JPH0782385A - Resin particle - Google Patents

Abstract

PURPOSE:To obtain resin particles having desired particle sizes, a sharp particle size distribution, and improved transparency, blocking resistance, and ultraviolet- intercepting capability by reacting a monomer having an arom. condensed polycyclic hydrocarbon backbone with other monomers. CONSTITUTION:A polycarboxylic acid, a polyhydric alcohol, and at least 10mol % monomer having an arom. condensed polycyclic hydrocarbon backbone are reacted with each other to give a polyester resin having a glass transition temperature 40 deg.C 1) or higher, a number-average mol.wt. of 1,000-20,000, and an ionic group content of 20-1,000eq./ton. The resin is pulverized, classified, and heated in an air or liq. flow to the softening point or higher, giving resin particles having an average particle size (D) of 1-100mum, a content of particles with diameters of 0.5-2.0D of 80% or higher, and a coefficient of variation of 30% or lower.

Description

Detailed Description of the Invention

[0001]

The present invention relates to an additive for paints, a coating agent for papers, a coating material for films, an in-line coating material, a matting agent, an antiblocking material, a carrier for chromatography, a drug. The present invention relates to resin particles that have been extensively used as carrier materials, powder coating materials, gap adjusting materials, toners for electrophotography, cosmetics, and the like, and particularly to resin particles having an excellent ultraviolet shielding effect.

[0002]

2. Description of the Related Art Heretofore, resin particles produced by a "polymerization granulation method" can be exemplified as the resin particles used for such an application. The polymerization granulation method can be roughly classified into an emulsion polymerization method, a suspension polymerization method, a seed polymerization method, and a dispersion polymerization method. The emulsion polymerization method is to obtain resin particles by polymerizing in water in a micelle of a polymerizable monomer stabilized with a surfactant. In the emulsion polymerization method, particles having a sharp particle size distribution can be obtained. However, since the particle size is determined by the size of micelles that can stably exist, the particle size is about 0.01.
It is limited to the range of about 0.5 μm, and it is impossible to obtain particles having a particle size of about 1 μm or more. Further, since the surfactant, which is essential for the stabilization of the micelles, remains on the surface of the produced particles, the use range of the obtained resin particles is limited.

The suspension polymerization method is a method of polymerizing the polymerizable monomer in a suspension system obtained by mechanically stirring water and the polymerizable monomer to obtain particles. In the suspension polymerization method, it is difficult to obtain fine polymer particles having a uniform particle size distribution because the particle size depends on mechanical stirring. The particle size range of the particles obtained by the suspension polymerization method is about 10 μm or more. In the seed polymerization method, the particles obtained by another method are used as seed particles, and the seed particles are swollen with a solvent and a polymerizable monomer, and the particles are polymerized in the swollen seed particles. Is a method of growing seed particles largely. In the seed polymerization method, in principle, particles having a sharp particle size distribution can be obtained by selecting an appropriate seed particle. It can be controlled by the swelling ratio of the particles and the polymerizable monomer. In the seed polymerization method, particles obtained by the emulsion polymerization method, that is, vinyl polymer particles are used as the seed. It is difficult to swell vinyl polymer particles with a polymerizable monomer. The swelling ratio is the interaction between the polymer constituting the seed particles and the monomer used for swelling,
Also, it is determined by the balance with the interfacial tension of the swollen particles, and the limit is actually about 2 to 10 times.

That is, the swelling ratio cannot be extremely increased, and there is a natural limit to the particle size range in which the swelling ratio can be grown at one time. Since increasing the particle size by 10 times corresponds to increasing the volume by 1000 times, it is necessary to repeat seed polymerization in order to realize this in seed polymerization. The two-step swelling seed polymerization method is a method devised for increasing the swelling rate of seed particles. Two-stage swelling
In the depolymerization method, first, the seed particles are swollen with an oligomer or a poorly water-soluble low molecular weight substance (: swelling agent) or the like, and then swollen with a polymerizable monomer. By this method, the swelling rate of the seed particles can be increased several thousand times. However, since the swelling agent remains in the particles obtained by the two-step swelling seed polymerization method, a step of removing them is essential. The seed polymerization method and the two-step swelling seed polymerization method are excellent methods in the sense that micron-order resin particles having a sharp particle size distribution are prepared, but the above-mentioned problems have been encountered. This makes it difficult to industrialize the depolymerization method. In the dispersion polymerization method, a polymerizable monomer, an initiator, and a stabilizer are dissolved in an organic solvent, and polymerization is initiated to form a polymer that is insoluble in the organic solvent by using an aggregate of oligomers generated in the initial stage as a particle nucleus. −
Is a method of growing the particles. The dispersion polymerization method is an excellent method for the purpose of producing micron-ordered resin particles having a sharp particle size distribution, but it is difficult to produce a mass product because an organic solvent is used as a medium, and thus the resin particle industrial Cannot be established as an effective production method.

[0005]

As described above, the resin particles obtained by the emulsion polymerization method and the suspension polymerization method have a limited particle size range and a broad particle size distribution. . The resin particles obtained by the seed polymerization method and the dispersion polymerization method have a sharp particle size distribution, but are very expensive. Further, the above-mentioned "polymerization granulation method", that is, the resin particles produced by emulsion polymerization, suspension polymerization, seed polymerization, and dispersion polymerization are, as is obvious from the production method, a vinyl-based polymer. Limited to resin particles. Such vinyl polymers generally do not have absorption in the ultraviolet region and have a poor ultraviolet shielding effect. Further, it is not impossible to add an ultraviolet ray-shielding effect by adding an ultraviolet ray absorber or the like, but generally, the ultraviolet ray absorber easily bleeds, and the addition amount cannot be increased without limitation. Therefore, there is a limit to the ultraviolet blocking effect that can be obtained.

[0006]

In view of the above situation, the present inventors have an arbitrary particle size and a sharp particle size distribution,
In addition, as a result of intensive studies to realize resin particles having an excellent ultraviolet shielding effect, the following invention has been reached. That is, the present invention comprises a monomer having an ionic group in the range of 20 to 1000 eq./ton and having 10 mol% or more of all constituent components as an aromatic polycyclic condensed ring hydrocarbon as a skeleton. With a polyester resin of
Within a range of 100 μm, 80 wt% or more of all particles are present within a range of 0.5D to 2.0D, and a coefficient of variation is 20%.
The resin particles have the following characteristics.

The particles of the present invention are mainly composed of polyester resin. The polyester resin is preferably used in an amount of 50 wt% or more of the total resin component, more preferably 80 wt% or more, further 90 wt% or more, further 95 wt% or more, still more preferably 98 wt% or more. The polyester resin in the present invention is mainly composed of polyvalent carboxylic acids and polyvalent alcohols. Examples of the polyvalent carboxylic acids used for the polyester resin include: terephthalic acid, isophthalic acid, orthophthalic acid, 1,
5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, anthracene dipropionic acid, anthracene dicarboxylic acid, diphenic acid, sulfoterephthalic acid, 5
-Sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7dicarboxylic acid, 5 [4-sulfophenoxy] isophthalic acid, sulfoterephthalic acid, and / or aromatic dicarboxylic acids such as metal salts and ammonium salts thereof. Aromatic oxycarboxylic acids such as p-oxybenzoic acid and p- (hydroxyethoxy) benzoic acid, succinic acid, adipic acid, azelaic acid, sebacic acid,
Aliphatic dicarboxylic acids such as dodecanedicarboxylic acid, aliphatic unsaturated polycarboxylic acids such as fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, and aromatic unsaturated polycarboxylic acids such as phenylenediacrylic acid Carboxylic acids-Alicyclic dicarboxylic acids such as hexahydrophthalic acid and tetrahydrophthalic acid-Trivalent or higher polyvalent carboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be exemplified.

In the present invention, a part of the polycarboxylic acids may be used together with the monocarboxylic acids. Aromatic monocarboxylic acids are preferred as the monocarboxylic acids. Examples of the aromatic monocarboxylic acid include benzoic acid, chlorobenzoic acid, bromobenzoic acid, parahydroxybenzoic acid, naphthalenecarboxylic acid, anthracenecarboxylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, salicylic acid, thiosalicylic acid, phenyl. Acetic acid and lower alkyl esters thereof, sulfobenzoic acid monoammonium salt, sulfobenzoic acid monosodium salt, cyclohexylaminocarbonylbenzoic acid, n-dodecylaminocarbonylbenzoic acid, tert-butyl benzoic acid, tert-butylnaphthalenecarboxylic acid Etc. can be used, and especially
It is more preferred to use charbutyl benzoic acid.
The amount of the aromatic monocarboxylic acid used is 2 to the acid component.
25mol%, 5-20mol%, 8-16mo
The use of l% is more preferred. In the present invention, 5 mol% or more of such a polycarboxylic acid component can be used as an unsaturated aliphatic polycarboxylic acid. As the unsaturated polycarboxylic acid in the present invention, fumaric acid and maleic acid are preferably used, and fumaric acid is more preferably used. The use of unsaturated polycarboxylic acid is required to be 5 mol% or more with respect to the acid component.
50 mol% is preferable, and 30 to 50 mol% is more preferable.

Examples of polyhydric alcohols used in the polyester resin include aliphatic polyhydric alcohols, alicyclic polyhydric alcohols, aromatic polyhydric alcohols and the like. As the aliphatic polyhydric alcohols, ethylene glycol
, Propylene glycol, 1,3-propanedioe
2,3-butanediol, 1,4-butanediol
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol
, Dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, polyethylene glycol
Examples include aliphatic diols such as propylene, polypropylene glycol and polytetramethylene glycol, triols such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and tetraols. it can.

・ Alicyclic polyvalent alcohols are 1,4
-Cyclohexanediol, 1,4-cyclohexanedimethanol, spiroglycol, hydrogenated bisphenol A, ethylene oxide adduct and propylene oxide adduct of hydrogenated bisphenol A, tricyclodecanediol , Tricyclodecane dimethanol, and the like. .As the aromatic polyhydric alcohols, ethylene oxide addition of para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, and 1,4-phenylene glycol Examples thereof include bisphenol A, bisphenol A, ethylene oxide adduct of bisphenol A, and propylene oxide adduct. Further, as the polyester polyol, lactone type polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone can be exemplified. Further, like the carboxylic acids, monoalcohols such as aliphatic alcohols, aromatic alcohols and alicyclic alcohols can be used.

An essential requirement of the polyester resin of the present invention is to use a monomer having an aromatic polycyclic condensed ring hydrocarbon as a skeleton as an essential component. As the aromatic polycyclic condensed ring hydrocarbon, indene, naphthalene, fluorene, phenanthrene, anthracene, pyrene, chrysene, naphthacene, benzophenanthrone, dibenzophenanthrene,
2H-indene, 3H-fluorene, 1,4-dihydronaphthalene, etc. can be exemplified, and in the present invention, monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, and / or polycarboxylic acids derived from these skeletons are used. Carboxylic acid, monoalcohol, glycol, trio
It is possible to use polyhydric alcohol, tetraol, and / or polyalcohol having a higher content. In addition to such polycyclic fused ring hydrocarbon carboxylic acid and alcohol, other substituents may be present as long as they do not hinder polyester polymerization.

The monomer having an aromatic polycyclic fused ring hydrocarbon as a skeleton used in the present invention is preferably one having naphthalene or anthracene as a skeleton, and more preferable specific compound is 2,6- Examples include naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, naphthalene methanol, naphthalene dimethanol, anthracene dicarboxylic acid, anthracene dipropionic acid, anthracene carboxylic acid, anthracene methanol, and anthracene dimethanol. be able to. The amount of addition of the monomer having such an aromatic polycyclic condensed ring hydrocarbon as a skeleton is indispensable to be 1 mol% or more with respect to either one of the carboxylic acids constituting the polyester and the alcohol. Yes. Preferably 10 mol% or more, more preferably 30 mol% or more, and even more preferably 50 mol% or more,
Even more than 51mol%, still more 70mol%
The above uses are preferred. Further, it is preferable to add the anthracene skeleton monomer in an amount exceeding 10 mol%. If the amount added is less than this range, a sufficient ultraviolet absorbing effect may not be obtained.

In the present invention, in addition to these, a monocyclic hydrocarbon,
A heteromonocyclic compound and / or a monomer having a condensed heterocyclic compound as a skeleton can be used. Cyclohexene as the monomer skeleton Tonariuru monocyclic hydrocarbon,
Examples thereof include cyclohexadiene, cyclopentene, cyclopentadiene, cyclopentylidene, and the like. Examples of the heteromonocyclic compound that can serve as a skeleton of the monomer include furan, thiophene, pyrrole, 2H-pyrrole, 2-pyrroline, pyrrolidine, oxazole, isoxazole and thiazo-
, Isothiazole, imidazole, 2H-imidazole
2-imidazoline, imidazolidine, pyrazole,
3-pyrazoline, pyrazolidine, 1H-1,2,3-triazol, 2H-1,2,3-triazol, 2H-
1,2,4-triazole, furazan, 1H-tetrazole, 2H-pyran, 4H-pyran, 4H-thiine, pyridine, piperidine, 4H-1,4-oxazine, morpholine, 4H-1,4- Examples thereof include thiazine, pyridazine, pyrimidine, pyrazine, piperazine, 1,3,5-triazine and the like.

Examples of the condensed heterocyclic compound which can be the skeleton of the monomer include benzofuran, isobenzofuran, benzothiophene, indol 3H-indole, indoline, isoindole, benzoxazole, benzothiazole, 1H. -Indazole, benzimidazole, 2
H-chromene, 4H-chromencoumarone, isocumalone, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, dibenzofuran, carbazol, xanthene, acridine, phenanthridine, 1,10-phenanthroline, phenazine, phenoxazine, thianthrene. , Indolizine, 4H-quinolidine, quinuclidine, 1,8-naphthyridine, purine,
Examples thereof include pteridine.

The glass transition point of the polyester resin in the present invention is preferably 40 ° C. or higher, 45 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 70 ° C. or higher. If the glass transition point is lower than this, blocking tends to occur during handling or storage, and it may be difficult to handle the resulting powder. The number average molecular weight of the polyester resin of the present invention is preferably in the range of 1,000 to 20,000. Further, the range of 2000 or more and 5000 or less is preferable, and the range of 3000 or more and 4000 or less is more preferable. In the present invention, particles made of a crosslinked resin obtained by incorporating a vinyl-based monomer into a polyester resin and then polymerizing it may be used. In this case, it is preferable to use the polyester resin using the above-mentioned unsaturated aliphatic polycarboxylic acid.

The particles of the present invention have a volume average diameter D of 1 to 100.
It is essential that the thickness is in the range of 1 μm, preferably in the range of 1 to 50 μm, more preferably in the range of 2 to 25 μm, still further in the range of 2 to 15 μm, and still more preferably in the range of 2 to 9 μm. If the volume average diameter is less than this range, it becomes difficult to handle the particles, and if it is more than this range, the particles may be rough and the touch may be impaired. The particle size distribution of the particles of the present invention is such that particles having a particle size in the range of 0.5D to 2.0D are 8
It is essential to occupy 0 wt% or more, preferably 85
wt% or more, further 90 wt% or more, and even 95 wt%
It is preferable to occupy at least%. According to another expression, the particle diameter range occupied by 70 wt% or more is 0.6D-1.
A range of 8D is preferred, a range of 0.7D to 1.5D is more preferred, a range of 0.8D to 1.3D is even more preferred, and a range of 0.9D to 1.2D is even more preferred. In addition, it is essential that the coefficient of variation, which is the value obtained by dividing the standard deviation by the average value, is 30% or less, and preferably 20%.
% Or less, more preferably 15% or less, and even 1
It is preferably 0% or less. In the present invention, single or plural independent holes and / or through holes may be formed inside the particles. Dyes, chemicals, fragrances, etc. can be charged in the pores, and they can be used for adjusting the apparent specific gravity for preventing the particles from settling, for sequentially releasing the fragrance, and the like.

In the present invention, the ionic group is 20 to 10.
00eq. It is essential to contain the polyester resin in the range of / ton. As the ionic group, a sulfonic acid group, a carboxyl group, a sulfuric acid group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group or an ammonium salt thereof,
It is an anionic group such as a metal salt or a cationic group such as a primary to tertiary amine group, and preferably an alkali metal sulfonate group or an ammonium carboxylate group can be used. It is preferable that these ionic groups are contained in a form copolymerized with polyester or introduced into the polymer terminal.

As the polyvalent carboxylic acid containing a metal sulfonate copolymerizable with polyester, sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4
Examples thereof include sulfonaphthalene-2,7 dicarboxylic acid, 5 [4-sulfophenoxy] isophthalic acid, and / or salts thereof. Further, by using a metal salt of sulfobenzoic acid together, a metal sulfonate base can be introduced at the polymer terminal. Examples of the salt include ammonium ions, salts of Li, Na, K, Mg, Ca, Cu, Fe and the like, and particularly preferred are K salt and Na salt. The carboxyl group can be added to the polymer terminal by introducing a polyvalent carboxylic acid such as trimellitic acid into the system at the final stage of polymerization of polyester. Further, by neutralizing this with ammonia, sodium hydroxide or the like, the carboxylate group can be exchanged. The content of these ionic groups is 2 with respect to the polyester resin.
0-500 eq. / Ton is indispensable, and more preferably 50 to 200 eq. / Ton. The ionic group may be a combination of a sulfonate group and a carboxylate group, and the ratio of the carboxylate group is about 0.8 to 10.0 times the sulfonate group. It is preferable to combine the above.

Such particles can also be obtained by pulverizing and classifying a polyester resin and then heat-treating it in an air stream or in a liquid stream at a temperature not lower than its softening temperature. Preferably, it is industrially produced by the method described below. can do. When it contains an ionic group, the polyester resin of the present invention exhibits water dispersibility. Water dispersibility means a state generally called emulsion or colloidal dispersion. The ionic group dissociates in the aqueous medium and forms an electric double layer at the interface between the polyester resin and water. When the polyester resin is present as fine microparticles in the water system, an electrostatic repulsive force is generated between the microparticles due to the action of the electric double layer, and the microparticles are stably dispersed in the water system. The resin particles in the invention are produced, for example, by dispersing an ionic group-containing polyester resin in water to prepare a polyester emulsion (or polyester dispersion),
It can be obtained by slowly agglomerating water-dispersed polyester microparticles in a plasticized state.

The aqueous dispersion of the ionic group-containing polyester resin is prepared by mixing the ionic group-containing polyester resin and the water-soluble organic compound in advance and then adding water, and the ionic group-containing polyester resin, the water-soluble organic compound and water. Can be obtained by a method of mixing and heating all at once. At that time, a surfactant or the like can be used together. As the water-soluble organic compound, ethanol, isopropanol,
Butanol, ethylene glycol, propylene glycol
, Methyl cellosolve, ethyl cellosolve, butyl cellosolve, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane and the like can be used. The water-soluble organic compound is preferably one that can be removed by azeotropic distillation after the ionic group-containing polyester resin is dispersed in water.

The polyester particles thus obtained are substantially spherical, have a sharp particle size distribution, and are capable of high-temperature dispersion dyeing at high density. The polyester particles thus obtained have a volume average particle diameter D of 1 to 100.
It can be freely controlled in the range of μm (depending on the electrolyte concentration, temperature, and time), and the particle size distribution is 0.5D to 2.
Particles in the range of 0D occupy 80% by weight or more of the whole, a coefficient of variation of 30% or less is sharp, and a substantially spherical polyester having an average sphericity (minor axis / major axis) of 0.8 or more. Become particles. The specificity of the particles of the present invention with respect to the particles of vinyl polymer obtained by suspension polymerization or the like is exhibited not only in the variety of physical properties of the polyester resin but also in the shape and particle size distribution of such polyester particles. In general, suspension-polymerized particles have a broad particle size distribution and only a coefficient of variation of about 30% or more can be obtained.

Different kinds of aqueous dispersions can be incorporated into the polyester particles of the present invention during the particle growth process.
The heterogeneous water dispersion includes, for example, known organic and inorganic dyes and pigments such as phthalocyanine pigments, quinacridone pigments, azo pigments, lake pigments, benzidine pigments, anthraquinone pigments, carbon black, and the like. Talc, titanium oxide,
Alumina, silica, and other metal oxides, ferrite, chromium oxide, cobalt oxide, and other magnetic powders, other acrylics,
Examples thereof include styrene-based organic polymer particles and water-dispersible waxes. Further, since the polyester particles of the present invention ensure stable dispersibility at the time of completion of particle growth, dyeing by post-processing, surface treatment, etc. are easy, and known disperse dyes, vat dyes, basic dyes, acid dyes are known. It can be dyed at a high density with a reactive dye, a reactive disperse dye, or the like.

In the present invention, the polyester particles thus obtained are used as seed particles, and the polyester particles are dispersed in an aqueous medium and a vinyl monomer is used in an amount of 1 to 95% by weight of a polyester resin and a vinyl resin. Monomer-5-9
It is also possible to obtain crosslinked polyester resin particles by swelling so as to be 9% by weight, preferably 40 to 90% by weight of polyester resin and 10 to 60% by weight of vinyl monomer, and further polymerizing and crosslinking. As the vinyl-based monomer used in the present invention, monofunctional and / or polyfunctional monomers can be used. For example, alkyl (meth) acrylate having 1 to 10 carbon atoms in the alkyl group, (meth) acrylic. (Meth) acrylic acid esters such as methoxyethyl acrylate, hydroxyethyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, methyl vinyl ketone, phenyl vinyl Unsaturated ketones such as ketone and methyl isopropenyl ketone, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate vinyl butanoate, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether and the like. , Vinyl halides and vinylides , Acrylamide and its alkyl-substituted products, styrene, divinylbenzene, styrene alkyl-substituted products, styrene halogen-substituted products, allyl alcohol and its esters or ethers, acrolein, vinyl aldehydes such as methacrolein, acrylonitrile, Vinyl monomers such as methacrylonitrile and vinylidene cyanide, and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, fumaric acid, maleic acid and itaconic acid, and salts thereof, vinyl sulfonic acid, acrylic sulfonic acid, parastyrene sulfonic acid. Unsaturated hydrocarbon sulfonic acids and salts thereof, double bond-containing phosphoric acid esters and salts thereof, pyridine, vinylpyrrolidone, vinylimidazole, vinylcarbazol, dimethylaminoethyl (meth Acrylate - DOO, diethylaminoethyl (Metaakurire - DOO or the like can be used.
In addition to these, ring-opening polymerization type monomers such as siloxanes, lactones, lactams and epoxy compounds may be used in combination.

The reaction initiator is not particularly limited, and a known initiator may be used. For example, benzoylperoxide, parachlorobenzoylperoxide, 2,4-dichlorobenzoylperoxide, caprylylperoxide, laurylperoxide, acetylperoxide, methylethylketoneperoxide, cyclohexanoneperoxide, bis (1-hydroxycyclohexyl). Peroxide), hydroxyheptylperoxide, t-butylhydroperoxide, p-menthanperoxide, cumenehydro, 2,5-dimethylhexyl-2,5-dihydroper
Oxide, di-t-butylperoxide, dicumylperoxide, 2,5-dimethyl-2,5-di (per)
Oxybenzoate), t-butylperbenzoate,
t-butyl peracetate, t-butyl per octet
, T-butyl peroxy oxyisobutyrate, di-t-butyl di-per phthalate, organic peroxide initiators such as peroxysuccinic acid, azoisobutyl nitrile, disoxybenzoyl, phenylacetaldehyde, phenylpyroglucose, An initiator such as a pinaconic acid derivative can be used. As the reaction accelerator, cobalt-based, vanadium-based, manganese-based, tertiary amine-based, quaternary ammonium salt-based,
A reaction accelerator such as a mercaptan type can be used. The crosslinked resin particles thus obtained maintain the particle size distribution of the polyester seed particles, and particles having a particle size in the range of 0.5D to 2.0D account for 80% by weight or more of the entire particles. , Preferably 85% by weight
Or more, more preferably 90% by weight or more, even more preferably 95% by weight or more, and the coefficient of variation is 30%.
Or less, preferably 20% or less, more preferably 15%
It can be below, more preferably 10% or less, and even more preferably 7% or less.

The polyester resin constituting the resin particles in the present invention contains a monomer having an aromatic polycyclic condensed ring hydrocarbon as a skeleton as an essential component, and therefore has a particularly excellent ultraviolet ray shielding effect, and Since a component having an ultraviolet absorbing effect is contained in a copolymerized state, there is no problem such as bleeding. Also, since it is a polymer, it is highly safe. These are actions that are difficult to obtain with an ultraviolet absorber.

The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto.

【Example】

[Polymerization of polyester resin] In an autoclave equipped with a thermometer and a stirrer, 1,5-naphthalenedicarboxylic acid dimethyl ester 134 parts by weight, isophthalic acid dimethyl ester 39 parts by weight, 5-sodium sulfoisophthalate dimethyl ester 6 parts by weight of ester 68 parts by weight of ethylene glycol, 114 parts by weight of neopentyl glycol, and 0.1 part by weight of tetrabutoxytitanate were charged and heated at 120 to 220 ° C. for 120 minutes to carry out a transesterification reaction. It was Then, set the temperature of the reaction system to 180 ° C.
Then, 32 parts by weight of fumaric acid and 0.1 part by weight of tert-butyl catechol were added, and the reaction was continued at 200 ° C. for 60 minutes. Then, the temperature of the reaction system was raised to 220 to 240 ° C. 1-1
As a result of continuing the reaction at 0 mmHg for 60 minutes, a copolyester resin (A1) was obtained. The composition, glass transition temperature, acid value, molecular weight and sodium sulfonate group equivalent of the obtained copolyester resin (A1) are shown in Table 1. Shown in. NMR analysis for polyester composition, DS for glass transition temperature
C, acid value was titrated, molecular weight was determined by GPC, and sodium sulfonate group equivalent was determined by S. Thereafter, the raw materials were changed and the same polymerization was carried out. Polyester resin (A
2), (A3), (A6), (A7) and (A8) were obtained.

[0027]

[Table 1] In an autoclave equipped with a thermometer and a stirrer, 9-anthracenecarboxylic acid methyl ester 35 parts by weight terephthalic acid dimethyl ester 78 parts by weight isophthalic acid dimethyl ester 78 parts by weight 5-sodium sulfoisophthalic acid dimethyl ester 3 parts by weight Parts ethylene glycol 60 parts by weight, bisphenol A propylene oxide adduct (average molecular weight 400) 240 parts by weight, and tetrabutoxy titanate 0.1 parts by weight were charged and heated at 150 to 220 ° C. for 180 minutes. A transesterification reaction was performed. Next, the temperature of the reaction system is set to 220 to 2
After the temperature was raised to 40 ° C., the system pressure was gradually reduced to 10 mmHg after 30 minutes, and the reaction was continued for 60 minutes. After that, the atmosphere in the autoclave was replaced with nitrogen gas and the pressure was adjusted to atmospheric pressure. The temperature was kept at 200 ° C., 8 parts by weight of trimellitic anhydride was added, and the reaction was carried out for 60 minutes. A copolyester resin (A4) shown in was obtained. Then, the raw materials were changed and the same polymerization was carried out to obtain a polyester resin (A5).

Table 1. Medium AMC is 9-anthracene carboxylic acid ADC is 9,10-anthracene dipropionic acid NDC is 1,5-naphthalene dicarboxylic acid TPA is terephthalic acid IPA is isophthalic acid SIP is 5-sodium sulfoisophthalic acid FA is fumaric acid MA is maleic acid Acid TMA is trimellitic acid AM is 9-anthracene methanol EG is ethylene glycol NPG is neopentyl glycol BPP is propylene oxide adduct of bisphenol A (average molecular weight 400) Tg is glass transition temperature.

[Preparation of Polyester Aqueous Micro Dispersion] 200 parts by weight of polyester resin (A1) and 150 parts by weight of dioxane were dissolved at 80 ° C., and then 500 parts of water at 80 ° C. was added to give a particle diameter of about 0.1 μm. An aqueous microdispersion of a copolyester resin was obtained. Further, the obtained water-based microdispersion was placed in a distillation flask and distilled until the distillate temperature reached 100 ° C., and after cooling, water was added to obtain a polyester water microdispersion (B1) having a solid content concentration of 30%. . Similarly, polyester water fine dispersions (B2), (B3) and (B6) using polyester resins (A2), (A3) and (A6)
Got 100 parts of butanol was added to 200 parts of the polyester resin (A4), dissolved at 90 ° C, and then cooled to 80 ° C. Further, 1N aqueous ammonia solution was added so that the acid value of the polyester resin would be the same amount, and the temperature was kept at 80 ° C.
After stirring for 0 minutes, 500 parts of water at 80 ° C. was added to obtain an aqueous polyester dispersion. Further obtained water dispersion 10
00 parts was placed in a distillation flask and distilled until the distillate temperature reached 100 ° C. and then cooled, to finally obtain a solvent-free water dispersion of polyester (B4) having a solid content of 30%. Similarly, a fine water dispersion (B5) was obtained from the polyester resin (A5). Below, Table 2. Shown in.

[0030]

[Table 2]

[Preparation of Particles] 300 parts by weight of polyester water fine dispersion (B1) was charged into a four-necked 1 liter separable flask equipped with a thermometer, a condenser and a stirring blade, and the temperature was raised to 80 ° C. Then, 40 parts by weight of a 20% by weight aqueous solution of dimethylaminoethyl methacrylate was added over 60 minutes (0.2 mol / l), and the temperature was raised to 9
The temperature was raised to 5 ° C. and stirring was continued for 300 minutes. The conductivity in the system increased from about 1 mS to 25 mS, and the pH decreased from 10.8 to 6.7. From this, it was confirmed that the added dimethylaminoethyl methacrylate (DAM) was completely hydrolyzed after almost all to form a salt of dimethylaminoethanol and methacrylic acid. Dispersed particles having a particle size of submicron order, which existed in the polyester water microdispersion, grew as coalesced particles with the lapse of time. Polyester spherical particles (C1) shown in Table 1 were obtained. Table 3. Medium, average particle size, particle size distribution, coefficient of variation
It was measured using A2. The sphericity was measured by processing a scanning electron micrograph of the particles with an image processing device Image Analyzer V1 [manufactured by Toyobo Co., Ltd.].
Similarly, the raw materials and conditions are changed in the same manner as described below. To obtain polyester particles (C2) to (C6). The container was replaced with a stainless steel closed container of Dye Tester Mini Color [made by texam giken], and polyester particles (C
7) to (C12) were obtained. It is understood that the particle size can be controlled by the DAM concentration and the temperature. Table 3. Shown in.

[0032]

[Table 3]

[Preparation of Crosslinked Particles] Polyester particles (C
Dilute the water dispersion of 1) with deionized water to adjust the solid content to 5
% To prepare an aqueous dispersion of polyester particles. 1000 parts by weight of the polyester aqueous dispersion was placed in a separable flask and gently stirred, and 1 part by weight of sodium chloride,
Distilled styrene 45 in which 1% by weight of benzoyl peroxide was dissolved
After adding 5 parts by weight of divinylbenzene and stirring for 30 minutes, the temperature of the system was raised to 80 ° C. and the reaction was continued for 300 minutes. After cooling the system to room temperature, the obtained particles were dehydrated and washed with a suction funnel and vacuum dried to obtain crosslinked polyester particles (D1). The average particle size, particle size distribution, coefficient of variation, and sphericity of the obtained particles were measured by the same method. Similarly, crosslinked polyester particles (D2) and (D5) were obtained from the polyester particles (C2) and (C5). (Shown in Table 4.)

[0034]

[Table 4]

(Preparation of Aqueous Binder) Polyester resin (A7) 200 parts by weight, butanol 150 parts by weight 8 parts
After dissolving at 0 ° C., 500 parts of water at 80 ° C. was added to obtain a water / alcohol solution of a transparent copolyester resin. The resulting solution was placed in a distillation flask and distilled until the distillate temperature reached 100 ° C. After cooling, water was added to the polyester aqueous binder (E) having a solid content of 30%.
1) was obtained. (Preparation of solvent-based binder) Polyester resin (A8)
200 parts by weight was dissolved in 300 parts by weight of ethyl acetate to obtain a polyester solvent binder (E2).

(Preparation of In-Line Coat Film) Polyester particles (C3) were added to the water-based binder (E1) in an amount of 30 parts by weight with respect to 100 parts by weight of the resin in the binder, and the coat was coated. It was a liquid. The obtained coating liquid was applied to a uniaxially stretched polyester film stretched 3.5 times in the longitudinal direction at 95 ° C., and then introduced into a preheating zone heated to 95 ° C. to dry the water. Continuously, grip the clip with a heating zone of 100 ° C and stretch it 3.5 times in the width direction, and then perform a relaxation treatment of 5% in the width direction with a heating zone of 225 ° C for 10 seconds. It heat-processed and the in-line coat film (F3) was obtained. Similarly, in-line coat films (F4) and (F6) are formed from polyester particles (C4) and (C6), and in-line coat films (F1) and (F1) are formed from crosslinked polyester particles (D1), (D2) and (D5). F2) and (F5) were obtained. Further, (F10) was obtained using only the binder (E1).

(Preparation of Off-Line Coat Film) Solvent-based binder (E2) and crosslinked polyester particles (D1)
30 parts by weight per 100 parts by weight of resin in the binder.
It was added so as to be a part by weight to obtain a coating liquid. The obtained coating solution was coated with a film coater into a polyester film having a thickness of 50 μm to a thickness of 25 μm and dried in a dry oven to form an offline coat film (F
7) was obtained. Similarly, the following crosslinked polyester particles (D
2), (D5) to in-line coat film (F
8) and (F9) were obtained. Further, (F11) was obtained using only the binder (E2).

(UV Shielding Ratio) With respect to the above materials, the UV blocking ratio was determined by using Hitachi Spectrophotometer U-3210 type. The measurement wavelength is 320 to 400 nm as A region,
The region B was set to 290 to 320 nm, and the average value of each region was obtained. The results are shown in Table 5. Shown in. When the coating liquid containing the particles of the present invention is used, the ultraviolet ray shielding rate is high, and particularly in the A region and B
It can be seen that the area is almost completely shielded.
In comparison, in the case of no particles obtained from the polyester resin (A6) having no condensed ring, and in the uncoated film and the film coated only with the binder, the shielding ratio in the B region is high, but in the A region. Incomplete.

[0039]

[Table 5]

[0040]

Industrial Applicability As described above, the polyester particles of the present invention have an excellent ultraviolet shielding effect, and further have excellent properties that are highly compatible with polyester binders and polyester films. is there.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masanori Kobayashi 2-1-1 Katata, Otsu City, Shiga Toyobo Co., Ltd. (72) Inventor Yozo Yamada 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd.

Claims (1)

[Claims] 1. From a monomer having an ionic group in the range of 20 to 1000 eq./ton and having 10 mol% or more of all constituent components as an aromatic polycyclic condensed ring hydrocarbon skeleton. Of which the average particle diameter D is 1
To 100 μm, 80% by weight or more of all particles are present in the range of 0.5D to 2.0D, and the coefficient of variation is 30.
Resin particles characterized by being less than or equal to%.