WO1993010043A1 - Fine particule composite spherique, sa production et composition polyester la contenant - Google Patents

Fine particule composite spherique, sa production et composition polyester la contenant Download PDF

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Publication number
WO1993010043A1
WO1993010043A1 PCT/JP1992/001494 JP9201494W WO9310043A1 WO 1993010043 A1 WO1993010043 A1 WO 1993010043A1 JP 9201494 W JP9201494 W JP 9201494W WO 9310043 A1 WO9310043 A1 WO 9310043A1
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Prior art keywords
fine particles
spherical fine
suspension
alcohol
metal
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PCT/JP1992/001494
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English (en)
Japanese (ja)
Inventor
Mitsuo Takeda
Yasuhiro Sakai
Shigehumi Kuramoto
Saburo Nakahara
Tadahiro Yoneda
Hideki Oishi
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Publication of WO1993010043A1 publication Critical patent/WO1993010043A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/146—After-treatment of sols
    • C01B33/149—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds

Definitions

  • the present invention uses amorphous silica as a main constituent material and has excellent affinity and dispersibility for various resins, rubbers, and the like.
  • the present invention relates to a composite spherical fine particle which is not easily aggregated by itself, a method for producing the same, and a polyester composition having improved slipperiness and abrasion resistance by blending an appropriate amount of the composite spherical fine particle.
  • BACKGROUND ART It is well known that inorganic fine particles and organic fine particles are blended as a modifier / filler with various resins and rubbers, and the resin and rubber compositions thus obtained can be used as films and sheets. It is widely used as a fiber, etc.
  • the present applicant has proposed a group consisting of silica fine particles and a polyester resin.
  • a method for forming uniform irregularities on the film surface when the film is formed by using spheres of fine particles with a sharp particle size distribution was proposed earlier (Japanese Patent Application Laid-Open No. 62-207356). No. Gazette etc.).
  • void-like defects are easily formed between the fine particles and the resin, and there is a problem that the fine particles fall off to generate scratches and shavings on the film surface.
  • the applicant of the present invention has proposed a silica-glycol composite fine particle having a spheroidized and sharp particle size distribution.
  • the method of modifying the compound by incorporating it into the material has also been previously proposed (JP-A-63-183934, JP-A-63-182204, etc.).
  • JP-A-63-183934, JP-A-63-182204, etc. JP-A-63-183934, JP-A-63-182204, etc.
  • these surface-treated silica fine particles have poor monodispersibility in the polyester resin and cause partial aggregation, or the adhesion between the surface-treated material and the silica fine particles is poor, and void formation may occur.
  • the intended purpose of suppression is not always effective.
  • a resin composition containing fine particles is exposed to a high temperature condition of, for example, 200 ° C. or more for kneading in a manufacturing process until it is processed into various molded articles, and is further extruded, stretched, etc. Strong stress is applied in the process. Therefore, even under such severe conditions, the proper structure and composition of the fine particles are stable, and the fine particles do not aggregate, and the affinity and adhesion between the fine particles and the resin are maintained well. It is considered that the original characteristics of the fine particles such as the average particle size, particle size distribution, shape, and refractive index of the fine particles are reflected in the function of the final molded product. Under the circumstance in which simply specifying the properties and composition of the raw material microparticles before forming the composition does not necessarily reflect the expected effects in the composition, the causal relationship between them is clarified, and effective improvement measures are taken. It is strongly desired to establish.
  • the present invention has been made in view of the above-mentioned circumstances, and has as its object the advantage that it is hard to aggregate itself and has excellent affinity for various resins and rubbers (hereinafter referred to as “resin”). In addition to exhibiting dispersibility, it has excellent stability that does not change even when subjected to strong stress under high temperature conditions, so that it can maximize the reforming effect such as void suppression
  • An object of the present invention is to provide a spherical fine particle and a method for producing the same.
  • composition of the particles is at least amorphous silica, oxides and Z or hydroxides of metals whose electronegativity of ions is less than 15.6.
  • the (water) oxide is localized on the surface of the fine particles, and the ratio of the (water) oxide of the metal in the fine particles is 0.01 to 20% by weight in terms of metal, and the ratio of the alcohol is The gist exists where it is 1-30% by weight.
  • metals constituting (hydr) oxides are, for the reasons described later, particularly those having an electronegativity of ions in the range of 8.0 or more and less than 15.6, especially Al, T i, Zr, Zn, Fe and Ce are preferred, and A1 is particularly preferred.
  • the (hydr) oxide of the metal may be either crystallographically amorphous or crystalline, but is preferably crystalline such as boehmite for the reasons described below. .
  • the composite spherical fine particles are not particularly limited in terms of particle diameter, particle size distribution, and the like, but those having a uniform particle size distribution are preferred for the reasons described below. % Or less is preferred. Further, the average particle diameter is preferably in the range of 0.05 to 10 jm, particularly preferably in the range of 0.1 to 5 Aim.
  • a suspension of spherical fine particles made of amorphous silica is mixed with a sol of a (hydr) oxide of a metal having an ionegativity of less than 15.6, Is a method of heating in the range of 100 to 250 ° C in the presence of two or more alcohols,
  • a (water) oxide sol of a metal and one or more alcohols (Y) which are the same or different from the above alcohols (X) in the range of 10 o to 250 ° cay
  • Siri-force-alcohol composite spherical fine particles in which one or two or more types of alcohols are bonded to spherical fine particles made of amorphous silica, the alcohol mainly containing at least one alcohol among the above-mentioned alcohols Mixing a suspension dispersed and contained in a neutral solvent with a metal (hydr) oxide sol having an electronegativity of ion of less than 15.6,
  • the composition obtained by blending the composite spherical fine particles with 0.0005 to 10% by weight in the polyester composition has a regrettable effect of the fine particles without causing defects such as voids. It gives a good polyester-based sheet, film, fiber, etc. with good slipperiness and abrasion resistance.
  • BEST MODE FOR CARRYING OUT THE INVENTION In the composite spherical fine particles of the present invention, as described above, a metal (hydr) oxide having an electronegativity of ions lower than 15.6 is localized on the surface of the spherical fine particles. Together with the alcohol.
  • the affinity of the fine particles with various resins and the like is increased, and the adhesive force with the resin and the like is increased. Has the effect of improving uniformity in resin and the like.
  • Alcohol in the fine particle manufacturing process To provide composite spherical fine particles that suppress aggregation and have sufficiently enhanced adhesion between metal (water) oxide and amorphous silica, and have no mechanical cohesion per se and excellent mechanical stability.
  • the fine particles themselves are not agglomerated, and can be easily and uniformly dispersed in a resin or the like as a powder or a dispersion. It is presumed to be due to the alcohol present on the surface including the inner surface of the pores, but it has been found that fine particles are prevented from adhering to each other to cause secondary aggregation, and in the case of a dispersion, the dispersion stability is high. In addition to the above, two effects are exhibited, such as further improving dispersibility in resin and the like.
  • the composite spherical fine particles have the characteristic of being a three-component composite as described above, the structural characteristic that metal (hydroxide) is localized on the surface, and the structural characteristic of being spherical.
  • metal (aqueous) oxides and alcohols each exert their respective effects, and only when the above characteristics and the effects of these components are combined, The effect such as dispersibility is maximized.
  • the metal (hydr) oxide localized on the surface of the spherical fine particles is strongly adhered to the surface of the particles, and is exposed to a considerable high temperature or subjected to a strong external force in a kneading process with a resin or the like. Even if it does, it does not easily fall off the surface of the fine particles, and its excellent modifying effect can be reflected as effectively as possible in the quality of the final product.
  • Amorphous silica which is one component of the composite spherical fine particles according to the present invention, is mainly composed of a three-dimensional network in which a silicon atom is mainly bonded to an oxygen atom (_Si-0-). It is a silicon-containing oxygen compound that is crystallographically amorphous and constitutes a network. Note that a metal element other than silicon as a main component may be partially incorporated in the amorphous network. At that time, if the ratio to silicon atoms is in the range of 0.2 or less in atomic ratio, it is included in the amorphous silicon force according to the present invention.
  • a metal having an electronegativity of less than 15.6 preferably 8.0 or more and less than 15.6 'is selected because of its high affinity for resins such as polyester.
  • resins such as polyester.
  • Metal (hydr) oxides with an electronegativity of 15.6 or more have insufficient affinity with the above resins.
  • the electronegativity (X i) of the metal ion in the present invention is defined by the following equation.
  • Specific examples of the metal having an electronegativity of an ion of less than 15.6 include alkaline metals such as Na and K, alkaline earth metals such as Mg and Ca, Ti, Zr, and Zn. And transition metals such as Al and rare earth metals such as Ce and La. However, from the viewpoint that they do not adversely affect the stability of the composite spherical fine particles and the matrix resin, they are particularly 8.0. As described above, a metal having an electronegativity of less than 15.6 is preferred.
  • (hydr) oxides of Al, Ti, Zr, Zn, Fe, and Ce have the effect of remarkably improving the dispersibility of the obtained composite spherical fine particles and the affinity with the resin.
  • A1 and its (hydr) oxide are the most preferred in terms of cost, action, availability, and the like.
  • the metal (hydr) oxide may be either crystallographically amorphous or crystalline.
  • the amorphous silica and the metal (hydr) oxide in the composite spherical fine particles according to the present invention may be used.
  • a crystalline material such as boehmite is particularly preferable in that it has excellent adhesion to the substrate.
  • the content of the (hydr) oxide of the above metal must be in the range of 0.01 to 20% by weight in terms of metal in terms of the ratio occupied in the composite spherical fine particles, and the content is insufficient.
  • the content is too large, the effect of modification by the composite is not sufficiently exerted.
  • the content is too large, aggregation tends to occur in the composite process.
  • a more preferable content is 0 in terms of metal.
  • the range is from 0.05 to 10% by weight.
  • Fine particles in which the metal (water) oxide is localized on the surface of the fine particles means that the concentration distribution of the metal (water) oxide is continuous from the center of the fine particles toward the surface. It means that the fine particles are gradually or discontinuously high on the surface.
  • the content of metal in the surface layer having a ratio of the thickness to the particle diameter of 0.2 or less measured from the outermost surface of the fine particles is determined by the number of metal atoms with respect to the total amount of metal contained in the fine particles.
  • Fine particles having a particle size of 50 to 100% in terms of are preferable because they have excellent sphericity and can be easily obtained as fine particles having a sharp particle size distribution.
  • the existence state of such a metal (water) oxide can be confirmed by, for example, ESCA.
  • the metal atom in the metal (water) oxide and / or the silicon atom in the amorphous silica, and the carbon atom adjacent to the hydroxyl group in the alcohol are It is thought to be due to a covalent or ionic bond firmly bonded via an oxygen atom, or a hydrogen bond between a hydroxyl group in metal (water) oxide and Z or a silanol group in amorphous silica and a hydroxyl group in alcohol.
  • Can be Whether or not alcohol is bound can be determined by whether or not alcohol evaporates when the modified fine particles are heated to near the boiling point of the alcohol. However, since it does not evaporate, it can be clearly distinguished from a mere mixed state.
  • the amount of alcohol bound to the fine particles should be in the range of 1 to 30% by weight based on the ratio in the composite spherical fine particles. If the amount is insufficient, it is difficult to obtain fine particles having excellent dispersibility. On the other hand, if the amount is too large, the mechanical strength of the obtained fine particles becomes insufficient, so that the reforming agent easily falls off when subjected to heat or external force, and it becomes impossible to prevent void defects and the like.
  • Alcohols include methanol, ethanol, isopropyl alcohol, n-butanol, stearyl alcohol, melicyl alcohol Aliphatic saturated monohydric alcohols such as coal, aliphatic unsaturated monohydric alcohols such as aryl alcohol, clotyl alcohol, and propargyl alcohol; cycloaliphatic monohydric alcohols such as cyclopentanol and cyclohexanol; benzyl alcohol; Monohydric alcohols such as cinnamyl alcohol, aromatic monohydric alcohols such as methyl phenylcarbinol, and heterocyclic monohydric alcohols such as furfuryl alcohol; ethylene glycol, propylene glycol, trimethylene glycol,
  • 1,4-monobutanediol 1,5—pentanediol, 1,6—hexanediol, 1,8-octanediol, 1,10—decanediol, aliphatic glycols such as pinacol, hydrobenzoy Aliphatic alcohols having an aromatic ring such as benzene, benzopinacol, phthalyl alcohol, cyclopentane-1,2-diol, cyclohexane
  • monohydric alcohols, glycols and trihydric alcohols having 1 to 10 carbon atoms are easily bonded to metal (hydroxide) and Z or amorphous silica as constituents of the fine particles. It is preferable because the amount of binding (content) can be easily adjusted.
  • the composite spherical fine particles of the present invention have a specific amount of metal (hydroxide) localized on the surface of the amorphous silicon force and an alcohol in a bonded state as essential components as described above.
  • metal hydrooxide
  • From the raw materials used in the production of the fine particles for example, acid radicals such as acetates and nitrates, ammonia, organic amines, halogens such as chlorine, etc. n D d, and organic compounds such as alkyl groups. It may contain a small amount of base, adsorbed moisture, etc. However, if the amount is too large, the above-mentioned characteristics of the present invention are inhibited or diluted, so that the content should be suppressed to 20% by weight or less.
  • the term "spherical" means that the difference between the major axis and the minor axis of the fine particles is small, and the composite spherical microparticles according to the present invention have a major axis / minor axis ratio of 1.0 'to 1.2. Particularly, those having a shape close to a true sphere are particularly preferable.
  • the composite spherical fine particles are not particularly limited in particle diameter, particle size distribution, and the like, but are appropriately selected and used according to the intended use of the fine particles so as to maximize the effect of use.
  • the composite spherical fine particles have a uniform particle size distribution, and more specifically, those having a particle diameter variation coefficient defined by the following [ ⁇ ] formula of 10% or less. Particularly preferred.
  • Average particle size (d) ⁇ Di / n
  • the composite spherical fine particles have better affinity for the resin than conventional fine particles, and the excellent affinity for the composite This is reflected in the improved properties of processed products, such as paints, fibers, and films, which contain spherical fine particles.
  • the effect of improving the affinity is particularly high, and the characteristics of the processed product as described above can be more effectively enhanced because the average particle size is 0.05 to 10 izm, especially 0.
  • a suspension (I) of spherical fine particles made of amorphous silica is converted into a sol of a metal (hydr) oxide having one or more electronegativities of ions of less than 15.6 and one or more alcohols. Heating to 100-250 ° C in the presence of.
  • an oxide and / or hydroxide sol of a metal less than 6 and one or more alcohols (Y) which are the same as or different from the alcohols (X) 100 Heating method to ⁇ 250 ° C.
  • Silica-alcohol composite spherical fine particles in which one or two or more types of alcohols are bonded to spherical fine particles made of amorphous silica are used as the main components of at least one of the above alcohols.
  • a hydrolysable metal compound having an electronegativity of less than 15.6 was added to a suspension (IV) containing spherical fine particles of amorphous silica, water and, if necessary, a hydrolysis catalyst. Later, the resulting suspension is heated in the range of 100-250 in the presence of one or more alcohols,-
  • a suspension of silica-alcohol composite spherical fine particles (II), in which one or two or more alcohols (X) are bonded to spherical fine particles made of amorphous silica, is hydrolyzable, After coexistence of a metal compound with a negative degree of less than 15 16, water and, if necessary, a hydrolysis catalyst, the resulting suspension is mixed with one or more of the above alcohols (X). a method of heating in the range of 1 0 0 ⁇ 250 e C under the coexistence of an alcohol (Y).
  • the suspensions (1), (II), (III) and (IV) used in the production methods (Pr-I) to (Pr-V) are amorphous silica spherical fine particles [suspension (1), (IV) silica-alcohol-composite spherical microparticles obtained by bonding at least one type of alcohol to amorphous silica or amorphous silica [suspension (11), (III)] dispersed in a solvent Means a suspension.
  • the method for producing the suspensions (I), (11), (HI), (IV) and the spherical fine particles dispersed and contained therein is not particularly limited, but in any case, the particle size distribution is excellent in sphericity. In that it is easy to obtain sharp spherical fine particles of T JP9 1
  • a method is preferred in which the compound is produced through the step (A) of hydrolyzing and / or condensing an organic silicon compound capable of hydrolysis and / or condensation in an organic solvent in the presence of water.
  • silicon alkoxides are used as the organosilicon compound, and the above-mentioned organic solvents are used, because spherical fine particles having a controlled particle size and particle size distribution are easily obtained. Alcohol is preferable, and fine particles having excellent sphericity are easily obtained, so that it is preferable to coexist with ammonia, organic amine or the like as a catalyst. —
  • step (A) the hydrolysis and condensation conditions, such as the type and concentration of the organosilicon compound, solvent, and catalyst used, the concentration of water, the temperature, and the method of adding the organosilicon compound, are controlled.
  • a suspension of spherical fine particles having a controlled particle size, particle size distribution, sphericity, etc. can be obtained.
  • the suspension (I) can be subjected to post-treatment such as heat concentration or solvent replacement. ), (II), (III), and (IV).
  • suspensions (1), (II), (II), (II), (II), (III) are controlled by controlling the hydrolysis / condensation conditions, the presence / absence of the post-treatment, and the control of the treatment method.
  • ⁇ ) and (IV) can be prepared respectively.
  • a sol is one in which a metal (aqueous) oxide is in the form of fine particles or a condensate in which a metal is bonded via oxygen, and is suspended, emulsified, or dissolved in a solvent containing water and / or alcohol.
  • a metal (aqueous) oxide is in the form of fine particles or a condensate in which a metal is bonded via oxygen, and is suspended, emulsified, or dissolved in a solvent containing water and / or alcohol.
  • an acid such as acetic acid, nitric acid, and hydrochloric acid derived from raw materials, emulsifiers, stabilizers, etc.
  • metal (aqueous) oxides used in the process of producing the sol or solvent components other than water and Z or alcohol.
  • These acid radicals, anionic surfactants, cationic surfactants, nonionic surfactants, (aqueous) oxides such as alkali metals and alkaline earth metals, and various kinds of electroly
  • the metal (water) oxide in the sol is, for example, a metal (water) of a metal having an electronegativity of less than 15-0.6, such as a silica sol which has been positively charged by coating with alumina.
  • a metal (aqueous) particles coated with oxides, or a metal with an ionegativity of 15.6 or more and a metal with an electronegativity of less than 15.6 The composite metal (water) oxide as a component is also included. Further, a small amount of a (hydr) oxide of a metal different from the metal may be mixed in the sol.
  • the alcohol sol is not limited to the amorphous (silicone) force and the metal (hydr) oxide having an electronegativity of less than 15.6 in the composite fine particles.
  • any of the alcohols exemplified above can be used. These alcohols can be used alone, or two or more of them can be used in combination.
  • an appropriate amount of water can be mixed and used, or a small amount of a solvent other than alcohol can be added. It doesn't matter.
  • the amount of the sol added to the suspensions (I), (II), and (III) varies depending on the type of the sol, the particle size of the spherical fine particles in each suspension, and the like. Although it is not possible to determine the ratio uniformly, for the reasons described above, the ratio of the metal equivalent in the finally obtained composite spherical fine particles is 0.01 to 0.1%. It is set so as to be in the range of 20% by weight, more preferably in the range of 0.05 to 10% by weight.
  • the suspension (I) encompasses all suspensions in which amorphous silica spherical fine particles are dispersed and contained in an arbitrary solvent.
  • the amorphous silica spherical fine particles as used herein means spherical fine particles composed of the above-mentioned amorphous silica, and the concentration of the fine particles in the suspension (I) is 1 to 50% by weight. Is preferable. When the concentration is less than 1% by weight, the productivity of the composite spherical fine particles is low, and when the concentration exceeds 50% by weight, it is difficult to obtain composite spherical fine particles having good composition uniformity and dispersibility. Become.
  • the components other than the amorphous silica spherical fine particles constituting the suspension (I) are not particularly limited, but it is necessary to allow alcohol to coexist during the subsequent heat treatment in a temperature range of 100 to 250 ° C. Therefore, it is preferable that one or two or more alcohols are previously contained in the suspension (I). Further, the alcohols are complex spherical fine particles having a uniform amount of -alcohol. It is preferable that the solvent is at least one component because it is easily obtained. Of course, other solvents such as water may coexist.
  • the content of the alcohol in the suspension (I) is the total amount of alcohol, and the weight ratio to the amorphous silica spherical fine particles in the suspension (I) is in the range of 0.01 to 50 times. preferable. If the content is less than 0.01, the binding of alcohol in the composite spherical fine particles may be non-uniform, and if the content exceeds 50, the productivity of the composite spherical fine particles deteriorates.
  • the suspension (I) described above and an amorphous material dispersed and contained in the suspension (I) The method for producing the silica spherical fine particles is not particularly limited, but a production method through the step (A) is preferable. For example, it is possible to obtain a suspension (la) containing alcohol of spherical fine particles obtained by hydrolysis / condensation reaction of silicon alkoxide in hydrous alcohol in the presence of the above-mentioned catalyst and containing alcohol as a main component.
  • the method for producing the suspension (I) from the suspension (la) is not particularly limited, and the suspension (la) may be used as it is as the suspension (I). Concentrated by removing some or all of the solvent component in the suspension (la) or part or all of the catalyst component under pressure or reduced pressure, or in the suspension (la) The suspension (I) can be obtained by subjecting the solvent component to solvent replacement with the same or different alcohol as the alcohol in the suspension (la).
  • a suspension (I) in which the amorphous silica spherical fine particles contain alcohol at least as a main component can be obtained.
  • amorphous silica fine spherical particles obtained by a wet method such as a de-alkali method of water glass or a dry method are dispersed in a solvent such as alcohol. And the like.
  • the suspension (I) obtained as described above is mixed with the above-mentioned metal (hydroxide) oxide sol and one or more alcohols in the range of 100 to 250, More preferably, 150 to 250.
  • the desired composite spherical fine particles can be obtained.
  • the method of coexisting the metal (hydroxide) sol and one or more alcohols during the heat treatment is not particularly limited. Preferred In general, prior to or during the heat treatment, a method is used in which a metal (aqueous) oxide sol and, if necessary, one or more alcohols are added to the suspension (I). Is done.
  • the above-mentioned alcohol is added as necessary when the suspension (I) already contains alcohol, and is always added when the suspension (I) does not contain alcohol.
  • the alcohol to be added may be the same as or different from the contained alcohol.
  • One or more metal (water) oxide sols are added to the suspension (I), but the method of addition is not particularly limited.
  • a general method for example, a method in which the whole amount of the sol is added to the suspension (I) at once or in several portions on the surface of the solution or in the solution while stirring the suspension (I), or A method of continuously adding at a high speed is employed.
  • two or more sols are added, they may be added as a mixture thereof or separately.
  • the order of addition of the metal (aqueous) oxide sol and the alcohol to the suspension (I) is not particularly limited, and they may be added simultaneously, for example.
  • the metal (water) oxide added as a sol is firmly bonded to the surface, and the coexisting alcohol is composed of amorphous silica and / or metal (water).
  • the composite spherical fine particles of the present invention bound to the oxide can be obtained as a suspension (I-L) (alcohol dispersion) or powder containing alcohol.
  • the suspension (IL) is prepared by preparing the suspension (I) in the presence of a metal (aqueous) oxide sol and one or more alcohols, 2 5 0. After heat treatment in the range of C, more preferably in the range of 150 ° C. to 250 ° C., or while heat treatment, at least one of the coexisting alcohols is finally left as a solvent, and It is obtained by removing the solvent component of At this time, a method such as solvent replacement is adopted as necessary.
  • the powder of the composite spherical fine particles can also be obtained by finally removing the solvent component completely in the method involving the above-mentioned suspension (IL).
  • IL suspension
  • Spherical microparticles with excellent secondary dispersibility and excellent secondary dispersibility can be obtained by using the vacuum flash evaporation method, in which heat treatment in the above temperature range and removal of solvent components can be performed simultaneously after adding two or more alcohols. This is particularly preferable.
  • This method uses a suspension (II) of spherical particles of an alcohol-alcohol complex in which one or more alcohols (X) are bonded to amorphous silica. 100 to 2 in the presence of a metal (hydr) oxide sol less than 15.6 and one or more alcohols (Y) which are the same or different from the alcohols (X) described above.
  • This is a method of heating to 50 ° C., wherein at least one of alcohols (X) and (Y) contains the above-mentioned amorphous silica and Z or the above metal (water).
  • the composite spherical fine particles bonded to the oxide are obtained.
  • the components and composition of the suspension (II) used are the same as those of the suspension (I) described above in the production method (Pr-I) except that alcohol is bonded to the amorphous silica spherical fine particles. is there. Also, alcohol here (X) and (Y) mean the same as the alcohol described as a component of the composite spherical fine particles.
  • the silica-alcohol composite spherical fine particles dispersed and contained in the suspension ( ⁇ ) and the suspension (II) described above are not particularly limited in the production method, but are the same as those in the suspension (I).
  • the method, that is, the production method through the above-mentioned step ( ⁇ ) is preferably adopted.
  • a suspension (la) containing amorphous alcohol spherical fine particles as a solvent as a main component can be obtained as described above.
  • a suspension (II) is obtained by heating the suspension (la) at a temperature of less than 100 ° C. or at a temperature of 100 ° C. or more in the presence of alcohol (X). be able to.
  • the silica-alcohol complex spherical in which the alcohol (X) is bonded to the amorphous silica is controlled by controlling the type of raw materials used and the reaction conditions such as the reaction temperature.
  • a suspension (Ila) of fine particles is obtained, and this can be used as it is as the suspension (II).
  • the suspension (IIa) can also be obtained by post-treatment such as heating and concentrating the suspension (Ila).
  • the alcohol (Y) may be present, for example, as a solvent component in the suspension (II), and the suspension (II) is added to the suspension (II) in the same manner as described in the production method (Pr-I). It may be added before or during the heat treatment in the range of 250 ° C.
  • the production method from the suspension (II) to the production of the composite spherical fine particles can be the same method as described in the production method (Pr-I), and can be carried out in the same manner as in the production method (Pr-I). Powder or alcohol dispersion of composite spherical fine particles Obtainable.
  • suspension ( ⁇ ) is converted to metal (water) oxide sol and alcohol
  • the type of alcohol introduced into the composite microparticles in a bound state by heat treatment with ( ⁇ ) is added to the alcohol (X) previously bound to the suspension ( ⁇ ) and added before the heating reaction, or It varies depending on the type and amount of the alcohol (II) already present as a solvent component in the suspension (II) or the heating reaction conditions. For example, in the case where the alcohol (X) bound to the fine particles in the suspension (II) remains as it is and remains as the bound alcohol of the composite spherical fine particles, (2) in the suspension ( ⁇ ) If all of the alcohol (X) bound to the microparticles in step (b) is replaced with alcohol ( ⁇ ) by transesterification etc. in the heating reaction step, (3) the alcohol bound to the microparticles in the suspension ( ⁇ )
  • the silica-alcohol composite fine particles in which alcohol is previously bonded to the surface of the amorphous silica spherical fine particles are dispersed in an alcoholic solvent containing at least one of the above alcohols as a main component.
  • Suspension ( ⁇ ) is used.
  • This suspension (III) The concentration of the silicic acid-alcohol composite spherical fine particles in the aqueous solution is preferably in the range of 1 to 50% by weight based on the total amount of the suspension. If the concentration is insufficient, the productivity of the composite spherical fine particles is poor.
  • the concentration of the alcohol which is the main component of the solvent in the suspension (III) is preferably in the range of 80 to 100% by weight based on the total solvent in the suspension, and the concentration is preferably 80% by weight. If the ratio is less than 1, the dispersibility of the spherical composite fine particles may be poor.
  • the amount of alcohol bound in the silica-alcohol composite spherical fine particles is preferably in the range of 1 to 30% by weight in terms of the ratio in the finally obtained composite spherical fine particles.
  • the particle size is insufficient, the dispersibility of the fine particles in the suspension ( ⁇ ) is deteriorated, and the sphericity, particle size distribution and dispersibility of the finally obtained composite spherical fine particles are deteriorated. If the amount is too large, the mechanical strength of the composite spherical fine particles becomes insufficient.
  • the method for producing the suspension (III) is not particularly limited.
  • one of the solvents in the suspension (la) or (Ila) obtained in the same manner as in the above method (Pr-I) or (Pr-II) By substituting a part or all of the solvent with an alcohol by heating, an alcohol suspension of spherical fine particles in which the alcohol is bonded to the amorphous silicon is obtained.
  • the heat treatment temperature is not particularly limited, but alcohol is more efficient.
  • the range of 100 to 250 is preferred from the viewpoint that easily bonded silica-alcohol composite spherical fine particles are easily obtained.
  • metal compound A A metal compound having an electronegativity of less than 15.6 (hereinafter referred to as metal compound A) will be described.
  • hydrolyzable metal compound refers to a compound that forms a (hydr) oxide of a metal through hydrolysis and Z or condensation reaction, and is a non-hydrolyzable compound directly bonded to the metal.
  • inorganic salts such as metal sulfates, hydrochlorides, and nitrates; metal alkoxides, metal acetates, metal oxalates and other metal acylate compounds; metal acetyl acetonates, and metals.
  • 0-diketone, glycol, hydroxycarb of metals such as glycolate examples include chelate compounds such as acid, keto ester, keto alcohol, amino alcohol, and quinoline.
  • the amount of the metal compound (A) added to the suspensions (IV) and (III) is the same as in the case of the metal (hydroxide) oxide sol and the type of the metal compound (A) and the amount of each metal compound (A). Since it depends on the particle diameter of the spherical fine particles in the suspension, it cannot be determined uniformly, but for the reasons described above, the ratio of the metal equivalent in the composite spherical fine particles finally obtained is 0. It is set so as to be in the range of 0.1 to 20% by weight, more preferably in the range of 0.05 to 10% by weight.
  • the form of addition of the metal compound (A) to the suspensions (IV) and (II) is not particularly limited, but the metal compound (A) such as an aqueous solution or an alcohol solution of the metal compound (A) can be uniformly dissolved, and It is preferable to add in a state of being dissolved in a solvent having high compatibility with the solvent of the suspension (IV) or the suspension ( ⁇ ).
  • the method of adding the metal compound is not particularly limited, and the above-described method of adding the sol is appropriately employed.
  • the metal (hydr) oxides constituting the composite spherical fine particles are hydrolyzed and / or degraded from the metal compound (A) at least in the presence of water. Alternatively, it is formed through a condensation reaction.
  • the amount of water required at that time is appropriately selected, but the amount of water is usually more than the stoichiometric amount of the hydrolysis and condensation reaction of the metal compound (A) with respect to the metal compound (A). It is preferred that
  • the hydrolysis catalyst is optionally present in a suspension to promote the hydrolysis of the metal compound (A) in the presence of water.
  • the hydrolysis catalyst include ammonia, primary amine, secondary amine, and Organic amines such as quaternary ammonium and quaternary ammonium; alkaline metal compounds such as sodium hydroxide; alkaline earth metal compounds such as calcium hydroxide; base catalysts such as hydrochloric acid; acids such as hydrochloric acid and nitric acid A catalyst and the like are exemplified, and are appropriately selected depending on the kind of the metal compound (A) and the like.
  • a low-boiling compound having high volatility is preferable, and ammonia is particularly preferable.
  • those which generate these catalyst components by heating or the like, for example, urea which generates ammonia by reaction with water upon heating, etc. are also included in the hydrolysis catalyst.
  • a suspension (IV) containing, as essential components, spherical fine particles composed of amorphous silicon and water and, if necessary, a hydrolysis catalyst, is used. After adding the compound (A), the obtained suspension is subjected to coexistence of one or more alcohols described above.
  • the metal (hydroxide) converted from the metal compound (A) by hydrolysis and / or condensation reaction is converted.
  • Spherical composite fine particles are obtained in which the alcohol localized on the surface and coexisting is bonded to amorphous silica and Z or metal (hydroxide).
  • the suspension (IV) the suspension in the above-mentioned production method (Pr-I) is used.
  • the suspension (IV) can be preferably used. After adding the above-mentioned metal compound (A) to the suspension (IV), the suspension is added in the presence of one or more alcohols in the range of 100 to 250 ° C, preferably 150 to 250 ° C. When heated in the range of 50 ° C, the desired composite spherical fine particles can be obtained.
  • the method of mixing the four components of the metal compound (A), water and the hydrolysis catalyst in the suspension (IV) described above is not particularly limited.
  • the metal compound (A) is added to the suspension (IV) containing at least water, but the water and the hydrolysis catalyst are added in advance in the suspension (IV) in an appropriate amount. If present, it is not necessary to add it, but it can be added at the same time as the addition of the metal compound (A) or at any time after the addition and before the heat treatment.
  • the alcohol coexisting during the heat treatment may be previously contained in the suspension (IV) described above, or may be added to the suspension (IV) at any stage until the heat treatment is completed. Good.
  • the metal (hydroxide) generated by hydrolysis of the metal compound (A) is firmly bonded to the surface, and the coexisting alcohol is present.
  • the composite spherical fine particles of the present invention bound to amorphous silica and / or metal (hydroxide) can be obtained as an alcohol dispersion or powder.
  • one or more alcohols (X) are converted to amorphous A suspension ( ⁇ ) of silica-alcohol composite spherical fine particles bonded to porous silica is used, and the metal compound (A), water and, if necessary, a hydrolysis catalyst are allowed to coexist in the suspension ( ⁇ ). After that, the obtained suspension is heated to a temperature of 100 to 250 ° C. in the coexistence of one or more alcohols (Y) which are the same as or different from the alcohol (X).
  • the metal (water) oxide converted from the metal compound (A) by hydrolysis and Z or a condensation reaction is localized on the surface, and the alcohols (X) and (Y ), Spherical particles of a complex in which at least one alcohol is bonded to the above-mentioned amorphous silica and Z or metal (hydroxide) are obtained.
  • the suspension ( ⁇ ) used in this method the suspension ( ⁇ ) used in the above-mentioned production method ( ⁇ - ⁇ ) can be used, and its preferred production method and embodiment are as described above.
  • the method for coexisting the metal compound (A), water and the hydrolysis catalyst in the above-mentioned suspension (II) is not particularly limited.
  • the metal compound (A) is added to the suspension ( ⁇ ), but water and a hydrolysis catalyst are used if the respective components are previously present in the suspension ( ⁇ ) in an appropriate amount. It is not necessary to add the metal compound (A) before, simultaneously with, or simultaneously with the addition of the metal compound (A) if there are any missing components in the suspension ( ⁇ ) or if these components are not contained at all. Later addition It can be added and replenished at any time before the heat treatment.
  • the alcohol (Y) coexisting during the heat treatment may be contained in advance in the above-mentioned suspension ( ⁇ ), as in the case of the above-mentioned production method (Pr-II), or the suspension ( Ii) may be added at any stage until the heat treatment is completed.
  • the metal (hydroxide) generated by hydrolysis of the metal compound (A) is firmly bonded to the surface, and the coexisting alcohol is amorphous.
  • the composite spherical fine particles of the present invention bound to silica and / or metal (hydroxide) can be obtained as an alcohol dispersion or powder.
  • the type of alcohol introduced in a bound state into the finally obtained composite spherical fine particles depends on the type and amount of alcohol (X) and (() or the heating conditions as in the case of the production method ( ⁇ - ⁇ ).
  • X type and amount of alcohol
  • ⁇ - ⁇ the heating conditions as in the case of the production method
  • the electronegativity of ion is less than 15.6 in the spherical fine particles made of amorphous silica, which is the object of the present invention.
  • Spherical composite fine particles having a composite composition in which a metal (hydr) oxide is localized and bound to alcohol are obtained as a powder or a dispersion.
  • the ester composition contains 0.05 to 5% by weight of composite spherical fine particles satisfying the above-mentioned requirements with respect to polyester.
  • This composition includes films, sheets and fibers. It is effectively used as a raw material for various molded objects.
  • the composite spherical fine particles blended as a constituent material of the polyester composition preferably have a sharp particle size distribution.
  • the coefficient of variation of the particle diameter defined by the above formula [II] is 1 It is preferably 0% or less.
  • the coefficient of variation of the particle diameter exceeds 10%, when the fine particles are blended with the polyester resin, not only the monodispersibility of the fine particles in the resin is deteriorated, but also the surface unevenness when the film is formed. It is difficult to obtain a uniform film.
  • the composite spherical fine particles preferably have an average particle diameter in the range of 0.05 to ⁇ circle around (2) ⁇ , particularly in the range of 0.1 to 5 tm.
  • the reason is that, when the average particle diameter is within this range, the effect of improving the affinity of the composite spherical fine particles to the polyester resin is remarkable as the effect of improving the characteristics of the molded product such as a film. It is because it is expressed in.
  • the average particle diameter becomes extremely fine particles of less than 0.05 ⁇ the dispersibility of the fine particles in the polyester resin tends to be rather deteriorated, and moreover, appropriate surface projections are formed on the obtained film.
  • the effect of improving the slipperiness of the film may not be sufficiently exerted.
  • the polyester composition may be dispersed in a polyester resin or the resulting polyester composition may be formed into a film or the like.
  • a problem such as cracking of fine particles or peeling of the surface layer may occur, or when the film is formed into a sheet, the surface flatness may not be satisfied.
  • the localization of the metal (water) oxide on the surface of the fine particles is a main cause of increasing the affinity of the fine particles with the polyester resin.
  • the content of the metal in the surface layer having a ratio of the thickness measured from the outermost surface of the fine particles to the particle diameter of 0.2 or less is reduced to the fine particles. It is particularly preferable that the content of the fine particles is 50 to 100% in terms of the number of metal atoms based on the total amount of the contained metal (water) oxides.
  • the affinity with the polyester resin is further improved as well as the height.
  • the metal (hydroxide) constituting the composite spherical fine particles may be a metal (hydroxide) of a metal having an ionegativity of less than 15.6 as defined by the above formula [I].
  • Negative metals are preferred.
  • (hydr) oxides of A 1, Ti, Zr, Zn, Fe, and Ce are particularly preferable in that they greatly enhance dispersibility in polyester resins and affinity with polyester resins.
  • a 1 is the most practical metal because its (aqueous) oxide raw material can be obtained easily and very inexpensively, and is also the most preferable metal because it exhibits particularly excellent effects in the above-mentioned aspects. You.
  • the composite spherical fine particles are applied to the polyester composition of the present invention.
  • Silica and metal (water) oxide It is desirable that the metal (hydroxide) be crystalline, such as boehmite, because of its excellent adhesion and excellent mechanical strength of the polyester composition.
  • the preferable ratio of the metal (hydr) oxide in the composite spherical fine particles is in the range of 0.01 to 20% by weight in terms of metal. If the content is insufficient, the polyester of the fine particles may be used. If the affinity for the resin is insufficient, and if the content is too large, the dispersibility of the fine particles in the polyester resin tends to deteriorate. Further, considering the affinity of the polyester resin of the fine particles and the ease of controlling the surface projection shape of the obtained polyester film, the uniformity of the surface irregularities, and the like, the more preferable content of the metal (hydroxide) is The range is 0.05 to 0.5% in terms of metal;
  • the preferred amount of the alcohol bound to the composite spherical fine particles is in the range of 1 to 30% by weight in terms of alcohol, when the content is insufficient.
  • the amount is too large, the mechanical strength of the fine particles becomes insufficient, and when the fine particles are dispersed in a polyester resin, or when the obtained polyester composition is processed into a film or the like, the fine particles are difficult to disperse. This can cause problems such as cracking.
  • the type of alcohol to be bonded is not particularly limited, and all of the above-mentioned alcohols can be applied. Among them, monohydric alcohols, glycols and trihydric alcohols having 1 to 10 carbon atoms are particularly preferred for the fine particles of the polyester resin. It is particularly preferable for enhancing dispersibility.
  • the polyester composition of the present invention contains 0.005 to 10% by weight of the composite spherical fine particles satisfying the above requirements as an essential component.
  • small amounts of other components such as antistatic agents, ultraviolet absorbers, antioxidants, heat stabilizers, light stabilizers, pigments, dyes, etc. are added to this polyester composition. can do.
  • polyester composition of the present invention As described above, a composite in which a specific metal (hydroxide) is localized on the surface of fine particles and a specific amount of alcohol is bonded.
  • the characteristic feature is that spherical fine particles are used.
  • any conventionally known polyester may be used as the polyester component and any conventionally known production method may be used.
  • the composition of the present invention can be obtained.
  • the method of adding the composite spherical fine particles to the polyester may be a method of adding it to the polyester as a powder or dispersing it in advance in glycol, which is a raw material of polyester such as ethylene glycol, propylene glycol, and 1,3-butadiol.
  • glycol which is a raw material of polyester such as ethylene glycol, propylene glycol, and 1,3-butadiol.
  • a method of adding a so-called glycol dispersion to the polyester may be employed.
  • These powders and glycol dispersions can be easily obtained according to any one of the above-described methods (Pr-I) to (Pr-V) for producing composite spherical fine particles.
  • the composite spheres and fine particles are added to the reaction system.
  • the timing of addition is not particularly limited, but is preferably at the beginning of the polycondensation reaction, for example, until the intrinsic viscosity becomes about 0.3 after the start of the reaction, and the addition method and the addition timing are not particularly limited.
  • the polyester composition in which the fine particles are dispersed very well Things are easy to obtain.
  • the content of the composite spherical fine particles in the polyester should be in the range of 0.05 to 10% by weight, preferably 0 to 1 to 3% by weight, based on the entire polyester composition. If the content is insufficient, the effect of improving the slipperiness / abrasion resistance is not sufficiently exhibited, while if too large, the surface flatness when formed into a film, a sheet, or the like may deteriorate.
  • fine particles other than the composite spherical fine particles for example, externally added particles and Z or polyester which have a shape such as a sphere, a lump, or a plate, and are insoluble in the polyester, Internal particles precipitated during synthesis may be included.
  • two or more kinds of composite spherical fine particles having different average particle diameters, chemical compositions and the like can be contained.
  • the polyester constituting the polyester composition of the present invention includes all polyester resins obtained by polycondensing a dicarboxylic acid component and a glycol component.
  • the dicarboxylic acid include terephthalic acid and naphthalenedicarboxylic acid.
  • Aromatic dicarboxylic acids such as acids are preferred.
  • Glycol components include ethylene glycol, trimethylene glycol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8 —Octanediol
  • aliphatic glycols such as 1,10-decanediol are preferred.
  • polyesters containing alkylene terephthalate and / or alkylene naphthalate as a main component are preferable, and those containing ethylene terephthalate and / or ethylene naphthalate as a main component are particularly preferable.
  • These polyesters are known per se and can be produced by a known method.
  • the thus obtained polyester composition is a composition in which the composite spherical fine particles are uniformly dispersed in a polyester in a monodispersed state. Even when subjected to considerable heat or external force, the composite spherical fine particles in the composition are obtained. Does not agglomerate or degrade in the composition. Therefore, by forming this into an arbitrary shape such as a film, sheet, or fiber by a known method, a molded article having characteristics (slipperiness, abrasion resistance, etc.) not seen in conventional examples can be obtained. Obtainable.
  • the polyester composition when a polyester film is to be obtained using the polyester composition, the polyester composition is heated to about 280 to 300 ° C., melt-extruded into a sheet, and then cooled and solidified. By doing so, an amorphous unstretched film can be obtained, and if necessary, for example, in the longitudinal and transverse directions, sequentially in the longitudinal, transverse, and longitudinal directions, or simultaneously in the longitudinal and transverse directions.
  • a biaxial stretching method or the like By adopting a biaxial stretching method or the like, a uniaxial or biaxially oriented film can be obtained.
  • the obtained stretched film is a film in which the generation of voids and the like is extremely suppressed as compared with the conventional film.
  • the surface composition analysis using an X-ray microphone analyzer and ESCA, etc., and the bulk composition analysis using fluorescent X-ray analysis and atomic absorption analysis were performed.
  • the sample was a powder
  • the sample was used as a measurement sample.
  • the sample was a suspension including a glycol dispersion, fine particles in the suspension were separated by centrifugation. after, and dried in vacuo at 9 0 e C, to obtain a powder specimen of the particles to completely remove volatile components, it was subjected to the measurement.
  • the fine particles are powder, about 5 g is precisely weighed using a sample from which physically adsorbed water and free residual volatile components have been removed by vacuum drying in advance at 90, and N NaOH aqueous solution of N Add to 25 Oml and stir at room temperature for 10 hours. As a result, all the hydrolyzable groups in the fine particles are hydrolyzed and extracted into the aqueous solution. Therefore, the amount of alcohol in the clarified liquid obtained by separating the fine particles from the suspension is determined by gas chromatography, and It was the amount of bound alcohol per 1 g of the body sample.
  • the fine particles are a suspension, a part of the suspension is heated to 90 and dried under vacuum until volatile components such as free glycol can be completely removed to obtain a dry powder. This dried powder was used as a sample for the same determination.
  • the powder is dispersed in pure water using an ultrasonic homogenizer to form a 5% by weight suspension, and this is used as a sample to prepare an electrophoretic zeta potential measurement device (Shimadzu). It was measured according to the manufacturing method of 122 type.
  • the suspension was diluted with pure water to obtain a suspension of 5% by weight, and the measurement was similarly performed.
  • composition ratio: 39: 39: 2: 10 2 g of styrene-methyl methacrylate-methacrylic acid-hydroxylmethacrylate methacrylate copolymer (composition ratio: 39: 39: 2: 10) is mixed with methylethylketone-toluene mixed solvent (mixing ratio; weight ratio 1: 1)
  • mixing ratio; weight ratio 1: 1 2 g of fine particle powder is added and mixed, and stirred to form a suspension. After stirring at 20 ° C. for 20 hours, the dispersion state of the fine particles in the suspension was observed with an optical microscope, and evaluated according to the following evaluation criteria.
  • the adsorption amount of the polyester resin was measured according to the following method. That is, 10 g of the fine particle powder was dissolved in a mixed solvent of methyl ethyl ketone-toluene (mixing ratio: 1: 1 by weight) with a polyester resin [Vylon 1-2, manufactured by Toyobo Co., Ltd.]. Add to 200 g of the solution, mix and stir. After stirring at 20 ° C for 100 hours, the fine particles and the solution were separated by centrifugation, and the amount of resin dissolved in the solution was quantified by removing the solvent in the solution. Based on this, the amount of resin adsorbed on the fine particles was determined.
  • Hydrolysis / condensation of tetramethyl silicate is carried out in a hydrated solvent using ammonia as a catalyst to obtain an average particle diameter of 0.1%.
  • silica fine particles were obtained. ⁇ Nigokarada further 1 0 0 e C less than the heating temperature concentrated suspension of fine particles by distilling off part of the solvent and ammonia as methanol (particle concentration 2 0 wt%) 5 0 0 Parts by weight were obtained.
  • the silica spherical fine particles in the suspension were fine particles in which methanol was bonded to amorphous silica. Do not stir the concentrated suspension.
  • Example 2 Instead of adding ceria sol in Example 1, 50 parts by weight of ethylene glycol, 11.3 parts by weight of alumina sol (Al 2 O 3 content: 10% by weight, main component of solvent: water) were sequentially added and mixed. Except for the above, a particulate (P-2) powder was obtained in the same manner as in Example 1.
  • Example 4 titania sol instead of alumina sol (T i 0 2 content: 1 0% by weight). 3 3 parts by weight, except that benzyl alcohol was added 5 wt% in place of the ethylene glycol is In the same manner as in Example 2, composite fine particle (P-4) powder was obtained.
  • Fine particles (Q-1) powder was obtained in the same manner as in Example 2 except that alumina sol was not added.
  • the fine particles obtained in Comparative Example 1 were heated in air at 40 CTC for 4 hours to obtain amorphous silica fine particles having no alcohol bonded thereto.
  • 100 parts by weight of the obtained amorphous silicon fine particles were mixed and dispersed in 400 parts by weight of ethylene glycol.
  • Alumina sol and the resulting dispersion in with stirring grounds rt (A 1 2 0 a content: 1 0% by weight, the solvent ingredient: water) was continued for 1 1 3 parts by weight was added and mixed for 4 hours with stirring. Thereafter, the mixture was heated to a temperature of 120 ° C., maintained at 120 ° C. for 2 hours, and then vacuum-dried at ⁇ 60 to obtain a composite spherical fine particle (P-5) powder.
  • the fine particles obtained in Comparative Example 1 were subjected to a heat treatment at 400 in air for 4 hours to obtain amorphous silica particles having no alcohol bonded thereto.
  • 100 parts by weight of the obtained amorphous silicon fine particles were mixed and dispersed in 300 parts by weight of ethylene glycol. Stirring the resulting dispersion while alumina sol at room temperature. (A 1 2 0 3 content: 1 0% by weight, solvent principal components:. Water) 1 1 3 parts by weight adding and mixing continued for 4 hours with stirring After heating, the temperature was maintained at 60 at 2 hours, followed by vacuum drying at 60 to obtain fine particles (Q-3) powder.
  • Water glass No. 3 (S i 0 2 content 2 9 wt%, S i 0 2 / N a 2 0 molar ratio 3.2) was Dilute with S i 0 2 concentration of 4 wt% and comprising as deionized water Using sodium silicate as a raw material, a spherical silicic acid with an average particle diameter of 60 nm is produced according to a production method including a process of producing a colloid aqueous solution of activated silicic acid by denitrification using a known cation exchange resin and an aging process. particles was obtained an aqueous suspension which is dispersed contained in water (S i 0 2 concentration of 1 0% by weight).
  • Fine particles (Q-4) were obtained in the same manner as in Example 7, except that ethylene glycol was not used.
  • the composite fine particles obtained in each Example were In addition, the fine particles have a surface composition different from that of the fine particles obtained in the comparative example, and therefore, the fine particles have improved dispersibility in a resin solution and improved affinity with resins such as polyester. Was confirmed.
  • the evaluation results are shown in Tables 1 and 2 together with the physical properties of each fine particle. Physical properties of fine particles
  • Example 1 ⁇ 1 ceria 10 methanolic 4.0 + 0. U4 ⁇ 150
  • Example 5 P-5 Alumina 0.53 Ethylene 3.0 + 0.6 ⁇ 5 120
  • Example 6 P-6 Alumina 0.1 Methanol 4.0 + 0.3 ⁇ 5 150
  • Example 7 Alumina 0.50 Ethyleng 6.0 + 0.3 ⁇ 3 150
  • a suspension of spherical silica fine particles having an average particle diameter of 1.5 ⁇ obtained in the same manner as in Example 1 was further heated at a temperature of 90 ° C or less, and a solvent such as methanol and a part of ammonia were distilled off. As a result, 500 parts by weight of a concentrated suspension of the particles (particle concentration: 20% by weight) was obtained.
  • the fine particles (P-8) contained in the dispersion had an alumina content of 0.44% by weight in terms of A1, and were confirmed to be spherical fine particles having 16% by weight of ethylene glycol bonded thereto. Was done.
  • Tables 3 and 4 show the physical properties of the fine particles (P-8).
  • a suspension of amorphous silica spherical fine particles having an average particle diameter of 0.2 m obtained in the same manner as in Example 1 was further heated at 90 ° C. at the following temperature to partially distill a solvent such as methanol and ammonia. By removing, 500 parts by weight of a concentrated suspension of the particles (particle concentration: 20% by weight) was obtained.
  • Example 8 In the same manner as in Example 6 except that no alumina sol was added in Example 8, ethylene glycol in which silica-ethylene glycol composite spherical fine particles (Q-5) were dispersed and contained at a ratio of 20% by weight was used. A call dispersion was obtained. Tables 3 and 4 show the physical properties of the fine particles (Q-5) contained in the dispersion.
  • Ethylene glycol containing spherical silica-ethylene glycol composite spherical fine particles obtained in exactly the same manner as in Comparative Example 5 in a proportion of 20% by weight.
  • 500 parts by weight of an alumina sol (amorphous, A 1 . 2 0 3 content: 1 0% by weight, the solvent ingredient: after addition of water) 9 4 parts by weight, by continuing stirring for 5 hours, composite spherical particles (P - 1 0 "is being contained dispersed
  • An ethylene glycol dispersion was obtained, and the physical properties of the fine particles (P-10) contained in the dispersion are shown in Tables 3 and 4. Obtained in Examples 8 to 10 and Comparative Example 5, respectively.
  • Example 8 P-8 Alumina 0.44 Ethylene 14 + 0.5 180
  • Polyester films containing the fine particles obtained in Examples 1 to 4, 6, 7 and Comparative Examples 1, 2, and 4 were prepared according to the following Examples and Comparative Examples. For, the dispersion state in the polyester resin and the adhesion between the polyester and the fine particles were evaluated based on the following criteria.
  • Example 2 In a state where 100 parts by weight of a commercially available polyethylene terephthalate pellet was melted at 280 ° C., 1 part by weight of the fine particles ′ ( ⁇ -1) powder obtained in Example 1 was added. After kneading, the mixture was rejected, and the obtained polyester composition was heated and stretched to obtain a film having a thickness of 0.05 mm.
  • Example 11 a film having a thickness of 0.05 mm was obtained in the same manner as in Example 11 except that 1 part by weight of each fine particle was added as shown in Table 5 instead of the fine particles (P-1).
  • the dispersion state of the fine particles and the adhesiveness between the polyester resin and the fine particles were examined by the following methods.
  • the dispersion state of the fine particles in the film was observed with an optical microscope, and evaluated according to the following criteria.
  • Adhesion between polyester and child The interface between the fine particles in the film and the polyester resin was observed with a scanning electron microscope, and measured according to the following criteria depending on the degree of void.
  • the evaluation results are shown in Table 5.
  • the dispersion state of the fine particles in the films obtained in Examples 11 to 16 was good, and the adhesion between the polyester and the fine particles was good.
  • the films obtained in Nos. 1 to 8 either the dispersion state of the fine particles or the adhesion was inferior.
  • Example 11 P—1 1 ⁇ ⁇ Example 12 P-2 1 ⁇ ⁇ Example 13 P-3 1 ⁇ ⁇ ⁇ Example 14 P—4 1 ⁇ ⁇ Comparative Example 6 Q-11 ⁇ X Comparative Example 7 Q—2 1 X ⁇ Example 15 P-6 1 ⁇ ⁇ Example 16 P— 71 1 ⁇ ⁇ Comparative Example 8 -4 1 XX INDUSTRIAL APPLICABILITY
  • the composite spherical fine particles of the present invention are hard to agglomerate, are excellent in sphericity, dispersibility, affinity with resin, stability, etc., and are multi-component composites having a specific surface composition. Spherical microparticles, which are extremely useful as modifiers incorporated in various resins, rubbers and the like.
  • the production method of the present invention it is possible to efficiently produce composite spherical fine particles having such characteristics, and according to this production method, the particle diameter and the particle size can be obtained without impairing the sphericity of the fine particles. Since the distribution and the surface composition can be arbitrarily controlled, it is useful as a method for producing composite spherical fine particles applicable to a wide range of fields.
  • the polyester composition of the present invention mainly comprises composite spherical fine particles having the above-described excellent properties
  • the composite spherical fine particles dispersed and contained therein are compared with the conventional polyester composition. Since it has high affinity with polyester resin and excellent dispersibility, it has extremely excellent mechanical properties and optical properties. For example, when the composition is formed into a film, the formation of voids is suppressed and a film having a high dispersibility of the fine particles is obtained, and the film suppresses generation of scratches based on the formation of voids, In addition, the problem of particle detachment during stress loading, which has been pointed out in the conventional film in the film winding process, and the generation of white powder resulting therefrom are eliminated.
  • the biaxially oriented polyester film has uniform and finely controlled uneven surface characteristics, excellent slipperiness and resistance to slippage. It has abrasion properties and extremely low durability with extremely low generation of scratches and white powder.
  • This biaxially oriented polyester film can be used for various wide-ranging applications because of these properties. For example, when used as a base film for magnetic recording such as for video, audio, and entertainment, it exhibits excellent electromagnetic conversion characteristics, running properties, wear resistance, and long-term durability. Also, when used for capacitor applications, a low coefficient of friction, excellent winding properties, low crushing load, high transparency, etc. can be obtained. Furthermore, it can be widely applied to other fields such as electric insulation, packaging and vapor deposition films.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Silicon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Fine particule composite sphérique comprenant une fine particule de silice amorphe sphérique et, situé sur sa surface, un oxyde et/ou hydroxyde d'un métal dont l'ion a une faible électronégativité, et contenant une quantité spécifiée d'un alcool lié à sa surface; procédé de production de ladite particule; et composition polyester comprenant une résine polyester ainsi que 0,005 à 10 % en poids de particules. La particule a intrinsèquement une faible tendance à s'agréger, elle est excellente du point de vue de la dispersibilité dans diverses résines et divers caoutchoucs, et elle présente d'excellentes propriétés en tant que matière de remplissage ou modificateur. On peut obtenir une composition polyester utile dans la production d'un film excellent de par sa capacité de glissement et sa résistance à l'usure par association d'une quantité appropriée des particules avec une résine polyester.
PCT/JP1992/001494 1991-11-16 1992-11-16 Fine particule composite spherique, sa production et composition polyester la contenant Ceased WO1993010043A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP32818291 1991-11-16
JP3/328182 1991-11-16

Publications (1)

Publication Number Publication Date
WO1993010043A1 true WO1993010043A1 (fr) 1993-05-27

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1992/001494 Ceased WO1993010043A1 (fr) 1991-11-16 1992-11-16 Fine particule composite spherique, sa production et composition polyester la contenant

Country Status (1)

Country Link
WO (1) WO1993010043A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012162438A (ja) * 2011-02-09 2012-08-30 Tokuyama Corp 球状シリカ−チタニア複合酸化物粒子及びその製造方法
JP2015063451A (ja) * 2013-08-28 2015-04-09 日揮触媒化成株式会社 金属酸化物粒子およびその製造方法ならびに用途
JP2019178303A (ja) * 2018-03-30 2019-10-17 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物、および、電子部品

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6158811A (ja) * 1984-08-15 1986-03-26 イー・アイ・デユポン・ド・ネモアース・アンド・コンパニー 金属酸化物で安定化したクロマトグラフイー充てん材

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6158811A (ja) * 1984-08-15 1986-03-26 イー・アイ・デユポン・ド・ネモアース・アンド・コンパニー 金属酸化物で安定化したクロマトグラフイー充てん材

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012162438A (ja) * 2011-02-09 2012-08-30 Tokuyama Corp 球状シリカ−チタニア複合酸化物粒子及びその製造方法
JP2015063451A (ja) * 2013-08-28 2015-04-09 日揮触媒化成株式会社 金属酸化物粒子およびその製造方法ならびに用途
JP2019178303A (ja) * 2018-03-30 2019-10-17 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物、および、電子部品
JP7032977B2 (ja) 2018-03-30 2022-03-09 太陽インキ製造株式会社 硬化性樹脂組成物、ドライフィルム、硬化物、および、電子部品

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