran. And it can obtain as a paste or a dispersion by disperse | distributing in these mixed solvents. After the separation operation, the colored resin spherical fine particles can be dried by conventionally known methods such as natural drying, dark-dark drying and hot air drying. Since the heat resistance, water resistance, solvent resistance, etc. of the target colored resin spherical microparticles | fine-particles further improve by carrying out heat processing at the temperature of 100-200 degreeC after a drying operation, it is preferable to carry out such heat processing as needed.

However, if the drying step is performed at a relatively high temperature, the heat treatment is performed at the same time, and therefore, it is better not to perform the heat treatment at this time.

In order to solve the aggregation state of the colored resin spherical fine particles after drying, it can be pulverized by a mill such as a ball mill, a hammer mill, a jet mill, and the like to obtain fine powder of colored resin spherical fine particles.

It is of course also possible to disperse the colored resin spherical fine particles after the drying operation in a solvent to form a paste or a dispersion.

The colored resin spherical fine particles of the present invention may have, for example, an average particle diameter in the range of 0.1-50 占 퐉 when produced by polycondensation in an emulsified state, but may have an average particle diameter other than this range.

In the present invention, the polycondensation in the emulsified state indicates that the polycondensation is carried out in a state where the droplets are dispersed in the dispersion medium, and is not limited to the emulsion polymerization, and also includes suspension polymerization and the like.

The colored resin spherical microparticles | fine-particles of this invention and its manufacturing method have the following superiority compared with the conventional thing.

(1) The colored resin spherical fine particles of the present invention are excellent in all the excellent physical properties of amino resins, such as heat resistance, solvent resistance, chemical resistance, and durability.

(2) The colored resin spherical fine particles of the present invention have excellent affinity between plastics such as thermoplastic resins and thermosetting resins, natural rubbers, synthetic rubbers, printing inks and vehicle paints.

(3) Since the colored resin spherical fine particles of the present invention have excellent coloring power, true spherical shape, and narrow particle size distribution, the fluidity during processing in the mixed use with the molding resin is improved, and workability is improved. Further, by mixing the colored resin spherical fine particles having different colors and particle diameters arbitrarily, it can be variously colored in a fashion different from the conventional pigments.

④ According to the method for producing colored resin spherical fine particles of the present invention, all excellent physical properties, for example, heat resistance, chemical resistance, and durability of amino resins are not lost, they are spherical, narrow in particle size distribution, and uniformly dispersed in inorganic pigments. Thus, colored resin spherical fine particles excellent in colorability can be produced.

(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 by an industrially advantageous method within the range of 0.1-5 mu m.

EXAMPLE

Hereinafter, specific examples and comparative examples of the present invention are shown, but the present invention is not limited to the following examples.

Table 1 summarizes and summarizes the synthesis conditions of Example 1-6 and Comparative Example 1-4.

Example 1

Into a flask equipped with a stirrer, a reflux condenser and a thermometer, 150 g (0.8 mol) of benzoguanamine, 162 g (formaldehyde 2.0 mol) of formalin at 37% concentration, and 0.65 g of aqueous sodium carbonate solution at 10% concentration were added and stirred at 94-95 ° C. The reaction was carried out at a temperature of 5 hours to obtain an initial reaction product having a methanol miscibility of 60% and acetone miscibility of 250%. 20 g of titanium oxide (TA-100, manufactured by Fuji Titanium Co., Ltd.) was added to the initial reaction product, followed by stirring for 30 minutes to obtain an initial reaction product colored white with titanium oxide. Separately, 10.5 g of Kuraray poval 205 (polyvinyl alcohol partial hydrolyzate made by Kushiray Co., Ltd.) was dissolved in 145 g of mol, and the aqueous solution was heated to 90 ° C., followed by a homomixer. Kaiser M type) was stirred at 6000 rpm. The initial reaction product colored in white was added to the aqueous solution of Gurayrefobal under stirring to obtain a white emulsion. The emulsion was cooled to 40 DEG C, 4.5 g of dodecylbenzenesulfonic acid was added thereto, gradually warmed up, heated and stirred for 2 hours at 50 DEG C, 70 DEG C and 80 DEG C in order, and cured by polycondensation. A suspension of colored resin spherical fine particles was obtained.

Observation of this suspension under an optical microscope (600 times magnification) revealed that the suspension became spherical fine particles having a particle diameter of about 4 m. The colored resin spheroidal fine particles were separated by filtration, washed with water, dried at 100 ° C. for 1 hour, heated at 150 ° C. for 3 hours, and then lightly pulverized with a mortar to prepare a main body of colored white resin particles having a clear white color. Got it.

The colored resin spherical microparticles obtained in this way were observed by an electron microscope with 200 microparticles by a scanning electron microscope (type S-570 manufactured by Hitachi Seisakusho Co., Ltd.) and had a particle diameter ratio (long diameter / short diameter) of 1.05, which was not granulated. Since titanium could not be observed, it was found that almost all of the added titanium oxide was dispersed in the colored resin spherical fine particles.

The average particle diameter of this colored resin spherical fine particle was 4.25 micrometers, and the particle size distribution was very sharp.

Moreover, the coloring property, heat resistance, dispersibility, and water resistance of this colored resin spherical microparticles | fine-particles were investigated as follows. These colored resin spherical fine particles were white resin spherical fine particles excellent in colorability, heat resistance, dispersibility and water resistance. The results are shown in Table 2.

Colorability compared the color of the pigment used and the obtained colored resin fine particles in color order, and evaluated the coloring degree based on the following reference | standard.

(Circle): The color difference of an inorganic pigment individual and colored resin microparticles | fine-particles is 10% or less.

(Triangle | delta): The color difference of an inorganic pigment only and colored resin microparticles | fine-particles exceeds 10% but less than 20%.

X: The color difference of an inorganic pigment alone and colored resin microparticles | fine-particles is 20% or more.

Heat resistance was processed at 180 degreeC for 2 hours according to JIS K-5101 (16), the change of shape was investigated, and the following reference | standard evaluated.

(Circle): The difference between the particle diameter ratio measured after a heat resistance test and the particle diameter ratio of an untreated product is less than 10%.

X: The difference between the particle diameter ratio measured after the heat resistance test and the particle diameter ratio of the untreated product is 10% or more.

The dispersibility is sufficiently kneaded with 20 g of printed varnish and 5 g of colored resin fine particles in accordance with JIS K-5101 (7), and then traces of grooves corresponding to three times the average particle diameter of the powder with a grind meter. The following criteria evaluated.

Pass: There are less than 3 lines in the trace of the groove.

Failed: There are three or more lines in the trace of the groove.

In accordance with JIS K-1501 (12), about 0.5 g of colored resin fine particles were placed in a glass test tube, 10 ml of water was added thereto, heated to 95 ° C, and allowed to cool. The color of the supernatant was evaluated and evaluated according to the following criteria.

Colorless and transparent: Good resistance to water as there is no detachment of pigment from colored resin fine particles.

Whitening: Poor water resistance because pigment is separated from colored resin fine particles.

Pale black: Poor water resistance due to the detachment of pigments from colored resin particles.

Example 2-4 and Comparative Example 1-3

Colored resin spherical fine particles were obtained in the same manner as in Example 1 except that the resin concentration, the pigment concentration, the emulsifier amount, and the stirring speed were set in the conditions shown in Table 1.

The results are shown in Table 2.

Example 5

In Example 1, colored resin spherical fine particles were obtained in the same manner as in Example 1 except that 20 g of Fe ₃ O ₄ (Spinel type manufactured by Mitsubishi Kinzo Co., Ltd.) was used instead of titanium oxide. These colored resin spherical fine particles had an average particle diameter of 5.11 µm (Coulter counter value), and were black spherical particles having the same spherical shape as in Example 1 and excellent in colorability, heat resistance, dispersibility, and water resistance.

The results are shown in Table 2.

Example 6

In a flask equipped with a stirrer, a reflux condenser and a thermometer, 112 g (0.6 mol) of benzoguanamine, 25 g (0.2 mol) of melamine, 145 g of formalin (1.8 mol) with a concentration of 37% and 0.65 g of an aqueous sodium carbonate solution with a concentration of 10% The mixture was stirred for 6 hours at 94-95 ° C. while stirring to obtain an initial reaction product having 35% methanol miscibility and 150% acetone miscibility. 15 g of carbon black (MA 600, manufactured by Mitsubishi Chemical Co., Ltd.) was added to the initial reaction product, followed by stirring for 30 minutes to obtain an initial reaction product colored black with carbon black. Separately, after heating the solution obtained by dissolving 7.5 g of Kuraret foam 205 (polyvinyl alcohol partial hydrolysis mole), the product was heated to 90 ° C., followed by a homomixer (M Tokushu-Giga Co., Ltd. M). Agitation) at 6000 rpm. The initial reaction product colored in black was added to the solution of Gureparpo Water under stirring to obtain a black emulsion. The weaning solution was cooled to 40 ° C., 4.1 g of dodecylbenzenesulfonic acid was added thereto, and the temperature was gradually elevated. A suspension of colored resin spherical fine particles was obtained. The suspension was observed under an optical microscope (600 times magnification) to find that it contained spherical fine particles having a particle diameter of about 6 µm. The colored resin spherical fine particles were separated by filtration, washed with water, dried at 100 ° C. for 1 hour, heated at 150 ° C. for 5 hours, and lightly pulverized with a mortar to obtain powder of spherical fine particles having a clear black color.

When the spherical fine particles thus obtained were observed with a scanning electron microscope, almost spherical carbon black was added because the spherical fine particles having a particle diameter ratio (long diameter / short diameter) of 1.06 were not observed. It was found to be dispersed in the spherical fine particles. The particle diameter of the colored resin spherical fine particles was measured with a Coulter counter (TA-2 type manufactured by Coulter, Inc.). The average particle diameter was 5.87 µm, and the particle size distribution was extremely sharp.

Moreover, these colored resin spherical microparticles | fine-particles were black resin spherical microparticles | fine-particles excellent in coloring property, heat resistance, dispersibility, and water resistance.

The results are shown in Table 2.

[Comparative Example 4]

2 g of acrylic acid, 240 g of methyl methacrylate, 29 g of divinylbenzene, 50 g of styrene resin, 1 g of azobisisobutyronitrile, carbon black (MA 600 made by Mitsubishi Chemical Co., Ltd.) in a flask equipped with a stirrer, a reflux cooler and a thermometer. ) 25g was added, the mixture was sufficiently stirred and uniformly mixed to obtain a black solution. Separately, an aqueous solution obtained by dissolving 17.g of Kuraray FOAL 205 (polyvinyl alcohol partial hydrolyzate of BUGASHI Co., Ltd.) in 600 g of water was added to a nitrogen solution using a homomixer (M type manufactured by Tokushu Giga Co., Ltd.). It stirred at 6000 rpm in gas atmosphere. The black solution was added to the aqueous solution of Gurayrepobal under stirring, followed by polymerization for 5 hours while heating and stirring at 80 ° C. to obtain a cured resin suspension colored in black. When the suspension was observed with an optical microscope (600 times), it was found that the particle diameter contained about 6 µm of spherical fine particles. The cured resin was filtered off from the suspension, washed with water, dried at 100 ° C., and ground with a mortar to obtain powder of cured spherical fine particles having a black color.

The cured resin spherical fine particles thus obtained were spherical fine particles having a particle diameter ratio (long diameter / short diameter) of 112 when observed with a scanning electron microscope, and carbon black which had not been granulated was observed.

The particle diameter of the spherical fine particles of this resin was measured by a coulter counter, and the average particle diameter was 6.23 micrometers, and the particle size distribution was wide. Moreover, this resin spherical microparticle was poor in colorability, dispersibility, and water resistance.

The results are shown in Table 2. Table 1 shows the synthesis conditions of Example 1-6 and Comparative Example 1-4.

TABLE 1

(Note) Resin concentration: [Resin weight / (Pigment weight + Resin weight)] × 100

Pigment Concentration: [Pigment weight / (Pigment weight + Resin weight)] × 100

Emulsifier amount: [emulsifier weight / (emulsifier weight + resin weight)] × 100

TABLE 2

(Note 1) Ratio of resin cured product: [Resin cured weight / (resin cured weight-pigment weight)] x 100

Pigment Ratio: [Pigment Weight / (Resin Lightweight Weight + Pigment Weight)] × 100

As can be seen from Table 2, the colored resin spherical fine particles of the examples of the present invention were spherical and were excellent in colorability, dispersibility, water resistance and heat resistance. On the other hand, in Comparative Example 1, since the ratio of the pigment was too high, dispersibility and water resistance were bad, and in Comparative Example 2, the ratio of the pigment was too low, so the colorability was bad. In Comparative Example 3, spherical fine particles could not be obtained. This is because the polycondensation was not performed in the emulsion state. In the comparative example 4, since the acrylic resin hardened | cured material was used instead of amino resin curability, coloring property, spray acid resistance, water resistance, and heat resistance were all bad.

Next, although the Example and the comparative example at the time of using the carbon black processed as an inorganic pigment in this invention are shown, this invention is not limited to the following Example. First, it is an example in the case of processing carbon black.

Reference Example 1

Epomin sp., 100 parts by weight of MA-600 (Mitsubishi Chemical Co., Ltd.) as a CB and a molecular weight of 30,000 as a CB in a Labo Plasto mill (manufactured by Tokyo Seiki Seisakusho Co., Ltd.). 200 parts by weight of -300 (manufactured by Epomin SP-300 Co., Ltd.) was kneaded at a temperature of 100-200 ° C. for 20 minutes with stirring, followed by cooling to obtain a treated carbon black. This is called CB (1).

Reference Example 2

Instead of using 200 parts by weight of polyethyleneimine in Reference Example 1 except that 100 parts by weight of Denacol EX-171 (manufactured by Denacol EX-171 manufactured by Nagase Chemicals Co., Ltd.), which is a lauryl alcohol polyethylene glycol glycidyl ether having a molecular weight of 902, was used. Carbon black treated in the same manner as in Convenience Example 1 was obtained. This is called CB (2).

Reference Example 3

A carbon black treated in the same manner as in Reference Example 1 was obtained except that 100 parts by weight of Fiji 1000 (PEG 100: manufactured by Ganto Chemical Co., Ltd.) having an average molecular weight of 1,000 polyethylene glycol was used instead of 200 parts by weight of polyethyleneimine. . This is called CB (3).

In Table 3, the synthesis conditions of Example 7-17 and Comparative Examples 5 and 6 were put together and shown.

Example 7

In a 4-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 187 g (1.0 mol) of benzoguanamine, 25 g (0.2 mol) of melamine, 243 g of formalin (3.0 mol of formaldehyde) and a concentration of 10% 0.95 g of aqueous sodium carbonate solution (%) was added and reacted at a temperature of 94-95 ° C. for 3 hours and 30 minutes to obtain an initial reaction product having 60% methanol miscibility and 250% acetone miscibility.

67.1 g of CB (2) obtained in Reference Example 2 was added to the initial reaction product, followed by stirring for 30 minutes to obtain an initial reaction product colored black by CB.

In particular, after heating up an aqueous solution obtained by dissolving 1.59 g of KURALE FOLF 205 (polyvinyl alcohol partial hydrolyzate made by Kushiboshi Co., Ltd.) in 183 g of water and raising the temperature to 90 ° C., homomix (HW- made by Tokushu Giga Co., Ltd.) M)) was stirred at 6000 rpm. Under agitation, the initial reaction product colored in black was added to the aqueous solution of Gurere foaming to obtain a black emulsion.

After the emulsion was cooled to 40 ° C, 4.62 g of dodecylbenzenesulfonic acid was added thereto, and the temperature was gradually increased. A black resin fine particle suspension was obtained.

Observation of the suspension with an optical microscope (600 times magnification) revealed that the suspension was composed of spherical fine particles having a particle diameter of about 5 mu m. The black resin fine particles were separated from the suspension by filtration, washed with water, dried at 100 ° C. for 1 hour, heated at 150 ° C. for 5 hours, and gently pulverized with a mortar to obtain a fine black powder particle having a clear black color.

The cured resin fine particles thus obtained were observed with respect to 200 fine particles by scanning electron microscopy, and since the spherical spherical fine particles having a particle diameter ratio (long diameter / short diameter) of 1.04 were not observed, carbon black which had not been granulated was added. It was found that the particles were dispersed in almost black resin particles. The particle diameter of the black resin fine particles was measured by a Coulter counter, and the average particle diameter was 5.05 탆, and the grain distribution was also very sharp.

Further, when the resin fine particles were examined for colorability, dispersibility, water resistance and the like as described above, it was found that they were black resin spherical fine particles excellent in any physical properties.

The results are shown in Table 5.

Example 8-10

In Example 7, instead of CB (2), CB (1) and (3) obtained in Reference Examples 1 and 3 and untreated CB (previous MA-600) were used in the same manner as in Example 7 except that Black resin fine particles were obtained by the method.

The results are shown in Table 5.

[Examples 11-16 and Comparative Examples 5,6]

In Example 7, black resin fine particles were obtained in the same manner as in Example 7, except that the amount of CB added, emulsifier amount, methanol miscibility, and acetone miscibility were set as the conditions shown in Tables 3 and 4.

The results are shown in Tables 5 and 6.

Example 17

The black resin fine particles were obtained by the same method as Example 7 except having changed benzoguanamine into cyclohexane carboguanamine in Example 7.

The results are shown in Table 6. In addition, the evaluation criteria of the coloring property of the colored resin microparticles | fine-particles of Example 7-17 and Comparative Examples 5 and 6 are as follows.

(Circle): The color difference of an inorganic pigment individual and colored resin fine particles is 5% or less.

(Triangle | delta): The color difference of inorganic pigment alone and colored resin microparticles | fine-particles exceeds 5% but less than 10%.

X: The color difference of an inorganic pigment alone and colored resin microparticles | fine-particles is 10% or more.

Table 3 and Table 4 show the synthesis conditions of Examples 7-17 and Comparative Examples 5 and 6.

TABLE 3

(Note) Resin concentration: [Resin weight / (Pigment weight + Resin weight)] × 100

Pigment Concentration: [Pigment weight / (Pigment weight + Resin weight)] × 100

Emulsifier amount: [emulsifier weight / (emulsifier weight + resin weight)] × 100

TABLE 4

(Note) Resin concentration: [Resin weight / (Pigment weight + Resin weight)] × 100

Pigment Concentration: [Pigment weight / (Pigment weight + Resin weight)] × 100

Emulsifier amount: [emulsifier weight / (emulsifier weight + resin weight)] × 100

TABLE 5

(Note 1) Ratio of resin cured product: [Resin cured weight / (resin cured weight + pigment weight)] x 100

Pigment Ratio: [Pigment Weight / (Resin Lightweight Weight + Pigment Weight)] × 100

TABLE 6

(Note 1) Ratio of resin cured product: [Resin cured weight / (resin cured weight + pigment weight)] × 100

Pigment Ratio: [Pigment Weight / (Resin Lightweight Weight + Pigment Weight)] × 100

As can be seen from Tables 5 and 6, the colored resin fine particles of the examples of the present invention are the tough resin spherical fine particles excellent in colorability, dispersibility, water resistance and heat resistance, and have better colorability than the CB untreated product.

In Comparative Example 5, since the CB content was in the range of 1-30%, the average particle diameter and the particle diameter ratio were large, and the dispersibility was low.

In Comparative Example 6, the CB content was poor in the range of 1-30%, resulting in poor colorability.

Example 18

10 g of the black resin spherical fine particles obtained in Example 7, 4 g of calcium stearate, and 1000 g of polypropylene cylindrical pellets (K-1014 manufactured by Chisso Corp.) were mixed with a high-speed mixer, followed by an injection molding machine (SG 25 type made by Sumitomo Heavy Industries, Ltd.), Temperature of 250 ° C.) to form plates having a thickness of 2 mm, 4 mm, and 6 mm, respectively. All of the plates obtained were smooth and glossy on the surface, had uniform black without staining, and were excellent in chemical resistance, solvent resistance, and water resistance.

Example 19

Injection molding machine (Sumitomo Heavy Machinery Co., Ltd. SG 25) after mixing 10 g of the fine resin spherical fine particles obtained in Example 7, 4 g of calcium stearate, and 1000 g of polyethylene cylindrical ferrite (J-40 manufactured by Nippon Petrochemicals Co., Ltd.) with a high speed mixer. 2 mm, 4 mm, and 6 mm plates were molded to each other at a mold and a temperature of 200 ° C.). All of the obtained plates had a smooth and glossy surface, had a uniform uneven black color, and was excellent in chemical resistance, solvent resistance, and water resistance.

Example 20

10 g of the black resin spherical fine particles obtained in Example 7, 4 g of calcium stearate, and 1000 g of polystyrene cylindrical pellets (XH803 manufactured by Asahi Kasei Co., Ltd.) were mixed with a high-speed mixer, followed by an injection molding machine (Sumitomo Heavy Industries, Ltd. SG) 25 mm, a temperature of 220 ° C.), and formed plates of 2 mm, 4 mm, and 6 mm in thickness, respectively. The plates obtained were all smooth and glossy, had a uniform black color without staining, and were excellent in chemical resistance, solvent resistance, and water resistance.

Example 21

To the black resin spherical fine particles obtained in Example 7, acryl polyone (trade name "Arotane 207" non-volatile content 50% manufactured by Nippon Shokubai Co., Ltd.) was 30% (= [black resin spherical content) The particles were mixed and dispersed so as to be fine particles / (black resin spherical fine particles + acrylic polyol)] × 100). Even if a strong disperser such as a sand mill was not used, the dispersion state was good. Thus obtained solution was mixed with polyfunctional isocyanate (manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name Sumidur) at a weight ratio of 9 (liquid I): 1. The dispersion thus obtained was diluted with a thinner of ethyl toluene acetate = 1: 1 to a viscosity that can be air sprayed to obtain a paint composition.

The coating composition was coated on a polystyrene plate with an air spray and then forcedly dried at 60 ° C. for 30 minutes. The surface of the obtained test plate had no glossiness and almost no gritty feeling when touched with a finger. Moreover, both acid resistance, alkali resistance, solvent resistance, and water resistance were all candles.

Example 22

The amount of the black resin globular fine particles obtained in Example 7 was 30% (= [Black globular spherical microparticles / (black resin) Spherical fine particles + acrylic resin)] × 100). Even if a strong disperser such as a sand mill was not used, the dispersion state was good. The dispersion thus obtained was diluted with a thinner of toluene: ethyl acetate = 1: 1 to a viscosity capable of air spraying to obtain a paint composition. After coating the coating composition on the polystyrene plate with an air spray, the surface of the test plate obtained by forcibly drying for 30 minutes at 60 ° C. had no gloss stains and almost no gritty feeling even when touched by a finger.

Moreover, all the acid resistance alkali resistance, solvent resistance, and water resistance were also favorable.

Example 23

In the combination of 40 g of the black resin spherical fine particles obtained in Example 7 and 140 g of the combined varnish for offset flat ink, three rolls without a dispersant were kneaded. The black resin globular particles were very well dispersed in the varnish.

4 g of ink solvent, 0.2 g of 6% cobalt drier and 1.5 g of 6% manganese drier were added and kneaded to 100 g of the obtained dispersion slurry to obtain a black ink of a uniform slurry. The printed matter printed by the offset printing machine using this was excellent in blackness.

Claims (8)

The emulsified mixture of the amino resin and the inorganic pigment is emulsified, the polycondensation reaction is carried out in the emulsified state, and the cured amino resin and the inorganic pigment are integrated so that the pigment ratio is 1-30% by weight based on the total amount of the cured amino resin and the inorganic pigment. The manufacturing method of colored resin spherical fine particles containing the thing. The amino compound and formaldehyde of claim 1, wherein the amino resin is 40-100% by weight of at least one guanamine selected from the group consisting of benzoguanamine, cyclohexanecarboguamine and cyclohexenecarboguamine. A process for producing colored resin spherical fine particles, which is an initial reaction product and is treated with a compound having an inorganic pigment having carbon black and a functional group having a functional group reactive and / or affinity. The compound according to claim 2, wherein the compound having a functional group having a reactivity and / or affinity for a functional group of carbon black is represented by the following general formula (1), Polyethylene glycol glycidyl represented by (wherein R is a hydrogen atom or at least one group selected from the group of alkyl groups and unsaturated aliphatic residues having 1 to 20 carbon atoms and n may be an integer of 1-30). It is at least one selected from the group consisting of ether compounds and derivatives thereof. The method for producing colored resin spherical fine particles according to any one of claims 1 to 3, wherein an emulsifier is used in an amount of 1-30% by weight based on the amino resin. The cured amino resin and the inorganic pigment are integrated, and the ratio of the inorganic pigment to the total cured amino resin and the inorganic pigment is 1-30% by weight, and the cured amino resin is benzoguanamine, cyclohexanecarboguamine and cyclo At least one guanamine selected from the group consisting of hexenecarboguamine is a reaction product of an amino compound with formaldehyde, which accounts for 40-100% by weight, and the inorganic pigment is carbon black and its functional and reactive and / or affinity The manufacturing method of the colored resin spherical microparticles | fine-particles which are processed by the compound which has. The method for producing colored resin spherical fine particles according to claim 5, wherein the proportion of the inorganic pigment is 5-20% by weight based on the total amount of the cured amino resin and the inorganic pigment. The method for producing colored resin spherical fine particles according to claim 5, which has an average particle diameter in the range of 0.1-50 탆. The method for producing colored resin spherical fine particles according to any one of claims 5 to 7, having a particle diameter ratio (long diameter / short diameter) in the range of 1.0 to 1.1.