JPH08208976A - Microbead containing fluorescent pigment and/or fluorescent dye - Google Patents

Abstract

PURPOSE: To obtain microbeads which contain a fluorescent pigment and/or a fluorescent dye and can form a coating film excellent in weatherability (especially light resistance), touch, wearing resistance, marring resistance colorability, durability, and appearance and to obtain a resin composition for coating which contains the microbeads as an essential component. CONSTITUTION: This microbeads comprise particles of a three-dimensionally crosslinked polyurethane polyurea which have an average particle diameter of 0.1-100μm and contain a fluorescent pigment and/or a fluorescent dye. They further contain an antioxidant and/or an ultraviolet absorber in an amount of 0.1-60wt.% based on the resin. These microbeads are used as an essential ingredient to produce a resin composition for coating.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a microbead containing a fluorescent pigment and / or a fluorescent dye, and a resin composition for coating material containing the microbead. More specifically, the present invention relates to a microbead which is a polyurethane polyurea particle having a three-dimensional crosslinked structure and comprising a fluorescent pigment and / or a fluorescent dye, and an antioxidant and / or an ultraviolet absorber, and A resin composition for paints, which contains microbeads as an essential component.

The coating resin composition of the present invention is
As a marking material or coated paper used for visually recognizable labels, emblems, stickers or striped tapes, or as a building material, in the field of paints and printing inks, and in the field of clothing. It has excellent weather resistance (especially light resistance), abrasion resistance, abrasion resistance and secondary processability, which is extremely practical for printing and forms a design coating film that also has visual and tactile properties. The present invention relates to a resin composition for paint.

[0003]

2. Description of the Related Art A resin composition for design paint using various microbeads has been known for a long time, that is, a resin composition for paint comprising various elastic or inelastic resin particles and a synthetic resin binder. The composition is well known and has been used as a coating material for imparting a design property.

However, conventional resin compositions for coatings using non-elastic resin particles are inferior in weather resistance, soft feeling (soft touch), scratch resistance, etc., while coating films using elastic resin particles are inferior. Then, although it is superior in terms of touch and scratch resistance to those of non-elastic resin particles, it also dissolves or swells in a solvent, and has durability (weathering resistance) in the outdoors under the light. Not enough was obtained.

In recent years, however, in order to improve these various drawbacks, for example, JP-A-48-51949, JP-A-62-67003, JP-A-62-149333 or JP-A-63-58610. It has been reported to use polyurethane polyurea particles formed by an interfacial polymerization reaction of polyisocyanate and polyamine as disclosed in Japanese Patent Publication No. 1993-242242.

However, in all of the particles obtained by such a method, the formation of the particles is carried out by the ureation reaction, and therefore, the formation of the outer wall of the particles is limited to the formation thereof. The particles have a hollow structure or a small pore (microvoid) structure.

In particular, such microvoided particles have many non-uniform holes, and therefore, when a coating film is formed in combination with a synthetic resin binder, scratch resistance or scratch resistance (with nails) It is difficult to make scratches when rubbed), and it tends to be inferior in strength.

It is known that these defects such as scratch resistance can be ameliorated by imparting strength to the synthetic resin binder itself to be combined with the elastic particles, and specific acrylic resins, polyester resins and melamine resins are known. , Phenol resin, epoxy resin, urethane resin, etc. are used.

However, the elastic particle-containing coating film using these resins as a binder component cannot improve both scratch resistance and soft feeling, and in order to exhibit such various performances, the binder itself. There is a so-called fatal drawback in that it is extremely limited in terms of the composition and the design of the paint, and cannot cope with the diversification and individualization of the design in various products.

At present, silica-based, wax-based, melamine / urea resins and the like are widely used as matting agents.
However, these matting agents generally have poor weather resistance, cracks occur on the surface after long-term exposure, and additives such as internal resins and UV absorbers decompose,
There is a problem that a chalking phenomenon is caused due to the protrusion on the resin surface.

In recent years, there has been an increasing demand for display items such as stickers and labels using fluorescent pigments and fluorescent dyes, painted items, clothing items, etc., centering on sports-related events, sporting goods, and outdoor exhibits. However, organic pigments, especially dye-based fluorescent pigments and fluorescent dyes, have poor weather resistance (particularly light resistance) and are said to lose their fluorescent properties, discolor, or fly (color disappears) within half a year to one year. However, even if these dyes and pigments are simply kneaded with a resin together with an antioxidant and / or an ultraviolet absorber, it is not easy to prevent discoloration or discoloration.

For this reason, conventionally, in a coating material using a fluorescent pigment or a fluorescent dye, an ultraviolet absorber and / or an antioxidant has been added to a coating resin to improve light resistance. However, UV absorbers and antioxidants generally have a problem of poor solubility in a resin composition, that is, a problem of compatibility with a resin, and if the amount of addition of them exceeds 5%, the resin composition becomes incompatible. Since it loses solubility and becomes cloudy and precipitates (choking) as a powder in the upper layer after resin curing, the amount added of these is limited, and a sufficient amount of UV absorber and antioxidant to obtain satisfactory weather resistance. It was difficult to add the agent.

Therefore, conventionally, after coating these coating resin compositions on an object, a UV absorber and / or an antioxidant as an overcoat on the coated surface of the coating resin composition in order to improve light resistance. A method of applying a clear layer composed of a resin composition containing an agent has been generally performed.

[0014]

Since the conventional resin particles do not have a sufficient three-dimensional crosslinked structure, they easily swell in a solvent and are not preferable in terms of weather resistance. Furthermore, since it has a hollow structure, it is also disadvantageous in terms of strength, which is important for scratch resistance, and in the end, the binder itself to be combined with such elastic particles is extremely limited. Also, as mentioned above, fluorescent pigments and fluorescent dyes, which are dye-based, have extremely weak light resistance, and there is a big problem that the fluorescence decreases, the color changes, or the color flies (the color disappears) in half a year to one year. Has been done.

Therefore, the problems to be solved by the present invention include a fluorescent pigment and / or a fluorescent dye, and have weather resistance (particularly light resistance), touch, abrasion resistance, scratch resistance, colorability, durability, and It is an object of the present invention to provide a microbead capable of forming a coating film having excellent visual feeling and a resin composition for coating material containing the microbead.

[0016]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies and studied with a focus on the problems to be solved by the invention as described above, and as a result, have sufficiently formed outer and inner walls of the particles. Moreover, a coating composition composed of specific polyurethane polyurea particles having a three-dimensional crosslinked structure and containing a fluorescent pigment and / or a fluorescent dye, and a binder resin,
In addition to being excellent in weather resistance, scratch resistance, durability and visual sensation, the resin composition for a coating material contains a metal material and its processed product, a plastic material and its processed product, wood and its processed product. The present invention has been completed by finding that various articles coated with leather, fibers, papers, etc. are extremely useful.

That is, the present invention is a microbead comprising polyurethane polyurea particles having a three-dimensional crosslinked structure and an average particle size of 0.1 to 100 μm, which is characterized by containing a fluorescent pigment and / or a fluorescent dye.

The present invention further comprises an antioxidant and / or an ultraviolet absorber, characterized in that it comprises a fluorescent pigment and / or a fluorescent dye, and has an average particle size of 0 with a three-dimensional crosslinked structure. Micro beads composed of polyurethane polyurea particles having a particle size of 1 to 100 μm, preferably
In particular, the microbeads are characterized by containing an antioxidant and / or an ultraviolet absorber in the range of 0.1% to 60% with respect to the resin weight part of the microbeads. The present invention also includes a coating resin composition containing these microbeads as an essential component.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a specific polyurethane polyurea particle having a three-dimensional cross-linking structure and containing a fluorescent pigment and / or a fluorescent dye, and an antioxidant and / or an ultraviolet absorber. Is an organic phase that is blended so as to be in excess with respect to the hydroxyl groups, and is capable of forming a three-dimensional crosslinked structure by the reaction, and an excess of isocyanate groups in the organic phase. It is obtained through an interfacial polymerization reaction with an equivalent amount of polyamine or less, and a urethanization reaction inside the particles. Furthermore, the particles have a specific initial elastic modulus of 50 to 500 kgf / cm ² . It is characterized by having film characteristics.

The polyurethane polyurea particles of the present invention are obtained from a polyisocyanate compound, a polyhydroxy compound and a polyamine compound. Any polyisocyanate compound known per se can be used. You can Typical examples thereof include tolylene diisocyanate, hydrogenated tolylene diisocyanate and diphenylmethane-4,4 '.
-Diisocyanate, hydrogenated diphenylmethane-4,4'-
Diisocyanate,

1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, 1,3-bis (α, α-dimethylisocyanate methyl) benzene, cyclohexyl-1,4 Aliphatic, aromatic or cycloaliphatic di- or triisocyanate monomers such as diisocyanates, oxadiazinetrione diisocyanates, isophorone diisocyanates or triphenylmethane diisocyanates;

Alternatively, various modified polyisocyanates such as tri- or higher functional polyisocyanurate type polyisocyanates or burette type polyisocyanates based on these various monomers;

Furthermore, at least one of the various monomers and modified polyisocyanates listed above and one of various polyhydroxy compounds such as polyhydric alcohol, polyester polyol, polycarbonate polyol, polybutadiene polyol or polypentadiene polyol. Examples thereof include urethane-modified polyisocyanate prepolymers having an isocyanate group at the end, which are obtained by the urethanization reaction with the above, and these may be used alone or in combination of two or more kinds.

Since the obtained polyurethane polyol urea particles (hereinafter, also referred to as polymer particles) are particularly excellent in toughness, the number average molecular weight of the polyisocyanate compound is in the range of 200 to 10,000. ,
It is desirable that it is within the range of 300 to 7,000, and more preferably within the range of 500 to 5,000.

In the above organic phase, the urethane-modified polyisocyanate compound obtained by the reaction of polycaprolactone polyester polyol and diisocyanate is contained in the total polyisocyanate compound in an amount of 10% by weight or more, preferably 20% by weight or more. If it is contained, the toughness of the polymer particles is further improved. In designing the polyisocyanate compound, an aliphatic and / or alicyclic isocyanate monomer is recommended especially when weather resistance and the like are taken into consideration.

On the other hand, the polyhydroxy compound as a component constituting the organic phase together with the polyisocyanate compound compensates for the lack of internal cross-linking due to the formation of the wall portion of the polymer particles, and further improves the mechanical strength of the particles. Although it is an extremely important component for improving the properties, any of those known per se can be used as the polyhydroxy compound.

Of these, only typical ones will be exemplified and they belong to any of the following groups. a) ethylene glycol, propylene glycol, 1,
3-propanediol, 1,4-butanediol, 1,3
-Butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-
Bis (hydroxytyl) cyclohexane, bisphenol A, hydrogenated bisphenol A,

Hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane,
Polyhydric alcohols such as 2,2,4-trimethyl-1,3-pentanediol, glycerin, hexanetriol, tris (2-hydroxyethyl) isocyanurate or pentaerythritol;

B) polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene tetramethylene glycol, polyoxypropylene tetramethylene glycol or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol;

C) by ring-opening polymerization of various polyhydric alcohols such as those listed above with ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether or allyl glycidyl ether. Modified polyether polyols obtained;

D) Polyester polyols obtained by cocondensation of at least one of the various polyhydric alcohols listed above with polyhydric carboxylic acids. The representative polycarboxylic acids mentioned here are succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid and citracone. acid,

Itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5
-Benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid.

E) by polycondensation reaction of at least one of the various polyhydric alcohols listed above with various lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone. The lactone-based polyester polyols obtained, or the lactone-modified polyester polyols obtained by the polycondensation reaction of the above-mentioned various polyhydric alcohols and polycarboxylic acids and the above-mentioned various lactones;

F) Bisphenol A type epoxy compound,
Hydrogenated bisphenol A type epoxy compound, monovalent and /
Epoxy modified polyester polyols obtained by using at least one of various epoxy compounds such as glycidyl ether of polyhydric alcohol or glycidyl ester of monobasic acid and / or polybasic acid at the time of preparing the polyester polyol. ; Furthermore,

G) polyester polyamide polyol,
Examples thereof include polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, and hydroxyl group-containing acrylic copolymer.

Of course, the polyhydroxy compounds shown in (a) to (g) may be used alone or in combination of two or more, but the number average molecular weight thereof is from 200 to 10. Within the range of 1,000, preferably 3
Within the range of 00 to 7,000, more preferably 500
It is preferably within the range of up to 5,000 for sufficient crosslinking inside the polymer particles.

In order to obtain tough polymer particles, it is preferable to use polyester polyol.
It is desirable to use lactone-based polyester polyols obtained by polycondensation reaction with lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone.

In the present invention, the ratio of the isocyanate group equivalent of the polyisocyanate compound to the hydroxyl group equivalent of the polyhydroxy compound is 1: 0.1 to 1: 0.9.
Of these components, preferably in the range of 1: 0.1 to 1: 0.8, more preferably in the range of 1: 0.1 to 1: 0.7. The composition ratio should be such that the mixture of both components themselves can be three-dimensionally crosslinked.

That is, when these mixtures are completely urethanized, it becomes a gel, and it is necessary to make the composition such that the fluidity cannot be obtained even by heating or diluting with a solvent.
The above two conditions in designing the organic phase are essential conditions for obtaining an internal crosslinked state that cannot be obtained only by the interfacial polymerization reaction by adding the polyamine compound described below, and are the basic requirements of the present invention. one of.

At this time, in order to reasonably and effectively effect the interfacial polymerization, an excess of isocyanate groups in the above-mentioned range is necessary, and such a range is set so that the outer wall of the particle is promptly formed. Is.

Further, in the present invention, since the urethanization reaction in the particles proceeds three-dimensionally, it is possible to improve the toughness and solvent resistance of the whole particles which have not been obtained conventionally. That is, in the design of the three-dimensional urethanization reaction inside the polymer particles, the polyisocyanate compound and / or polyhydroxy compound having a functionality of 3 or more is contained in the total amount of the polyisocyanate compound and the polyhydroxy compound contained in the organic phase. By containing 0.1 mol% or more, preferably 0.2 mol% or more, and more preferably 0.3 mol% or more, a good three-dimensional crosslinked state inside the particle can be obtained.

The polyisocyanate groups in the organic phase are consumed with the progress of the interfacial polymerization reaction with the polyamine described below, so that the equivalent ratio of the isocyanate groups and the hydroxyl groups in the polymer particles approaches, and the inside of the polymer particles The crosslinking density of the polyurethane polyurea further increases with the progress of the urethanization reaction, and various properties such as toughness and durability of the polyurethane polyurea particles used in the present invention are further improved.

In general, a fluorescent pigment is a powder of a fluorescent dye as a solid solution in a synthetic resin, which is completely different from ordinary organic synthetic pigments. Exceptionally, there are pigment-dye types such as ordinary organic pigments, but most of them are not practical at present. As the fluorescent pigment used in the present invention, any of these known and commonly used fluorescent pigments can be used.

Here, to give a representative specific example of the synthetic resin solid solution type, for example, brilliant
Brilliant sulfoflavine FF,
Fluorescent dyes such as Basic yellow HG (Basic yellow HG), Eosine, Rhodamine 6G, Rhodamine B, acrylic resin, vinyl chloride resin, alkyd resin, aromatic sphonamide resin,

A fluorescent dye is dyed or dissolved using urea resin, melamine resin, benzoguanamine resin, etc.,
The obtained colored lump resin is crushed, and FZ-2
000, FZ-5000, FZ-6000, FZ-30
40, FA-40, FA-200, FR-50, SB-
10 and the like (all manufactured by Shin Roihi Co., Ltd.) are typical.

Further, as a typical example of the fluorescent dye,
Water-soluble non-reactive type 5B-E, H10GF-FS (manufactured by Mitsubishi Kasei Hoechst Co., Ltd.), water-soluble reactive type CD
-BH, H-10GF-FS, 5GH (manufactured by Hodogaya Chemical Co., Ltd.), and as non-reactive kneading type, Macrolex (Macrolex), Fluor Red G (Fluor Red
G) (manufactured by Bayer Co., Ltd.), HF-G, HF-4G,
FL-7G, BlueS (Sumitomo Chemical Co., Ltd.), SF
-4G, SF-B, SF-G, Blue-FR (made by Nippon Kayaku Co., Ltd.) are mentioned.

Further, other organic pigments, inorganic pigments and extender pigments can be used in combination with the fluorescent pigment. Among them, if I mention only representative ones,
Examples of organic pigments include insoluble azo pigments such as benzine yellow, Hansa yellow or lake red 4R; soluble azo pigments such as lake red C, carmine 6B or bordeaux 10.

Copper phthalocyanine type such as phthalocyanine blue or phthalocyanine green; basic dyed lake such as rhodamine lake or methyl violet lake; acid dyed lake such as quinoline lake or fast sky blue; mordant dye type pigment such as alizarin lake; anthraquinone Vat dyes such as thioindigo or perinone; quinacridone pigments such as Shinkashared B; dioxazine pigments such as dioxazine violet; condensed azo pigments such as chromophtal;

As the inorganic pigment, chromate salts such as yellow lead, zinc chromate or molybdate orange; ferrocyan compounds such as dark blue; metal compounds such as titanium white, zinc white, mapico yellow, iron black, red iron oxide or chromium oxide green. Sulfides such as cadmium yellow, cadmium red or mercury sulfide; sulphates such as barium sulphate or lead sulphate; silicates such as calcium silicate or ultramarine.

Examples include carbonates such as calcium carbonate or magnesium carbonate; phosphates such as cobalt violet or manganese purple; metal powders such as aluminum, gold powder, silver powder or brass powder; or pearl pigments. Examples of extender pigments include precipitated barium sulfate, barium carbonate, flour, gypsum, alumina white, clay, silica, silica white, talc, calcium silicate or precipitated magnesium carbonate, and the like. Of course, carbon black which does not belong to both can be used.

As the antioxidant and the ultraviolet absorber, any of those known and commonly used can be used in the present invention.
Specific examples of the antioxidant include naphthylamine-based, diphenylamine-based, p-phenylenediamine-based and mixtures thereof, quinoline-based, hydroquinone derivatives, monophenol-based, bisphenol-based, trisphenol-based,
Examples thereof include polyphenol type, thiobisphenol type, hindered phenol type and phosphite type.

The ultraviolet absorber is sometimes called an ultraviolet inhibitor or a light stabilizer, and as an example, a salicylic acid derivative,
Benzophenone-based, benzotriazole-based, hindered amine-based light stabilizers and the like can be used. These antioxidants and ultraviolet absorbers are used together when the pigment is kneaded. Alternatively, the polyisocyanate compound and the polyhydroxy compound can be mixed in advance. The weather resistance can be improved by combining two or more kinds of antioxidants and ultraviolet absorbers during kneading and mixing.

There are no particular restrictions on the amount of the antioxidant or ultraviolet absorber added to the microbeads containing the antioxidant and / or ultraviolet absorber of the present invention. % -60%,
Although it can be contained in the microbeads, it is preferably 1% to 30%, more preferably 1% to 15%.

The resin composition for coatings, which contains microbeads containing the antioxidant and / or the ultraviolet absorber of the present invention as an essential component, is an ultraviolet absorber in an arbitrary amount required for obtaining light resistance. In addition, it has an advantage that an antioxidant can be contained in the microbeads and the chalking does not occur.

These pigments are mixed with one or more of the above-mentioned polyhydroxy compounds in advance and uniformly kneaded to be used as a mill base. If necessary, the pigment may be chemically kneaded before use or during kneading. Surface treatment, combining two or more kinds of pigments during kneading, or using additives such as pigment dispersants and color separation inhibitors commonly used in the paint industry and printing ink industry. it can.

The kneading is carried out by using a known and commonly used disperser such as a ball mill, a pebble mill, a sand mill, an attritor, a roll mill, a high speed impeller disperser or a high speed stone mill. It is also possible to adjust the viscosity of the kneading system by adding active organic solvents.

Suitable organic solvents are aromatic or aliphatic hydrocarbons, esters, ethers and ketones, among which benzene, toluene, xylene,
Cyclohexane, methylcyclohexane, diphenyl ether or mineral spirits are suitable.

The ratio of the resin to the pigment in the mill-base kneading step is 1 to 900 parts by weight, preferably 2 to 800 parts by weight, and particularly preferably 5 to 500 parts by weight, based on 100 parts by weight of the resin solid content. Is appropriate. In the case of dyes, it is 0.
A range of 001 to 20 parts by weight, preferably 0.01 to 5 parts by weight is suitable.

The mill base thus obtained and the polyhydroxy compound or polyisocyanate compound are blended as described above and uniformly mixed to obtain a hydrophobic organic phase (1). In the hydrophobic organic phase (1), The ratio of the pigment contained in the above is 0.1 part by weight with respect to 100 parts by weight of the total resin solid content.
5 to 200 parts by weight, preferably 1 to 150 parts by weight, and more preferably 2 to 100 parts by weight are suitable.

The hydrophobic organic phase (1) was finely dispersed in the aqueous phase (2), and the polyamine compound was added in an amount of 0.1 equivalent to 1 equivalent of excess isocyanate groups contained in the organic phase.
It is preferably from 0.3 to 1.
By adding so that the amount becomes 0 equivalent, more preferably at 0.4 to 0.9 equivalent, the urea reaction at the particle interface is performed, and the urethanization reaction is performed inside the polymer particles. Very strong, pigmented polyurethane polyurea particles are obtained.

Suitable polyamine compounds for use in the present invention are known and conventional diamines, polyamines or mixtures thereof. Among them, 1,2-ethylenediamine and bis-diamine are mentioned, of which only representative ones are mentioned. (3-aminopropyl) -amine, hydrazine, hydrazine-2-ethanol, bis- (2-methylaminoethyl) -methylamine, 1,4-diaminocyclohexane,

3-amino-1-methylaminopropane,
N-hydroxyethylethylenediamine, N-methyl-
Bis- (3-aminopropyl) -amine, tetraethylenediamine, hexamethylenediamine, 1-aminoethyl-1,2-ethylenediamine, bis- (N, N'-aminoethyl) -1,2-ethylenediamine, diethylenetriamine, tetra Ethylene pentamine, pentaethylene hexamine,

Phenylenediamine, toluylenediamine, 2,4,6-triaminotoluentrydihydrochloride, 1,3,8-triaminonaphthalene, isophoronediamine, xylylenediamine, hydrogenated xylylenediamine, 4,4 '. -Diaminodiphenylmethane or hydrogenation 4,
4'-diaminodiphenylmethane, or

Derivatives of these polyamine monomers may be mentioned, but from the viewpoint of weather resistance, aliphatic and / or
Alternatively, it is desirable to use an alicyclic amine. In the present invention, the organic phase dispersed in the aqueous phase is itself non-reactive, and the viscosity of this hydrophobic organic solvent is added as necessary to reduce the viscosity, and dispersed in the aqueous phase. It is possible to improve the sex. The amount of organic solvent is 5 in the total organic phase.
An amount of 0% by weight or less, preferably 40% by weight or less, and more preferably 30% by weight or less is suitable.

Suitable organic solvents are aromatic or aliphatic hydrocarbons, esters, ethers and ketones, among which benzene, toluene, xylene, cyclohexane, methylcyclohexane, diphenyl ether or Mineral spirits are suitable.

If necessary, these organic solvents may be distilled off during the formation of the polymer particles or after the formation of the polymer particles by a treatment such as heating or reduced pressure. The aqueous phase in which the organic phase is dispersed is polyvinyl alcohol, hydroxyalkyl cellulose, carboxyalkyl cellulose,
One or more kinds selected from various protective colloids such as gum arabic, polyacrylate, polyacrylamide, polyvinylpyrrolidone and ethylene-maleic anhydride copolymer are contained in an amount of 0.2 to 20% by weight.

The aqueous phase may contain 0.2 to 10% by weight of various nonionic, anionic or cationic surfactants. In the present invention,
The polymer particles are characterized in that they are positively urethane-reacted inside the polymer particles. However, the urethane-reaction reaction between a hydroxyl group and an isocyanate group is particularly based on an aliphatic or alicyclic isocyanate group. In this case, the rate tends to be slower than that of the urea reaction with an amino group.

Further, the reactivity between water and isocyanate is extremely slow as compared with the reactivity with hydroxyl group, and the permeation of water into the inside of particles can be neglected due to the isolation effect by the outer wall formed by the addition of the polyamine compound. The object of the present invention, which is to carry out the urethanization reaction in the particles, is tentatively achieved by raising the reaction temperature and then taking time.

However, cobalt naphthenate, zinc naphthenate, stannous chloride, stannic chloride, tetra-n-butyltin, tri-n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, Dimethyltin dichloride,

One or more of various organometallic catalysts such as dibutyltin diacetate, dibutyltin dilaurate, tin octenoate or potassium oleate are added to the hydrophobic organic phase in an amount of 5 to 10,000 ppm, preferably 10%. ~ 5,
By adding within the range of 000 ppm, tough crosslinked polymer particles are formed in an extremely short time. These organometallic catalysts promote the reaction between isocyanate groups and hydroxyl groups very effectively.

Adding the above-mentioned organometallic catalyst to the organic phase prior to water dispersion (fine dispersion) causes the viscosity of the organic phase to increase, resulting in dispersibility in the water phase. Is not practical, and the addition of the organometallic catalyst after the addition of the polyamine causes the outer wall of the polymer particles to be formed, so that the organometallic catalyst is It tends to be difficult to be incorporated into the polymer particles, and as a result, the effect of accelerating the urethanization reaction inside the polymer particles tends to be reduced, the timing for adding the organometallic catalyst is to add water for dispersing the organic phase to the aqueous phase. Most suitable is during the dispersing step, or between the dispersing step and the middle of the step of adding the polyamine.

The microbeads comprising polyurethane polyurea particles having a three-dimensional crosslinked structure, which contain the fluorescent pigment and / or the fluorescent dye of the present invention, have an average particle diameter of 0.1 to 100.
It can be obtained in the range of μm. The particle size to be sought depends on the use of the microbeads and is not particularly limited, but for paint resins, it is preferably 1 to 80 μm.
m, and more preferably 1 to 50 μm.

When the microbeads comprising the polyurethane polyurea particles of the present invention are used as a coating resin composition, the binder resin to be used together may basically be any one capable of forming a coating film. Of these, only typical ones are exemplified by polyurethane resin, acrylic resin, alkyd resin, polyester resin, melamine resin, urea resin, epoxy resin, polyamide resin, vinyl acetate resin, vinyl chloride. Resins and various synthetic resins such as fluorine resins;

In addition to various rubbers such as natural rubber and synthetic rubber, there are various natural polymer compounds such as cellulose, which can be used alone.
Combinations of two or more species may be used. It goes without saying that it is appropriate to use a resin having excellent weather resistance as the binder resin for the resin composition for coating material which requires weather resistance used in the present invention.

Then, as a method for preparing the coating composition,
It is recommended to use a method in which a binder resin whose particle size is adjusted in advance and polymer particles are blended. The mixing ratio of polyurethane polyurea particles and binder resin is
The solid content weight ratio of binder resin / polymer particles is 1/9
The range of 9 to 99/1 is suitable.

The coating composition of the present invention thus obtained is, if necessary, diluted with a solvent or water capable of diluting the binder resin among them, and then applied with a brush, a roll coater, a flow coater, or spray coating. Alternatively, various base materials can be coated by various known and commonly used coating methods such as dip coating.

That is, the composition of the present invention obtained as described above is, for example, ABS resin, AS resin, polyester resin, polyphenylene oxide resin, polyurethane resin, polycarbonate resin, polyamide resin (among others,
Nylon), various plastics such as PS resin, polypropylene resin, acrylic resin, vinyl chloride resin or epoxy resin, or synthetic fibers made of them.

Various metal materials such as steel plate, zinc iron plate, galvanized steel plate, tin plate, copper plate, aluminum plate or zinc plate; various woods such as rosewood, ebony, rosewood, teak, oak, sina, cherry tree or lauan Various types of paper such as fine paper, coated paper, kraft paper or roll paper;
Alternatively, it can be satisfactorily applied to various kinds of leather such as natural leather or synthetic leather such as urethane, nylon or vinyl chloride, and is useful in a very wide range of applications.

[0079]

EXAMPLES Next, the present invention will be described more concretely by reference examples, examples and comparative examples. In the following, all parts and% are based on weight unless otherwise specified.

The raw material components used will be described in advance. The polyisocyanate compound is as follows. Solid of "Bernock Y6-572-80T" (manufactured by Dainippon Ink and Chemicals, Inc., hexamethylene diisocyanate-adduct type polyisocyanate compound; number average molecular weight = 880, isocyanate group content = 10.4% in terms of solid content) Minutes were used.
It is abbreviated as I-1.

"Bernock DN-901S" (manufactured by Dainippon Ink and Chemicals, Inc., isocyanurate type polyisocyanate compound obtained using hexamethylene diisocyanate; isocyanate group content = 23.0)
%); Hereinafter, this is abbreviated as PI-2.

Further, a polycaprolactone polyester polyol having a hydroxyl value of 168.5, which is obtained by a polycondensation reaction of trimethylolpropane and ε-caprolactone, was also used, which is hereinafter abbreviated as PO-1.

The hydroxyl value obtained by the condensation reaction of hexamethoxymethylolmelamine with neopentylglycol, isophthalic acid and phthalic anhydride is 11
A triazine-based polyester polyol having a number average molecular weight of 1,500 and a number of 2.2 was used, which is hereinafter abbreviated as PO-2. Further, ethylenediamine was used as the polyamine. This is abbreviated as EDA.

(Reference Example 1) (Preparation Example of Polyurethane Polyurea Particles Containing Pigment) First, 27 parts of PO-1, "Shin-Leuhi Color FZ-6"
073 "(a fluorescent pigment manufactured by Shin Roihi Co., Ltd.) and 20 parts of toluene were mixed and dispersed in a sand grinder for 1 hour to obtain a red fluorescent pigment mill base. Hereinafter, this is abbreviated as MB-1.

Then, the PVA was added to a 1 liter flask.
-420K "559 parts of 0.18% aqueous solution, 25% E
5 parts of MB-1 prepared by charging 15 parts of DA aqueous solution and preliminarily prepared in another container at 20 ° C. with a homomixer at 7,000 to 7,500 rpm while stirring.
9.3 copies, PO-1 27 copies, PI-1 43 copies, PI
-85 parts of -2 and 42 parts of toluene, further 7 parts of Tinuvin 900 (manufactured by Ciba-Geigy, benzotriazole type) as an ultraviolet absorber, and Sanol LS- as an antioxidant.
A mixed organic phase consisting of 7 parts of 292 (manufactured by Sankyo Co., Ltd.) was added, 2.0 parts of DBTDL was further added, and the mixture was stirred for 1 minute to obtain a dispersion liquid.

Next, this dispersion was prepared in advance, and "PV
200 parts of 0.012% aqueous solution of "A-420K" and 2
Transfer to another flask charged with 4 parts of a 5% EDA aqueous solution while stirring with a paddle type stirring blade at 200 rpm.
After being kept at room temperature (about 25 ° C) for 2 hours, the temperature was raised to 50 ° C, the temperature was kept for 1 hour, and the temperature was kept at 80 ° C for 2 hours to continue the reaction. A suspension of polyurea particles was obtained. The average particle size of the obtained polymer particles was 29 μm. The particles did not swell or dissolve in acetone, and no outflow of the red pigment was observed even in acetone.

(Reference Example 2) (Preparation Example of Polyurethane Polyurea Particles Containing Pigment) 27 parts of PO-1 "Shin-Leuhi Color FZ-501"
2 "(fluorescent pigment manufactured by Shin Roihi Co., Ltd.) and 20 parts of toluene were mixed and dispersed for 1 hour with a sand grinder to obtain a green fluorescent pigment mill base.
Hereinafter, this is abbreviated as MB-2.

Then, the PVA was added to a 1 liter flask.
-420K "559 parts of 0.18% aqueous solution, 25% E
15 parts of a DA aqueous solution was charged, and while stirring at 20 ° C. using a homomixer at 7,000 to 7,500 rpm, 59.3 parts of MB-2 prepared in another container in advance, 27 copies of PO-1, 43 copies of PI-1, P
85 parts of I-2 and 42 parts of toluene, 7 parts of Tinuvin 900 (a benzotriazole type manufactured by Ciba-Geigy) as an ultraviolet absorber, and SANOL LS as an antioxidant.
-292 (manufactured by Sankyo Co., Ltd.) was added to the organic phase, 7 parts of DBTDL was further added, and the mixture was stirred for 1 minute to obtain a dispersion liquid.

Next, this dispersion was prepared in advance, and "PV
200 parts of 0.012% aqueous solution of "A-420K" and 2
The mixture was transferred to another flask charged with 4 parts of a 5% EDA aqueous solution while stirring at 200 rpm with a paddler type stirring blade. Hold at room temperature (about 25 ℃) for 2 hours, then at 50 ℃
The temperature was raised to 1 hour, and the temperature was maintained for 1 hour and then at 80 ° C. for 2 hours to continue the reaction, to obtain a suspension of the desired pigmented green polyurethane polyurea particles. The average particle size of the obtained polymer particles was 21 μm. The particles did not swell or dissolve in acetone, and no outflow of the green pigment was observed in acetone.

Reference Example 3 (Preparation Example of Polyurethane Polyurea Particles Containing Dye) Fluorescent Dye HF-4G (Sumitomo Chemical Co., Ltd.) 1.0
3 copies, 30 copies of PO-2, 73.8 copies of PI-1, PI
-29.2 parts, and a mixture of toluene 13.4 parts were prepared in advance by using a homomixer in 297.4 parts of water and 19 parts of a 3% "PVA-420K" aqueous solution.
While stirring at 15,000 rpm, add the organic phase,
Further, as a UV absorber, Tinuvin 1130 (manufactured by Ciba-Geigy, hydroxyl group-containing benzotriazole type) 3.5 parts,
As an antioxidant, 3.5 parts of Sanol LS-292 (manufactured by Sankyo Co., Ltd.) was mixed, and 0.1% of DBTDL was further added.
(Toluene solution) 1.3 parts was added and stirred for 3 minutes to obtain a dispersion liquid.

Then, this dispersion was added to another flask prepared in advance, 0.5 part of a 3% aqueous solution of "PVA-420K", 114.3 parts of water, and a 25% solution of EDA 1
1.76 parts was charged and the mixture was stirred and the dispersion was transferred.
After holding at room temperature (about 25 ° C) for 2 hours, the temperature was raised to 50 ° C, the temperature was kept for 1 hour, and the temperature was kept at 80 ° C for 2 hours to continue the reaction, and the red polyurethane polyurea particles were suspended. A suspension was obtained. The average particle size of the obtained polymer particles is 5μ.
It was m. These particles neither swell nor dissolve in acetone,
No red dye efflux was observed in acetone.

Reference Example 4 Preparation Example of Polyurethane Polyurea Particles Containing Dye Fluorescent dye "SF-G" (manufactured by Nippon Kayaku Co., Ltd.) 1.
8 copies, 30 copies of PO-2, 73.8 copies of PI-1, PI
-29.2 and a mixture of toluene 13.4 parts were prepared in advance by using a homomixer in 297.4 parts of water and 19 parts of a 3% "PVA-420K" aqueous solution.
While stirring at 15,000 rpm, add the organic phase,
Further, as a UV absorber, Tinuvin 1130 (manufactured by Ciba-Geigy, hydroxyl group-containing benzotriazole type) 3.5 parts,
As an antioxidant, 3.5 parts of Sanol LS-292 (manufactured by Sankyo Co., Ltd.) was mixed, and 0.1% of DBTDL was further added.
(Toluene solution) 1.3 parts was added and stirred for 3 minutes to obtain a dispersion liquid.

Next, this dispersion was added to another flask prepared in advance and 0.5% of a 3% aqueous solution of "PVA-420K" was added.
Parts, 114.3 parts water and 11.76% 25% solution of EDA.
And the mixture was stirred and the dispersion was transferred. After holding at room temperature (about 25 ° C) for 2 hours, the temperature was raised to 50 ° C, the temperature was kept for 1 hour, and the temperature was kept at 80 ° C for 2 hours to continue the reaction, and the red polyurethane polyurea particles were suspended. A suspension was obtained. The average particle size of the obtained polymer particles was 4 μm. The particles did not swell or dissolve in acetone, and no outflow of yellow dye was observed in acetone.

Examples 1 to 4 In the combinations shown in Table 1, 20 parts of polymer particles and 22.5 parts of binder resin were used.
And PWC (particle weight concentration)
Thus, various desired resin compositions for coatings were obtained in which the content was 50%. In the table, "D7-885" is a polyester polyol manufactured by Dainippon Ink and Chemicals, Inc., "DN-98".
0] is polyisocyanate manufactured by Dainippon Ink and Chemicals, Inc.

(Comparative Examples 1 to 4) In the combinations shown in Table 2, 2.8 parts of pigment and 22.5 parts of binder resin were uniformly mixed, and 0.17 parts of dye and binder were added. Resin 22.5 parts was mixed uniformly to obtain a resin composition for paint.

[0096]

[Table 1]

[0097]

[Table 2]

The coating resin compositions obtained in Examples and Comparative Examples were each coated on an ABS resin plate to give a dry film thickness of 50 μm.
It was applied so that it would be, and dried and cured at 60 ° C. for 30 minutes. Then, after leaving at room temperature for 1 week, the following coating film performances were evaluated. The results are shown in Table 3.

(Appearance) The specular gloss of 60 degrees was measured with a gloss meter, and the matte state of the coated surface was visually judged and evaluated as follows. ⊚: The gloss is 2 or less, and the coated surface is in a completely matte state. X: The gloss is 2 or more, and uneven gloss on the coated surface is recognized.

(Tactile sensation) It was judged by the degree of soft sensation by touching with a hand. ◎: Extremely soft ○: Quite soft X: Hard and rigid.

(Scratch resistance) 3 # 000 steel wool
The surface was rubbed with a surface pressure of 0 g / cm ^{2 and} the state of the coated surface was visually determined after 1 hour. ⊚: No trace is attached. ○: A slight mark is attached. X: Scratches remain clearly.

(Colorability) The fluorescent state of the coated surface was visually determined. ⊚: Bright fluorescent color. X: Dull color.

(Light resistance) The change in color tone of the coated surface over time was judged by the color difference from the initial color tone using a dew panel light control weather meter (manufactured by SUGA tester). Color difference: ΔE was measured. The larger the value, the larger the color change and the poorer the light resistance. The color fading was visually evaluated. ⊚: No change in color. ○: There is a slight change in color. X: There is a change in color.

Comparative Example 5 The coating resin composition used in Comparative Example 1 was coated on an ABS resin plate so that the dry film thickness was 50 μm, and dried and cured at 60 ° C. for 30 minutes,
Further, as a binder, "D7-885" (polyester polyol manufactured by Dainippon Ink and Chemicals, Inc.) 18.
1 part, "DN-980" (polyisocyanate manufactured by Dainippon Ink and Chemicals, Inc.) 7.4 parts, UV absorber TINUVIN 900 (manufactured by Ciba Geigy, benzotriazole type) 0.25 part, antioxidant Sanol LS -292 (manufactured by Sankyo Co., Ltd.) of 0.25 part of a clear paint was applied so that the film thickness would be 50 μm. After drying and curing at 60 ° C. for 30 minutes, it was left at room temperature for 1 week to evaluate the coating film performance. The results are shown in Table 3.

[0105]

[Table 3]

In Comparative Example 5, according to the conventional coating method,
Although an overcoated product was prepared and its weather resistance was examined, it is understood that the single coating of the present invention exhibits more preferable coating performance, although the coating is performed twice.

[0107]

INDUSTRIAL APPLICABILITY The present invention is a fluorescent pigment and / or a fluorescent pigment which is excellent in light resistance (weather resistance) and can form a coating film having excellent wear resistance, scratch resistance, colorability, durability, and visual feeling. It is possible to provide a microbead containing a dye and having an average particle diameter of 0.1 to 100 μm, and a resin composition for coating including the microbead.

Claims (4)

[Claims] 1. An average particle size of 0.3, having a three-dimensional crosslinked structure, characterized by containing a fluorescent pigment and / or a fluorescent dye.
Microbeads consisting of polyurethane polyurea particles of 1-100 μm. 2. The microbeads according to claim 1, further comprising an antioxidant and / or an ultraviolet absorber. 3. An antioxidant and / or an ultraviolet absorber is used in an amount of 0.1% to 60% with respect to the resin weight part of the microbeads.
The microbeads according to claim 2, wherein the microbeads are contained in the range of. 4. A resin composition for coating, which comprises the microbeads according to any one of claims 1 to 3 as an essential constituent component.