JPH05192562A - Colloid solution, production thereof and synthetic resin molding containing colloid particle - Google Patents

Abstract

PURPOSE:To obtain a stable colloid soln. and a synthetic resin molding being excellent as a film-shaped molding. CONSTITUTION:A colloid soln. contains org-inorg. composite colloid particles wherein inorg. compd. particles with a small mean particle diameter are parent particles onto the surfaces of which are stuck child particles made of a synthetic resin or the surfaces of the parent particles are coated with a synthetic resin film. As the parent particles, an inorg. compd. colloid particle with a mean particle diameter of at most 1,000 nm, pref. in the range of 800-7nm is used. As the method for preparation thereof, a parent particle and a child particle which respectively exhibit the different change in xsi potential in a region of the same electric charge to the change in pH of a colloid soln. Namely, in a mixed colloid soln. of the parent particle and the child particle having a negative xsi potential, the value of pH is changed in the range of 2-7 and in a mixed colloid soln. of the parent particle and the child particle, having a positive xsi potential, the value of pH is changed in the range of 5-7. Repulsion force between the parent particles and the baby particles is weakened thereby and onto the surface of the parent particle the child particle are stuck.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colloidal solution containing organic / inorganic composite colloidal particles, a method for producing the same, and a synthetic resin molding containing the organic / inorganic composite colloidal particles.

[0002]

2. Description of the Related Art A method for producing a colloidal system composed of composite particles in which polymer latex is adhered to the surface of spherical silica particles has been reported (Polymer Papers vo
l. 44, No. 6, P. 483-489 (198
7)). The colloidal system described in this report relates to a hetero-aggregate of spherical silica particles having a relatively large particle size of 1590 nm. In the case of such a large particle size, the particles settle when left for a long time. As a result, a stable colloidal solution cannot be obtained.

Further, the same publication discloses a method of preparing an organic-inorganic composite aggregate by causing hetero-aggregation by mixing two kinds of particles having different signs of charges at a predetermined particle number ratio. There is. However, in this method, since a hetero-aggregate is formed by passing through a region where the ζ potential is 0, if the particle size of the colloidal particles that are the mother particles is small, the stability as a single particle is lacking, and the intermediary of the child particles occurs. There has been a problem that mother particles are aggregated and a stable colloidal solution in which colloidal particles are monodispersed cannot be obtained.

On the other hand, conventionally, synthetic resins such as acrylic resin, polyvinyl chloride, polystyrene, polyester, polyethylene, phenol resin, melamine resin, silicone resin and fluororesin are used as fibers, films for magnetic tapes and other molded products. Although widely used, colloidal particles such as silica are contained in these synthetic resins to give appropriate irregularities to the surface of the molded product to improve the surface smoothness of the molded product (for example, , JP-A-6
2-18424).

However, the conventional colloidal particles which have not been surface-modified are added to the synthetic resin and have poor adhesion to the synthetic resin. In particular, when the colloidal particles are formed into a film or the like, voids are generated at the interface with the colloidal particles. Moreover, there are still problems such as colloidal particles falling off when used as a magnetic tape.

[0006]

An object of the present invention is to use inorganic compound particles having a small average particle diameter as a mother particle, and child particles made of a synthetic resin are attached to the surface of the mother particle, or the surface of the mother particle is coated with a synthetic resin film. It is an object of the present invention to provide a stable colloidal solution containing the prepared organic / inorganic composite colloidal particles and a method for producing the same.

Another object of the present invention is to obtain a synthetic resin molded product obtained by dispersing the above colloidal solution in a reaction system of a synthetic resin, particularly an organic resin suitable as a film-shaped molded product such as a magnetic tape. It is intended to provide a synthetic resin molded body containing inorganic composite colloidal particles.

[0008]

The structure of the present invention will be described below. 1. Colloidal Solution As the mother particles of the colloidal solution according to the present invention, inorganic compound colloidal particles having an average particle size of 1000 nm or less, preferably 800 to 7 nm are used. When the particle size of the inorganic compound colloidal particles exceeds 1000 nm, the stability as a colloidal solution is poor, and when it is used as an additive for a synthetic resin, when the synthetic resin is formed into a film, there are many coarse projections on the film surface. Therefore, it is not preferable.

As the inorganic compound colloidal particles, it is possible to use single or composite oxide colloidal particles or a mixture thereof. For example, examples of the single colloidal particles include silica, alumina, titania, zirconia, iron oxide, and the like.Examples of the composite oxide colloidal particles include composite oxide colloidal particles of the above oxides and other inorganic oxides. Be done. In particular, silica and inorganic oxides other than silica, such as 3A group, 3B group, 4A group, and 4 of the periodic table.
Oxides of metal or non-metal elements of Group B, Group 5A, Group 5B, Group 6A, specifically Al ₂ O ₃ , B ₂ O ₃ , TiO _2.
3 , ZrO ₃ , SnO ₂ , Ce ₂ O ₃ , P ₂ O ₅ , Sb
Preference is given to composite oxide colloidal particles consisting of one or more of ₂ O ₃ , MoO ₃ , WO _{3 and the} like.

It is considered that these colloidal particles have pores inside, the specific surface area is large, and the ζ potential of the colloidal particles themselves is high. Therefore, the change in ζ potential due to pH adjustment is small and the pH adjusting operation is easy. Is. In addition, even if child particles made of synthetic resin are attached to the surface of the colloidal particles or a coating film of synthetic resin is formed, the colloidal solution is particularly stable. The composite ratio (molar ratio) of silica to the inorganic oxide is appropriately in the range of 0.5 to 20.
When the molar ratio exceeds 20, the specific surface area of the inorganic compound colloidal particles becomes small, while when it is less than 0.5, the specific surface area of the colloidal particles hardly increases. In addition, the stability of the colloidal solution becomes poor, which is not preferable.

Regarding the colloidal solution in which the above-mentioned composite oxide colloidal particles composed of silica and an inorganic oxide other than silica are dispersed and a method for producing the same, Japanese Patent Application No. 3-83578 filed by the applicant of the present application has been filed. It is described in.

In the present invention, the synthetic resin that adheres or forms a film on the surface of the mother particles is an acrylic resin,
Polystyrene, polyethylene, polyester, polyvinyl chloride, phenol resin, fluororesin, melamine resin,
Examples thereof include silicone resin, benzoguanamine resin, vinylidene fluoride resin and the like.

The average particle size of the child particles adhering to the surface of the mother particles is 1/5 to 1/1 / the average particle size of the mother particles.
It is desirable to be in the range of 40, preferably 1/10 to 1/30. When this average particle diameter ratio exceeds 1/5, aggregates of mother particles are likely to occur through the child particles, while when the particle diameter ratio is less than 1/40, aggregates of child particles are formed. It tends to occur, and it is a stable organic substance in a monodisperse state.
It is not desirable because it is difficult to obtain inorganic composite colloidal particles.

The ratio of the synthetic resin and the inorganic oxide in the organic-inorganic composite colloidal particles is preferably in the range of 0.1 to 50 parts by weight based on 100 parts by weight of the inorganic oxide. When the proportion of the synthetic resin is less than 0.1 part by weight, the desired effect of the present invention cannot be obtained when the organic / inorganic composite colloidal particles are added to the synthetic resin described later. Further, when the proportion of the synthetic resin exceeds 50 parts by weight, the thickness of the coating film formed on the surface of the mother particles simply increases, and when the organic / inorganic composite colloidal particles are added to the synthetic resin described later. The effect remains the same and it is not economical.

The colloidal solution containing the organic-inorganic composite colloidal particles according to the present invention is in the concentration range of a usual colloidal solution, for example, in the range of 5 to 40% by weight, and water and / or
Alternatively, an organic solvent is used as the dispersion medium. As the organic solvent, alcohols, glycols, esters, ketones and aromatic compounds can be used, and specifically, methanol,
Ethanol, butanol, isopropyl alcohol, n
Examples include usual organic solvents such as butyl alcohol, ethylene glycol, propylene glycol, ethyl cellosolve, methyl cellosolve, methyl ethyl ketone, acetone and toluene.

2. Method for Producing Colloidal Solution A method for producing a colloidal solution according to the present invention is a method for producing a colloidal solution having a negative ζ potential as a base particle.
After mixing a colloidal aqueous solution containing, as child particles, synthetic resin colloidal particles having a ζ potential of the same sign as the mother particles, the mixed colloidal aqueous solution is treated with a cation exchange resin, or An acid is added to adjust the pH of the mixed colloidal aqueous solution to a range of 2 to 7.

As the colloidal aqueous solution containing the inorganic compound colloidal particles, a commercially available colloidal aqueous solution or the colloidal aqueous solution described in Japanese Patent Application No. 3-83578 can be used. According to the invention according to the above application, an alkali metal silicate and an alkali-soluble inorganic compound,
Alkali metal silicate is added to an aqueous alkali solution having a pH of 10 or more at the same time to generate colloidal particles without controlling the pH of the reaction solution, or in a dispersion of pH 10 or more in which seed particles are dispersed. An alkali-soluble inorganic compound is added at the same time, and the particles of the composite oxide are grown by using seed particles as nuclei without controlling the pH of this dispersion liquid. A colloidal solution of inorganic oxide is produced.
The colloidal particles produced by such a method have a negative ζ potential, and the value is about −30 to −50 mV.

An aqueous solution containing colloid particles made of a synthetic resin having a negative ζ potential is mixed with the colloidal aqueous solution, and the mixed colloidal aqueous solution is treated with a cation exchange resin, or an acid is added to the mixed colloidal aqueous solution. When the pH of the aqueous colloid solution is adjusted to be in the range of 2 to 7, preferably in the range of 3 to 5, a stable aqueous colloid solution containing organic-inorganic composite colloid particles in which the child particles are attached to the surface of the mother particles is obtained. Be done.

The colloidal aqueous solution containing the synthetic resin colloidal particles can be selected from commercially available ones. Further, as the acid to be added, either a mineral acid or an organic acid can be used. The colloidal solution using water as a dispersion medium obtained by such a method can be made into a colloidal solution using an organic solvent as a dispersion medium by an ordinary method such as ultrafiltration or solvent substitution by heating.

Another method for producing a colloidal solution according to the present invention is to prepare a colloidal aqueous solution having a pH of 4.5 or less containing inorganic compound colloidal particles having a positive ζ potential as a mother particle, and a ζ having the same sign as the mother particle. After mixing a colloidal aqueous solution containing synthetic resin colloidal particles having an electric potential as child particles, the mixed colloidal aqueous solution is treated with an anion exchange resin, or alkali is added to adjust the pH of the mixed colloidal aqueous solution to 5 to 7 It is characterized by adjusting to the range of.
As the alkali to be added, ammonia, caustic soda,
Inorganic or organic basic compounds such as amines can be used.

The above-mentioned manufacturing method uses the pH of the colloidal solution.
The mother particles and the daughter particles exhibiting different changes in the ζ electric potential within the region of the same sign with respect to the change are used to attach the daughter particles to the surface of the mother particles. That is, in the case of a mixed colloidal solution of mother particles and child particles having a negative ζ potential, p
When the H value is changed in the range of 2 to 7 and the mixed colloidal solution of mother particles and child particles having a positive ζ potential is
When the value is changed in the range of 5 to 7, the ζ potential of either the mother particle or the child particle does not change so much,
The ζ potential of the other particle approaches zero. Therefore, the repulsive force between the mother particles and the child particles is weakened, and the child particles adhere to the surface of the mother particles. As a result, the surface of the mother particle to which the child particles are attached has a high ζ.
Since it has an electric potential, a stable colloidal solution can be obtained.

Further, in the method of the present invention, the colloidal aqueous solution and / or the colloidal organic solvent solution containing the organic / inorganic composite colloidal particles in which the child particles made of the synthetic resin are attached to the surface of the mother particles are the synthetic resin as the child particles. A stable colloidal solution containing organic-inorganic composite colloidal particles having a coating film of the synthetic resin formed on the surface of the mother particles is heated by heating to a temperature not lower than the softening temperature, preferably about 1 to 10 ° C. I will get it.

3. Molding of synthetic resin containing colloidal particles
Body A synthetic resin molded article containing colloidal particles according to the present invention is prepared by blending a colloidal solution containing water or an organic solvent as a dispersion medium in a reaction system of a synthetic resin raw material to produce the organic-inorganic composite colloidal particles. It is desirable to contain 0.01 to 10% by weight, preferably 0.5 to 8% by weight. When the content is less than 0.01, the effect of adding the organic-inorganic composite colloidal particles is not sufficiently exhibited, and when it exceeds 10% by weight, the characteristics of the synthetic resin are impaired, which is not desirable.

Examples of synthetic resins containing organic / inorganic composite colloidal particles include melamine resins such as alkyd melamine and acryl melamine, urea resins, polyester resins such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyethylene, Examples thereof include polypropylene, polystyrene, polyvinyl chloride, acrylic resin, phenol resin, urethane resin, silicone resin, and fluorine resin. The synthetic resin and the synthetic resin that adheres or forms a coating on the surface of the mother particles may be the same resin or different resins.

The synthetic resin molded product of the present invention can be obtained by a commonly used method. For example, in the case of a polyethylene terephthalate (PET) film molded product, an organic / inorganic composite colloidal solution containing ethylene glycol as a dispersion medium is added to the polyester reaction system for polycondensation. This colloidal solution may be added before the transesterification or esterification reaction at the time of polyester production and during the initial stage of the polycondensation reaction. The polyester in which the organic / inorganic composite colloidal particles are blended can be formed into a biaxially stretched film molded body by a conventional method.

[0026]

EXAMPLES The present invention will be specifically described below with reference to examples. Reference Example 1 A mixture of 100 g of silica sol having an average particle size of 480 nm and SiO ₂ concentration of 20% by weight and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and in this mother liquor, 9.4 kg of a 1.5 wt% sodium silicate aqueous solution as SiO ₂ and 9.4 kg of a 0.5 wt% sodium aluminate aqueous solution as Al ₂ O _3. Was added at the same time. The addition rate was 26 ml / min, during which the temperature of the reaction solution was maintained at 80 ° C. The pH of the reaction solution was 12.5 immediately after addition.
, And then changed little. After the addition is complete
The reaction solution was cooled to room temperature to obtain a SiO ₂ · Al ₂ O ₃ composite oxide colloidal solution.

The average particle diameter of the colloidal particles dispersed in this complex oxide colloidal solution was 500 nm, and the specific surface area of the colloidal particles was 180 m ² / g. The specific surface area is determined by the titration method [Analytical Ch
entity Vol. 28, No. 12 (195
6)] and the average particle diameter was measured by the dynamic light scattering method. The obtained composite oxide colloidal solution was washed with water using an ultrafiltration membrane and concentrated to obtain a 20% by weight colloidal solution as an oxide.

Example 1 Colloidal aqueous solution containing silica-alumina composite oxide colloidal particles having an average particle size of 500 nm obtained in Reference Example 1 (oxide concentration 20% by weight, pH 10.1, zeta potential -30).
mV) 50 g and a colloidal aqueous solution of polymethylmethacrylate (PMMA) particles having an SO ₃ Na terminal group having an average particle diameter of 32 nm (manufactured by Nippon Paint, Microgel E).
-2002, ζ potential -23 mV, concentration 29.5% by weight)
3.8 g was mixed to obtain a mixed colloidal aqueous solution having a pH of 9.8.

While stirring this mixed colloidal aqueous solution at room temperature, a strongly acidic ion exchange resin (DI, manufactured by Mitsubishi Kasei Co., Ltd.) was added.
AION, SK-1B) is gradually added until the pH of the aqueous colloid solution reaches 4.6, and after stirring for 2 hours, the ion exchange resin is removed, the solid content concentration is adjusted, and the silica-alumina composite oxidation is performed. A stable colloidal aqueous solution was obtained in which organic-inorganic composite colloidal particles in which PMMA particles were uniformly attached as child particles to the surface of mother particles composed of organic colloidal particles were monodispersed. The ζ-potential of the organic / inorganic composite colloidal particles in this colloidal aqueous solution was −18 mV. A scanning electron micrograph of the colloidal particles is shown in FIG.

Next, 90 g of ethylene glycol was added to this colloidal aqueous solution, and the mixture was heated to 110 ° C. by a rotary evaporator to evaporate the water, and a PMMA film was formed on the surface of the mother particles containing ethylene glycol as the dispersion medium. A stable colloidal solution containing organic-inorganic composite colloidal particles was obtained. A partial scanning electron micrograph of a cross section of the colloidal particles in this colloidal solution is shown in FIG.

In the organic-inorganic composite colloidal particles shown in FIG. 1, the particles of PMMA are attached to the surface of the mother particles, whereas the organic-inorganic composite colloidal particles shown in FIG. It is observed that the PMMA film is formed on the surface of the mother particles. The conditions for preparing the above colloidal solution are summarized in Table 1, and the properties of the colloidal solution are shown in Table 2.

Example 2 In Example 1, instead of the aqueous colloidal solution of PMMA particles, an aqueous colloidal solution of polystyrene (PST) particles having an average particle diameter of 55 nm and having SO ₃ Na terminal groups (manufactured by Nippon Paint, Microgel E-5001). , Ζ potential-2
0 mV, concentration 19.7 wt%) 6.4 g was used, except that silica-alumina composite oxide colloidal particles were used as mother particles and PST particles were attached as child particles to the surface thereof in the same manner as in Example 1. A stable colloidal aqueous solution in which organic / inorganic composite colloidal particles were monodispersed was obtained.

Then, this colloidal aqueous solution was heated and solvent-substituted with ethylene glycol in the same manner as in Example 1 to obtain a stable colloidal solution containing organic-inorganic composite colloidal particles having a PST film formed on the surface of mother particles. Prepared.
The preparation conditions and properties of this colloidal solution are shown in Tables 1 and 2.

Example 3 Average particle size 300 nm prepared by the same method as in Reference Example 1
Aqueous colloidal solution containing colloidal particles of silica / alumina composite oxide of (oxide concentration 20% by weight, specific surface area 35
0 m ² / g, pH 10.5, ζ potential -30 mV) 50 g
And a colloidal aqueous solution of silicone particles having an average particle diameter of 27 nm and having COONa end groups (Toray Dow Corning Silicone BY-22-840, ζ potential -21 m
V, concentration 32.6% by weight) 4.9 g,
A mixed colloidal solution of 10.0 was obtained. This mixed colloidal solution was treated in the same manner as in Example 1 to monodisperse organic-inorganic composite colloidal particles having a silicone coating formed on the surface of mother particles composed of silica-alumina composite oxide colloidal particles. A stable aqueous colloid solution was obtained.

Next, this colloidal aqueous solution is heated at 110 ° C. for 2 hours, further subjected to cation exchange, ethyl alcohol is added, and the dispersion medium is replaced by the ultrafiltration membrane method to use ethyl alcohol as the dispersion medium. A colloidal solution containing organic / inorganic composite colloidal particles in which child particles composed of silicone particles were attached to the surface of mother particles was prepared. The preparation conditions and properties of this colloidal solution are shown in Tables 1 and 2.

Example 4 A colloidal aqueous solution containing commercially available silica colloidal particles having an average particle size of 697 nm (manufactured by Catalysts & Chemicals Industries, silica concentration 10
% By weight, specific surface area 4 m ^{2 /} g, pH 9.6, ζ potential-2
3 mV) 100 g and SO ₃ Na having an average particle diameter of 58 nm
A colloidal aqueous solution of PMMA particles having an end group (manufactured by Nippon Paint, Microgel E-2002, ζ potential -24
mV, concentration 19.8% by weight) 5.7 g, and 1% hydrochloric acid aqueous solution was gradually added to the obtained mixed colloid solution until the pH became 5.0, and the surface of the mother particles composed of silica colloid particles was mixed. A stable colloidal aqueous solution was obtained in which organic / inorganic composite colloidal particles having PMMA particles attached thereto as the child particles were monodispersed.

This aqueous colloidal solution was heated and solvent-substituted with ethylene glycol in the same manner as in Example 1 to prepare a stable colloidal solution containing organic-inorganic composite colloidal particles having a PMMA coating film formed on the surface of the mother particles. .. The preparation conditions and properties of this colloidal solution are shown in Tables 1 and 2.

Example 5 A mixed solution of 100 g of silica sol having an average particle size of 600 nm and a SiO ₂ concentration of 40% by weight, 2000 g of ethyl alcohol and 3.8 g of 28% aqueous ammonia solution was prepared. After holding this mixed solution at 15 ° C., a mixed solution of 4.8 g of aluminum isopropoxide and 235.2 g of isopropyl alcohol and 22.8 g of 0.1% by weight ammonia aqueous solution were added over 2 hours. After that, stirring was continued for 1 hour, the mixture was heated to 60 ° C., aged for 1 hour, and then cooled to room temperature to obtain an alumina-modified silica colloidal solution.

Next, this colloidal solution was washed with water by an ultrafiltration membrane method and concentrated to obtain a 5% by weight colloidal aqueous solution as an oxide. The pH of the aqueous solution was 9.5 and the ζ potential was -7 mV. Further, a 1% hydrochloric acid aqueous solution was gradually added to this aqueous solution with stirring until the pH was 4.2, and a positive ζ was added.
An aqueous solution of colloidal particles having a potential of 18 mV was obtained. This colloidal solution was concentrated by an ultrafiltration membrane method to prepare a stable aqueous colloidal solution having an oxide content of 20% by weight and an average particle size of 638 nm.

50 g of the above colloidal aqueous solution and a colloidal aqueous solution of silicone particles having an NH ₂ terminal group having an average particle diameter of 29 nm (manufactured by Toray Dow Corning Silicone, B
3.6 g of Y-22-830, ζ potential of 28 mV, and concentration of 19.3% by weight) were mixed to obtain a mixed colloidal solution of pH 4.7. While stirring this mixed colloidal solution at room temperature,
Weakly basic ion exchange resin (Mitsubishi Kasei, DIAION,
WA20) is gradually added until the pH of the aqueous colloid solution becomes 6.7, stirring is continued for 2 hours, then the ion exchange resin is removed, and silicone particles as child particles are formed on the surface of mother particles made of alumina-modified silica colloid particles as child particles. A stable colloidal aqueous solution in which the organic-inorganic composite colloidal particles uniformly adhered to each other were monodispersed was obtained.

Next, this colloidal aqueous solution was heated and solvent-substituted with ethylene glycol in the same manner as in Example 1 to obtain a stable colloidal solution containing organic-inorganic composite colloidal particles having a silicone film formed on the surface of mother particles. Prepared. The preparation conditions and properties of this colloidal solution are shown in Tables 1 and 2.

Comparative Example 1 Instead of the colloidal solution of PMMA particles used in Example 4, N having a positive ζ potential of 10 mV and an average particle size of 62 nm was used.
A colloidal aqueous solution of PMMA particles having an H ₂ end group (manufactured by Nippon Paint, Microgel SKKE-4, concentration 2
(9.6 wt%) 5.0 g was mixed with the silica colloid aqueous solution used in Example 4 and stirred at room temperature. When this mixed colloidal solution was allowed to stand for a while, precipitation of aggregated silica colloidal particles was observed, and a stable colloidal solution could not be obtained. The preparation conditions and properties of this colloidal solution are shown in Tables 1 and 2.

[0043]

[Table 1] Preparation conditions for colloidal solution Mixing adjustment of particle size of mother particles and child particles pH Average particle size (A ) Average particle size (B ) ratio (B / A ) Weight ratio Example 1 500nm 32nm 0.064 0.112 4.6 Implementation Example 2 500 55 0.110 0.126 4.6 Example 3 300 27 0.090 0.160 4.6 Example 4 697 58 0.083 0.113 5.0 Example 5 638 29 0.045 0.069 6.7 Comparative Example 1 697 62 0.089 0.148 5.0

[0044]

[Table 2] Properties of colloidal solution Average particle of solid particles of dispersion medium Stability of synthetic resin ( * 1 ) Concentration ratio of aggregate diameter (* 2 ) (* 3 ) ( * 4 ) Example 1 Water 10 wt% None − − ○ Example 1 No Eg 10 510 nm 10.8 wt% ○ Example 2 No water 10 − − ○ Example 2 No Eg 10 520 13.6 ○ Example 3 No water 10 − − ○ Example 3 No Et 10 340 14.9 ○ Implementation Example 4 No water 10 − − ○ Example 4 Eg 10 no 730 12.4 ○ Example 5 Water 10 no − − ○ Example 5 Eg 10 no 660 5.8 ○ Comparative Example 1 Water 10 yes − − × * 1) Eg; ethylene Glycol Et; Ethyl alcohol * 2) The particle size of the composite colloidal particles was measured with an ultracentrifugation automatic particle size distribution analyzer. * 3) Percentage of synthetic resin attached or coated on the mother particles. Separate the colloidal particles with a small centrifuge and
With respect to the sample dried at 50 ° C. for 20 hours, the weight loss of 150 to 1000 ° C. was determined as the amount of synthetic resin by a thermogravimetric analyzer. * 4) ◯: Colloidal particles do not aggregate even if left for one week. X: Immediately agglomeration of colloid particles was observed and precipitation occurred.

Example 6 A polyester film is manufactured by mixing the organic-inorganic composite colloidal solution of the present invention with a reaction system of a synthetic resin raw material. 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, 0.01 parts by weight of calcium acetate as a transesterification catalyst, and 0.03 parts by weight of antimony trioxide as a polycondensation catalyst are added, and the mixture is heated to 220 ° C. and methanol is added. Distilled off to complete the transesterification reaction.

Subsequently, 0.04 part by weight of trimethyl phosphate and 0.4 part by weight of an organic / inorganic composite colloidal solution containing ethylene glycol prepared in Example 1 as a dispersion medium were added to the system. Then, the system was gradually depressurized and ethylene glycol was distilled off at a temperature of 290 ° C. under a reduced pressure of 1 mmHg, and a polycondensation reaction was carried out for 4 hours to obtain a polyester having an intrinsic viscosity of 0.62. Intrinsic viscosity is polyester (15
(Parts by weight) and tetrachloroethane (10 parts by weight) were dissolved in a mixed solvent and measured at 25 ° C. by an Ostwald viscometer.

The polyester obtained was processed with an extruder to obtain 29
A sheet was formed at 0 to 300 ° C., and biaxially stretched at 90 to 100 ° C. to obtain a 25 μm film. This polyester film had few voids at the interface of colloidal particles and had uniform particle irregularities, and aggregated particles were not observed. The observation of voids and agglomerated particles was performed with a transmission electron microscope.

[0048]

INDUSTRIAL APPLICABILITY The colloidal solution according to the present invention is stable for a long period of time and is used as an additive (filler) to a synthetic resin, as well as an antistatic agent, an antiblocking agent, a filler for supporting an organic substance, a dye or a metal, Cosmetics, toners, additives for improving the texture of fibers, waterproofness or abrasion resistance, auxiliaries such as lubricants, leveling agents, defoamers, fillers for paints, resin hard coat agents, slippery steel sheets It is suitable for use as an imparting agent.

Further, the synthetic resin molding containing the colloidal particles according to the present invention can be molded into a fiber, a film, or any other desired shape according to various uses. The colloidal particles have an adhesiveness with the synthetic resin. Since it has good and uniform unevenness, it exhibits a particularly excellent effect in improving the surface smoothness of the film molded product.

[Brief description of drawings]

FIG. 1 is a scanning electron micrograph of the colloidal particles obtained in Example 1.

FIG. 2 is a partial scanning electron micrograph of a cross section of the colloidal particles obtained in Example 1.

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[Procedure amendment]

[Submission date] December 14, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Change

[Correction content]

[Brief description of drawings]

FIG. 1 is a scanning electron micrograph showing the particle structure of colloidal particles obtained in Example 1.

2 is a scanning electron micrograph showing a particle structure of a cross section of the colloidal particles obtained in Example 1. FIG.

Claims (6)

[Claims] 1. An inorganic compound colloidal particle having an average particle diameter of 1000 nm or less is used as a mother particle, and child particles made of a synthetic resin are attached to the surface of the mother particle, or the surface of the mother particle is a synthetic resin film. A colloidal solution containing organic-inorganic composite colloidal particles coated with. 2. The colloidal solution according to claim 1, wherein the dispersion medium is water and / or an organic solvent. 3. A colloid containing, as a mother particle, a colloidal aqueous solution having a pH of 8 or more containing inorganic compound colloidal particles having a negative ζ potential as a mother particle, and colloidal particles made of a synthetic resin having a ζ potential having the same sign as the mother particle as a child particle. A method for producing a colloidal solution, which comprises mixing an aqueous solution and then adjusting the pH of the mixed colloidal aqueous solution to a range of 2 to 7 to attach the child particles to the surface of the mother particles. 4. A colloidal aqueous solution having a pH of 4.5 or less containing, as mother particles, colloidal particles of an inorganic compound having a positive ζ potential, colloidal particles made of a synthetic resin having a ζ potential having the same sign as the mother particles are used as child particles. A method for producing a colloidal solution, comprising: mixing a colloidal aqueous solution containing the mixture, adjusting the pH of the mixed colloidal aqueous solution to a range of 5 to 7, and attaching the child particles to the surface of the mother particles. 5. The colloidal solution containing colloidal particles having child particles attached to the surface of the mother particles is heated to a temperature equal to or higher than the softening temperature of the synthetic resin to be the child particles. A method for producing the colloidal solution described. 6. An inorganic compound colloidal particle having an average particle diameter of 1000 nm or less is used as a mother particle, and child particles made of a synthetic resin are attached to the surface of the mother particle, or the surface of the mother particle is a synthetic resin film. A synthetic resin molded product containing organic-inorganic composite colloidal particles coated with.