JP2001288369A - Resin composition and resin film made from the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having characteristics of both polyester and particles and having good moldability and heat resistance in the molding for producing a molded product. SOLUTION: This resin composition comprises a resin and particles and is characterized by that the particles are inorganic particles composed mainly of silicon, have lower intensity of hydroxy-bonded silicon than that of hydroxy- unbonded one when observed by 29Si CP-MASNMR analysis and are contained in the resin composition at a rate of 25-90 wt.%. The resin film is characterized by being made from the resin composition, or in the case of a laminated film, at least one layer thereof is characterized by being made from the resin composition described in one of the claim 1-7 (See the specification).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which combines the properties of a resin and inorganic particles, but also resists deformation into a film or the like, and a resin film comprising the same.

[0002]

2. Description of the Related Art It has been widely practiced to incorporate fine particles such as inorganic particles into a resin such as polyester. And it is widely used as fiber, film and other molded products.

[0003] The purpose of adding particles is to improve slipperiness and abrasion resistance and to function as a bulking agent.

[0004] Particles generally include silicon oxide, aluminum oxide, titanium oxide, calcium carbonate, barium sulfate,
Inorganic particles such as calcium phosphate, talc, kaolin, zeolite, calcium fluoride, lithium fluoride, and molybdenum sulfide, and organic particles such as silicone resin, fluorine resin, cross-linked polystyrene resin, cross-linked acrylic resin, and also formed during polyester polymerization Precipitated particles are used.

However, as the amount of added particles increases, the fluidity of the composition decreases, and it is difficult to obtain a molded product, or even if it is obtained, the yield is low. It was difficult to obtain moldability.

[0006] In recent years, studies have been actively conducted to form an advanced composite state such as an inorganic substance and an organic substance or a polymer alloy as a nanocomposite. However, the resin itself may be deteriorated, and a practical product can be obtained. There are limitations on the type of resin.

On the other hand, when a large amount of particles are contained, if heat is applied during molding or the like, the problem that the matrix resin is deteriorated by the action of the particles must be considered.

[0008]

SUMMARY OF THE INVENTION In view of the background of the prior art, the present invention relates to a resin having both the properties of polyester and the properties of particles, and having good moldability and heat resistance even when formed into a molded article. It is intended to provide a composition and a resin film comprising the composition.

[0009]

The present invention employs the following means in order to solve the above-mentioned problems. That is, the resin composition of the present invention is a resin composition obtained by adding particles to a resin, wherein the particles are inorganic particles containing silicon as a main component and ²⁹ Si CP-MAS NMR.
The strength of the hydroxyl-bonded silicon as observed by analysis is smaller than the strength of the non-hydroxyl-bonded silicon, and the resin composition contains 25 to 90% by weight of the particles, and The resin film of the present invention is characterized by being constituted by such a resin composition, and at least one layer of the laminated film is formed from the resin composition according to any one of claims 1 to 7. Characterized in that it is a layer consisting of Is achieved.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a resin composition having both the above-mentioned problems, that is, the properties of polyester and the properties of particles, and also having good moldability and heat resistance when molded articles are formed, and a resin film comprising the same. The present inventors have conducted intensive studies and have made the resin contain specific inorganic particles in a specific amount. As a result, they have surprisingly found that such a problem can be solved all at once.

The resin used in the present invention is not particularly limited. However, considering that it is used as a moldable resin, polyester, polyamide, polyetheretherketone, polyketone, polyether, polystyrene, Polyolefin, chlorinated vinyl or vinyl acetate,
Vinyl-based resins such as acrylic acid compounds, silicone resins, fluorine resins, epoxy resins, urea resins, phenolic resins, and, among these, wholly aromatic ones or liquid crystalline resins, and the like. For example, a copolymer such as a styrene-acrylonitrile-butylene copolymer or a mixture thereof may be used. Among them, polyesters, polyamides, polyolefin resins and epoxy resins which can be melt-molded are preferred, and polyesters are particularly preferred.

For example, the polyester is composed of a dicarboxylic acid component and a glycol component, and is produced by, for example, an esterification or transesterification reaction of a dicarboxylic acid or an ester-forming derivative thereof with a glycol, and a subsequent polycondensation reaction. .

The type of polyester is not particularly limited as long as it can be formed into a molded product such as a film. Suitable polyesters that can be molded into molded articles such as films include those using an aromatic dicarboxylic acid as the dicarboxylic acid component, such as polyethylene terephthalate, polyethylene-p-oxybenzoate,
Polyethylene-1,2-bis (2-chlorophenoxy)
Ethane-4,4'-dicarboxylate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate, polyethylene-2,6-naphthalenedicarboxylate, polybutylene terephthalate, polycyclohexane- 1,4-dimethylene terephthalate, etc., among which polyethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polybutylene terephthalate, poly-1,3-trimethylene terephthalate, and copolymers or blends thereof Is preferably used.

Of course, these polyesters are copolyesters, and the copolymerization components thereof include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids other than the acid components and glycol components constituting the polyester. Glycol components such as acid components, aromatic glycols, aliphatic glycols and alicyclic glycols may be copolymerized, and such components include, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid,
Phthalic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxyethane dicarboxylic acid, 5
Aromatic dicarboxylic acids such as sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, aliphatic dicarboxylic acids such as dimer acid, maleic acid, fumaric acid, 1,4-cyclohexanedicarboxylic acid, decalin dicarboxylic acid And the like can be used.

The glycol components include ethylene glycol, 1,3-trimethylene glycol, 1,4-
Aliphatic glycols such as butanediol, 1,5-pentanediol, neopentyl glycol, diethylene glycol, 1,6-hexanediol, and 1,10-decanediol; 1,2-cyclohexanedimethanol;
Alicyclic glycols such as 4-cyclohexanedimethanol and hydrogenated bisphenol A can be mentioned.
Among these glycol components, ethylene glycol,
1,3-Trimethylene glycol, 1,4-butanediol, and 1,4-cyclohexanedimethanol are preferably employed.

The above-mentioned acid component and glycol component may be used alone or in combination of two or more. Further, these copolymer components may be by-produced when producing the polyester.

Further, the amount of carboxy terminal groups in the polyester composition is preferably from 10 to 100 equivalents / ton. The lower limit is preferably 12 equivalents / ton, more preferably 15 equivalents / ton. The upper limit is preferably 80 equivalents / ton, more preferably 70 equivalents / ton. When the content is in such a range, a material having good heat resistance and moldability can be obtained.

The amount of the diol condensate in the polyester composition is preferably 5% by weight or less. The lower limit is preferably 4.5% by weight or less, more preferably 4% by weight or less, and particularly preferably 3.5% by weight or less. The upper limit is not particularly limited, but is preferably 0.5% by weight or more from the viewpoint of obtaining appropriate moldability. When the amount of the diol condensate exceeds 5% by weight, the heat resistance is deteriorated, and the diol condensate is easily deformed at low temperature or low stress, so that the function as a molded article is easily hindered.

Further, the resin used in the resin composition of the present invention is preferably a crystalline thermoplastic resin. In this case, the crystallization temperature at elevated temperature of the resin composition is Tc, and the crystallization temperature at high temperature is Is Tc ′, (Tc′−Tc) is 85
C. or lower, more preferably 75.degree. C. or lower, even more preferably 70.degree. C. or lower. Although the lower limit is not particularly limited, about 45 ° C. is one standard. When the glass transition temperature is Tg, (Tc-T
g) is preferably 20 ° C. or higher. It is more preferably at least 30 ° C, further preferably at least 40 ° C, particularly preferably at least 50 ° C. Although the upper limit is not particularly limited, about 100 ° C. is one standard. By using such a resin composition, mechanical properties, gas barrier properties, and heat deformation resistance are good, and whitening, tearing, cracking, and embrittlement in molding processing such as stretching can be suppressed, and the thickness is 100 μm or less. , Preferably 75 μm or less, more preferably 50 μm or less, particularly preferably 30 μm or less.

The particles used in the present invention are inorganic particles containing silicon as a main component. Here, the term “main component” means that the metal element occupies 50% or more as a weight ratio in terms of oxide, preferably 55% or more, more preferably 6% or more.
0%. The upper limit is preferably 90% or less, more preferably 80% or less. When the content ratio is small, it becomes difficult to control the fluidity, the fluidity when a large number of particles are blended is deteriorated, and it becomes difficult to form a molded body itself,
Conversely, when the amount is large, it is difficult to control the dispersibility, and the molded product becomes brittle. In addition, there is an adverse effect on moldability.

Further, the particles used in the present invention preferably contain at least two kinds of metal elements as metal elements other than silicon. It is more preferably at least 3 components, particularly preferably at least 4 components. It is preferable that the above conditions be satisfied except for the alkali metal and the alkaline earth metal. The particles are oxides, and as a metal element other than silicon, aluminum oxide is 0.8: 1 in terms of silicon oxide ratio.
０．２0.2: 1 content is preferable. When such conditions are satisfied, properties such as moldability and mechanical properties of a molded article can be improved.

The particles used in the present invention are characterized in that the peak intensity of hydroxyl-bonded silicon is smaller than that of non-hydroxyl-bonded silicon in ²⁹ Si CP-MAS NMR analysis in the method described in the following Examples. Here, the intensity is represented by the peak area, and the ratio of the peak area obtained by dividing the peak intensity of the hydroxyl-bonded silicon by the intensity of the non-hydroxyl-bonded silicon is more preferably 0.8 or less, still more preferably 0 or less. 0.7, particularly preferably 0.6 or less. The lower limit is not particularly limited, but is not more than 0.
About 1 is appropriate. The method for measuring hydroxyl-bonded silicon in such an example is a method in which silicon having hydroxyl groups bonded is essentially emphasized and observed.

In the present invention, the specific particles are:
It is necessary to contain 25 to 90% by weight. The lower limit is preferably at least 30% by weight, more preferably 4% by weight.
It is at least 5% by weight, particularly preferably at least 50% by weight.
By setting the content in such a range, a composite function of the particles and the matrix such as heat resistance and mechanical properties can be obtained, and also good processing suitability such as moldability can be obtained. The upper limit is preferably 80% by weight or less, more preferably 75% by weight.
Or less, particularly preferably 70% by weight or less. It is preferable in terms of such a range that the molding is facilitated and the yield and the like are improved, but in particular, the film or the blow molding may be stretched, but when applied to a molding method requiring followability in such a deformation operation. , The upper limit is 80
It is preferable that the content be not more than% by weight.

The average particle size of the particles is as follows:
0.005 to 20 μm is preferred. The lower limit is preferably 0.01 μm or more, more preferably 0.07 μm.
μm or more, particularly preferably 0.1 μm or more. The upper limit is preferably 15 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. The present invention can be suitably processed into a film or a sheet-like material. At this time, if the average particle diameter is equal to or more than the lower limit, good characteristics in terms of slipperiness and abrasion resistance can be obtained. Further, if the average particle size is not more than the upper limit, the dropout of the particles in the processing step and the influence on the surface configuration at the time of the surface processing become negligible, and the yield and the product quality are improved.

The bulk density of the particles is as follows:
5.0 g / cm^ThreeThe following is preferred. More preferred
Or 4.0 g / cm^ThreeHereinafter, more preferably 3.5 g
/ Cm ^ThreeBelow, particularly preferably 3.0 g / cm^ThreeBelow
is there. The present invention contains a large amount of such specific particles.
The weight tends to be heavier, so is it a point of weight reduction?
Therefore, it is preferable to employ particles that satisfy the requirements.
It is. There is no particular lower limit, but the particle strength
0.3g / cm^ThreeAbove
That's right.

Also, when the particles used in the present invention are particles containing the same silicon as a main component and particles having different average particle diameters, the packing state in the composition can be improved. In addition, since the moldability as compared with the content is improved, it is preferably employed. Such an embodiment can be employed by performing mathematical processing from the particle size distribution curve.

The present invention does not prevent the inclusion of two or more types of particles, and further improves the slipperiness such as strength, the mechanical properties, and the composite functions such as flame retardancy, concealment and whiteness. From the expression, for example, aluminum, zinc,
Inorganic particles such as iron, titanium, zirconium, molybdenum, cerium, yttrium, tin, barium, calcium, magnesium, sodium, potassium, etc. oxides, sulfides, sulfates, nitrates, halides, carbonates, phosphates, etc. Can be used. In addition, acrylic acid, styrene, fluorine resin, organic particles and the like having a constituent component such as a silicone resin can also be used in combination as appropriate, but in order to more clearly exhibit composite characteristics,
It is preferred to use mainly inorganic particles.

Next, the method for producing the resin composition of the present invention will be described by way of an example, but the present invention is not limited to such description.

The method for obtaining the particles used in the present invention is not particularly limited as long as it satisfies the requirements of the present invention, but it is effective to control the shape, composition and surface active groups of the particles to obtain them. is there. For example, metal particles are oxidized in an oxidizing atmosphere at a temperature of 900 ° C. or higher, or
A method of heat treatment under high heat of 0 ° C. or more to degenerate hydroxyl groups while synthesizing particles, heating a metal ingot to evaporate a metal element, and, for example, in the case of an oxide, introducing nuclei into an oxidizing atmosphere. A method of performing growth, a method of baking the surface of particles obtained by a dry or wet method with microwaves or the like, or a method of treating an inorganic functional group on the surface with an organic substance to modify the surface. Among them, it is preferable and convenient to employ a method of treating metal oxide particles under high heat. The average particle size can be controlled by adjusting the particle growth time, atmosphere concentration, temperature, and the like. Examples of the post-treatment include a method in which particles are highly dispersed and a surface treatment is performed with a silane coupling agent, and a method in which the particles are highly dispersed and the surface is coated with an organic substance. Among them, a method of degenerating a hydroxyl group on the surface of a particle under high heat is preferably employed because it is industrially simple and efficient to achieve the object of the present invention.

At this time, the object of the present invention can be easily achieved by synthesizing particles by monitoring the amount of hydroxyl groups in ²⁹ Si CP-MAS NMR analysis. Also, as a control of the particle size, known classifying operation or pulverizing operation alone or in combination, to obtain particles of a required particle size, particle size distribution, or particles of a preferable particle size range by appropriately controlling the particle synthesis conditions. Can be prepared. The shape is preferably a spherical particle having a ratio of the major axis / minor axis on the projection plane of the particle of 1.1 or less.

As a method of introducing a metal element other than silicon into the particles, a method of melting the silicon into an alloy, a method of mixing fine powder to obtain a solid phase reaction, and a mixture of corresponding salts (preferably Is a solution state), a method of chemically treating a product obtained by the reaction, a method of using a natural mineral, and the like. Among them, a method of obtaining from a mixture of salts and a method of using a natural mineral are convenient. It is preferably adopted.

The method for incorporating the particles used in the present invention into a resin is not particularly limited, but may be a method of adding the resin before or during the polymerization step, or a uniaxial method having a vent port after the polymerization. Alternatively, a method of injecting powder or slurry into a twin-screw kneader, a method of dissolving a resin in a solution and dispersing particles therein, and the like, include a method of adding a resin or a resin during a polymerization step. A method of dissolving in a solution and adding particles is preferable because the present invention can be easily achieved.

At this time, when a slurry of the particles is used,
It may be an organic solvent or an aqueous solvent. Organic solvent slurries can also be obtained from water slurries by solvent displacement.

Hereinafter, a typical example is a polyester resin.
The addition to the resin will be described in more detail.

In addition to the polyester resin,
The mode of adding before or during the polymerization is preferably adopted from the viewpoint of dispersibility. As the polymerization method, for example, a so-called transesterification method using a dialkyl ester of dicarboxylic acid and glycol and a so-called direct polymerization method using dicarboxylic acid and glycol are preferably employed.

In the present invention, the amount of the carboxy terminal group of the catalyst or the polymer to be used can be appropriately adjusted. For example, an alkali metal acetate or the like is used as a transesterification catalyst, and a polymerization reaction catalyst is used. For example, an antimony oxide catalyst containing less germanium oxide or bismuth can be used, and among them, a germanium oxide catalyst is preferably used. Also,
A combination use of a transition metal compound such as cobalt or an alkoxy titanate can be preferably employed. By appropriately controlling the reaction conditions, the amount of the carboxy terminal group, the amount of the glycol condensate, the molecular weight distribution, and the like can be adjusted, and the thermal characteristics can be adjusted by designing the resin composition in addition to these. As the reaction conditions, for example, after adding particles and performing nitrogen replacement, the final degree of pressure reduction is 1 Pa or less, and the final temperature is 3 Pa.
A method of carrying out the polymerization at a temperature of not higher than 00 ° C.

The resin composition thus prepared can be molded by a known method. For example, to explain a specific method for producing a film made of the polyester composition of the present invention described above, after drying the polyester composition, melt-extruded to obtain an unstretched sheet, subsequently biaxially stretched, heat-treated, There is a method. The resin composition of the present invention has excellent moldability and can be preferably formed into a uniaxially or biaxially stretched film. Biaxial stretching can be suitably performed in any of longitudinal and transverse sequential stretching or biaxial simultaneous stretching. The stretching ratio is usually 2.0 to 2.0
A value of 5.0 is appropriate. Also, after biaxial stretching, further vertical,
It may be redrawn in any of the transverse directions. Further, the concentration of the particles can be adjusted by appropriately mixing the polyester containing each particle material and the polyester resin not containing the particles.
When used for a recording material such as synthetic paper, the temperature may be lower than Tg + 100 ° C. or 1000%.
An embodiment in which the film is stretched at a high speed of not less than / min is preferably employed.

Further, the resin composition of the present invention can be preferably used for a laminated film. When implemented as a laminated film, for example, a plurality of feeders, prepare an extruder, charge and melt each raw material, or obtained by laminating and extruding using a pinol at the time of melt molding,
After forming one layer, it can be cast and molded thereon. In the former case, the lamination thickness can be adjusted by making the melt viscosity of the raw materials as equal as possible and controlling the amount extruded from each extruder. In the present invention, any embodiment of a film using the composition of the present invention for the inner layer and a film using the composition of the present invention for at least one of the outer layers can be preferably used. In the film of the present invention, it is preferable to use the composition of the present invention for the outer layer, particularly when it is important to use the film for bending stiffness or recording material use, and to improve thermal properties such as heat conductivity and heat resistance. When hiding, hiding, whiteness, and smoothness of the film surface are important functions, the composition of the present invention is preferably used for the inner layer.

The resin composition and the film of the present invention may contain terminal blocking agents, ultraviolet absorbers, antioxidants, antistatic agents, surfactants, pigments, fluorescent brighteners, etc., as long as the purpose is not impaired. May be contained.

The thickness unevenness of the film of the present invention relative to the total film thickness is preferably 20% or less, more preferably 14% or less, and further preferably 10% or less.
There is no particular lower limit, but from the viewpoint of productivity 2%
It is about. When the thickness unevenness exceeds 20%, the quality as a molded article is inferior, and there is a concern that workability and flatness may deteriorate.

Further, if necessary, a coating layer can be formed on the film of the present invention. For forming the coating layer, a method of forming the coating layer at any time during the film forming process or off-line after the film formation is adopted, but since there is little concern that scratches are generated and the productivity is good, coating is performed at the time of film formation. Is preferred. For example, a method in which a coating agent is applied using a metaling bar, a gravure coater, or the like after casting and stretching, and drying and stretching are performed at the same time is employed.

[0042]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

The method of measuring the characteristic value in the present invention was performed by the following method. A. Average particle size and particle size distribution of particles
Observe at a magnification of 10,000 or more using M). The thickness of the section of the TEM is about 100 nm, and measurement is performed in 100 or more visual fields at different locations. The average diameter d of the particles is determined as an equivalent circle equivalent diameter. B. Chemical composition of particles Determined by X-ray fluorescence and atomic absorption spectrometry. C. Hydroxyl group ratio: ²⁹ Si CP-MAS NMR (CP-MA
S: Cross Polarization Magic Angle Spinning) The polyester composition was appropriately cut, introduced into a probe, and measured. The measurement conditions are as follows. The measurement was carried out at Toray Research Center Co., Ltd.

Measuring apparatus: Nuclear magnetic resonance (NMR) analyzer, CMX-300 NMR system, manufactured by CHEMAGNETICS Co., Ltd. Measurement conditions: Temperature: room temperature Resonant frequency: 59.642 Hz Pulse width: 90 ° pulse (4.4 μsec) Pulse repetition time: 7 seconds Data point: Data point 16k Sampling point 1k Spectral width: 50,000 Hz Pulse mode: Single Pulse with Proton Decoupling Number of times of accumulation: ６6400 Sample rotation speed: 5 kHz Data processing: Fourier transform was performed using an exponential function type window. The broadening factor was 100 Hz.

GRAMS was used for peak division.

In the spectrum chart obtained by the above measurement, the intensities (peak areas) of hydroxyl-bonded silicon (Si (OH) ₂ , SiOH) and non-hydroxyl-bonded silicon (SiO ₂ ) were determined, and the ratio was determined. D. Thermal properties (Tg, Tc, Tc ') A few mg of the polyester composition was introduced into an aluminum pan, and the robots DSC and RD manufactured by Seiko Electronic Industry Co., Ltd.
It was measured using C220. The measurement data was obtained from the behavior at the time of reheating, after being heated until it was once melted, rapidly cooled with liquid nitrogen.

The measuring conditions were as follows: under a nitrogen atmosphere, the temperature rising rate was 20 ° C./min, and the temperature decreasing rate was 20 ° C./min. E. FIG. Bulk density of particles 200 g of the particles are collected, the particles are introduced into a measuring cylinder, and the volume is measured by applying vibration to reduce the volume until the weight becomes constant. The bulk density was calculated by the following equation.

E. Bulk density = 200 / volume (cm ³ ) Intrinsic viscosity of polyester composition Using o-chlorophenol as a solvent, the intrinsic viscosity was measured at 25 ° C using an Oswald viscometer. The value is obtained by correcting the amount of added particles. E. FIG. Carboxy terminal group amount The polymer was dissolved in a mixed solvent of ortho-cresol / chloroform (weight ratio 7: 3) at 90 to 100 ° C, and determined by potentiometric titration using an alkali. The value is obtained by correcting the amount of added particles. F. Diol Condensate Amount 0.5 g of a sample was solvolyzed and analyzed by gas chromatography. G. FIG. Thickness unevenness of film The thickness was measured at least 500 points arbitrarily sampled from a film roll, and determined by the following equation.

(Maximum thickness−minimum thickness) / average thickness × 100 (%) Film Lamination Thickness The depth direction distribution of the particle concentration is measured using a secondary ion mass spectrometer, X-ray photoelectron spectroscopy, infrared analysis, or a confocal microscope. After obtaining a maximum value in the depth direction with respect to the surface, a depth that is の of the maximum value was defined as a lamination thickness. In addition, when the lamination thickness is small, it can be determined not only from the depth distribution of the particle concentration but also from the observation of the cross section of the film or a thin film level difference measuring instrument. I. Flame retardancy of the film Prepare a film of thickness 0.5mm, width 1.0cm, length 20cm, ignite from the bottom at 45 ° tilt, keeping the short side horizontal, observe the fire spread behavior, Judgment was made based on the following criteria.

◎: Spread within 3 cm ○: Spread within 5 cm △: Spread within 10 cm ×: Spread over 15 cm Example 1 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol Was subjected to a transesterification reaction using 0.09 part by weight of lithium acetate as a catalyst according to a conventional method.

On the other hand, the average particle size is 12.5 μm (1.2 μm
And a mixture of particles of the same composition having a peak at a position of 21 μm), SiO ₂ : Al ₂ O ₃ : Fe ₂ O ₃ : CaO: MgO
= 62.1: 22.8: 6.2: 2.1: 1.2 (weight ratio in terms of oxide), bulk density 1.2 g / cm ³ , hydroxyl group ratio 0.23, primary particle size ratio 1.05 composite oxide particles (manufactured by Chugoku Electric Power Co., Inc.) were dispersed in an ethylene glycol slurry, and further subjected to a dispersion treatment with a high-pressure homogenizer to prepare a composite oxide slurry having 20% by weight of the particles.

The slurry was added to the solution after the transesterification reaction, and the distillation of ethylene glycol was repeated.

Thereafter, 0.08 part by weight of antimony trioxide and 0.1 part by weight of trimethyl phosphate as a phosphorus compound were added, followed by a polycondensation reaction according to a conventional method to obtain a polyester composition having an intrinsic viscosity of 0.67 g / dl. I got The carboxy terminal group content of the polyester is 62 equivalents / ton, the glycol condensate content is 3.1% by weight,
c-Tg was 55 ° C and Tc′-Tc was 67 ° C.

Next, the obtained polyester composition is sufficiently dried, then supplied to an extruder, melted at 285 ° C., extruded into a sheet shape from a T-type die, cooled and solidified with a cooling drum at 30 ° C., and unstretched. A film was obtained. Next, the unstretched film was simultaneously stretched 3.0 times in the longitudinal direction and 3.0 times in the transverse direction at 100 ° C., and then subjected to a heat treatment at 200 ° C. to obtain a film having a total thickness of 50 μm. The obtained resin composition had good moldability. Table 1 summarizes the characteristics of the film.

The film was recordable with a pencil, a ballpoint pen, a fountain pen, and a thermal transfer ribbon, and had good characteristics as a recording material. In addition, it had moderate flexibility, and the phenomenon of cracking or chipping was not recognized even when a folding operation or a tearing operation was performed. Example 2 SiO ₂ : Al ₂ O ₃ : Fe ₂ O ₃ : CaO: MgO = 5
0.4: 33.5: 5.58: 5.05: 1.98 (weight ratio in terms of oxide) and a composite oxide particle having a primary particle size ratio of 1.05 (manufactured by Chugoku Electric Power Co., Inc.) Pulverization treatment and dispersion treatment were performed to obtain particles having an average particle size of 2.4 μm (bulk density: 1.5 g / cm ³ , hydroxyl group ratio: 0.48). A slurry was prepared using the particles, and polymerization was performed in the same manner as in Example 1 (resin composition A).

On the other hand, 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol and 0.0 part of lithium acetate were used.
9 parts by weight, 0.4 parts by weight of colloidal silica particles having an average particle diameter of 0.3 μm were mixed, and a transesterification reaction was carried out according to a conventional method, and thereafter, 0.08 parts by weight of antimony trioxide,
0.1 part by weight of trimethyl phosphate was added, and a polycondensation reaction was performed according to a conventional method to obtain a polyester composition having an intrinsic viscosity of 0.65 (resin composition B).

Next, two extruders were prepared, and the resin composition A and the resin composition B were supplied so that the lamination thickness shown in Table 1 was obtained. Each of the extruders was melted at 285.degree. And cooled and solidified with a cooling drum at 30 ° C. to obtain an unstretched film. Next, the unstretched film was heated to 95 ° C., stretched 3.2 times in the machine direction, and
The film was stretched 3.0 times in the transverse direction by heating to 0 ° C., and heat-treated at 200 ° C. to obtain a film. Table 1 shows the properties of the obtained film.

The obtained resin composition had good moldability. Table 1 summarizes the properties of the resin composition and the film.

On the surface of the film, 100 parts of Co powder, 15 parts by weight of polyurethane resin, 5 parts of vinyl chloride / vinyl acetate copolymer resin, 5 parts of nitrocellulose resin, 3 parts of aluminum oxide powder (average diameter 0.3 μm), A magnetic paint having a composition of 100 parts of methyl ethyl ketone, 100 parts of toluene and 2 parts of stearic acid is applied, dried and heat-cured. Then, a back coat layer containing carbon black and a thermosetting urethane resin is formed on the back surface, and slits are formed. Then, a magnetic tape was obtained. The magnetic tape had high bending stiffness, good head touch, and good recording and reproducing characteristics. Example 3 SiO ₂ : Al ₂ O ₃ : Fe ₂ O ₃ : CaO: MgO = 5
0.4: 33.5: 5.58: 5.05: 1.98 (weight ratio in terms of oxide) and a composite oxide particle having a primary particle size ratio of 1.05 (manufactured by Chugoku Electric Power Co., Inc.) Pulverization treatment and dispersion treatment were performed to obtain particles having an average particle size of 5.2 μm (bulk density: 1.3 g / cm ³ , hydroxyl group ratio: 0.33). A slurry was prepared using the particles, and polymerization was carried out in the same manner as in Example 1 except that the blending amount of the particles was 60 parts by weight with respect to the polyester (resin composition C).

Next, in the same manner as in Example 2, the polyester resin B and the polyester resin C were respectively supplied so as to have the lamination thickness shown in Table 1, and each was melted at 285 ° C.
It was extruded into a sheet from a die and cooled and solidified with a cooling drum at 30 ° C. to obtain an unstretched film. Next, the unstretched film was heated to 95 ° C. and stretched 2.7 times in the machine direction, and further heated to 100 ° C. and stretched 2.5 times in the transverse direction.
Heat treatment was performed at 0 ° C. to obtain a polyester film. The obtained film had good moldability. Table 1 summarizes the properties of the resin composition and the film. Example 4 A polyester resin having an intrinsic viscosity of 0.67 was obtained in the same manner as in Example 1 except that the operation of adding particles was not performed.

Next, using a vent-type extruder provided with a vent hole connected to a vacuum line, composite oxide particles (SiO ₂ : Al ₂ O ₃ : Fe ₂ O ₃ : Ca) were added to the polyester resin.
O: MgO = 50.4: 33.5: 5.58: 5.0
5: 1.98 (in terms of oxide, weight ratio), average particle size 18μ
m, bulk density 1.1 g / cm ³ , hydroxyl group ratio 0.23,
The particle diameter ratio of the primary particles was 1.05 (manufactured by Chugoku Electric Power Co., Inc.), and the generated gas was removed while kneading and dispersing the particles to obtain a polyester composition having a particle concentration of 45% by weight.

The polyester composition was formed into a film in the same manner as in Example 1, but the film was broken at the time of film formation probably because of poor dispersibility of the particles. The stability of the film formation was not as good as that of Example 1, but the moldability was not good. Table 1 summarizes the properties of the resin composition and the film. Regarding the film surface properties, although the surface was rough and there was no problem in practice, there was some concern about the quality. Example 5 Agglomerated silica having an average particle diameter of 22.5 μm (manufactured by Micron Corporation) was added to a solvent, dispersed with a high-pressure homogenizer, and then treated with an epoxy-based silane coupling agent to obtain surface-treated silica particles. (Hydroxyl ratio 0.82).
Next, using the particles, the compounding amount was 2
A transesterification reaction and a polycondensation reaction were carried out in the same manner as in Example 1 except that the amount was changed to 7% by weight.

The physical properties of the polyester composition discharged during the reaction were an intrinsic viscosity of 0.45, and were fragile and could not withstand the subsequent processing at all.

Then, the polyester composition is heated under vacuum and a solid-phase polycondensation reaction is carried out to reduce the intrinsic viscosity to 0.6.
Thus, a polyester composition was obtained.

Table 1 shows the properties of the resin composition and the film.
Summarized in The fluidity of the resin composition was not always satisfactory, and the moldability was barely good.

The polymerization operation was carried out in the same manner with the concentration being 40 parts by weight per polyester, but the tendency of thickening was further strengthened, and no resin which could withstand the subsequent molding was obtained. Comparative Example 1 Agglomerated silica having an average particle diameter of 18 μm (hydroxyl ratio 2.5)
And the particle content to 40% with respect to the polyester composition.
A transesterification reaction and a polycondensation reaction were carried out in the same manner as in Example 1 except that the amount was changed to wt%. However, the viscosity increased during the polycondensation reaction, and the progress of the reaction became difficult on the way.

The physical properties of the polyester composition discharged during the reaction were an intrinsic viscosity of 0.34 and were brittle, so that it could not withstand the subsequent processing at all. Comparative Example 2 Agglomerated silica having an average particle size of 2.2 μm was treated with an epoxy silane coupling agent in a dry manner to obtain surface-treated silica particles (hydroxyl ratio 1.2). Next, the particle content was set to 25% by weight based on the polyester composition, and
, A transesterification reaction and a polycondensation reaction were carried out. However, the viscosity increased during the polycondensation reaction, and the progress of the reaction became difficult on the way.

The physical properties of the polyester composition discharged in the course of the reaction were an intrinsic viscosity of 0.45 and were brittle, so that it could not withstand the subsequent processing at all. Comparative Example 3 Using a water glass method, SiO ₂ : Al ₂ O ₃ = 73.3:
26.4 (in terms of oxide, weight ratio), hydroxyl group ratio 3.2,
Monodisperse aluminum silicate particles having an average particle diameter of 0.3 μm were synthesized, and then subjected to solvent replacement to obtain a 20% by weight ethylene glycol slurry. Using the slurry, a transesterification reaction and a polycondensation reaction were carried out in the same manner as in Example 1 except that the particle content was adjusted to 25% by weight based on the polyester composition. However, the viscosity increased during the polycondensation reaction, the viscosity increased during the polycondensation reaction, and the progress of the reaction became difficult during the reaction.

The physical properties of the polyester composition discharged during the reaction were an intrinsic viscosity of 0.4, and were brittle and could not withstand the subsequent processing at all.

[0070]

[Table 1]

[0071]

As described above, the present invention has good moldability even when a very large deformation such as a film is given, while containing a large amount of particles. In addition, excellent productivity, and
Due to the combined effect with the particles, new functions that cannot be expected from the inherent properties of the resin, such as improvement in flame retardancy and mechanical properties, can be exhibited.

Since the composition of the present invention has excellent processability, it can be processed into various forms as a molding material by using fibers, sheets, or injection molding or drawing. Besides its excellent mechanical and thermal properties,
Taking advantage of the composite characteristics of a hybrid material, when it is made into a film, it can be used not only for recording materials such as magnetic recording media, base films for ink ribbons or synthetic paper, but also for interior uses such as wallpaper and floor sheets, drinking cans, etc. For bonding metal plates, packaging materials and housing materials for electrical equipment, IC sealing materials, capacitors, carrier films for electronic components, bonding for wiring boards and coatings, glass components, optical applications It can be used for various general industrial uses such as members, thermosensitive stencil printing, packaging containers and the like. Also, since it has excellent processing characteristics, it also has an excellent product yield.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08K 3/34 C08K 3/34 C08L 67/00 C08L 67/00 F term (reference) 4F071 AA01 AA44 AA86 AA87 AB26 AD02 AE11 AE17 BA01 BB06 BB07 BC01 4F100 AA02A AA17A AA18 AA19 AA20 AA23 AK01A AK41A AK42 BA01 DE01A EJ37A EJ38 JA05A JA11A JB16A JJ03 JL01 JL02 YY00A 4J002 BB001 BB241 BC02 CF01 001 001 001

Claims (10)

[Claims] 1. A resin composition comprising particles contained in a resin, wherein the particles are inorganic particles containing silicon as a main component,
The strength of hydroxyl-bonded silicon as observed by ²⁹ Si CP-MAS NMR analysis is lower than the strength of non-hydroxyl-bonded silicon, and 25 to 90% by weight of the particles in the resin composition.
A resin composition characterized by containing: 2. The resin composition according to claim 1, wherein the particles contain at least two kinds of metal elements as metal elements other than silicon. 3. The particles have an average particle diameter of 0.005 to 20 μm and a bulk density of 5.0 g / g.
The resin composition according to claim 1, wherein the resin composition is not more than cm ³ . 4. The resin is a crystalline thermoplastic resin,
And (Tc'-Tc) is not more than 85 [deg.] C. when a crystallization temperature (Tc) at the time of temperature rise and a crystallization temperature (Tc ') at the time of temperature decrease. The resin composition according to any one of the above. 5. The resin composition according to claim 1, wherein a difference (Tc-Tg) between a temperature rise crystallization temperature and a glass transition temperature (Tg) of the resin composition is 20 ° C. or more. 3. The resin composition according to item 1. 6. The resin composition according to claim 1, wherein said resin is a thermoplastic polyester resin. 7. The resin composition according to claim 1, wherein the resin composition is obtained by adding particles at any stage of a polymerization reaction. 8. A resin film comprising the resin composition according to claim 1. 9. A resin film, wherein at least one layer of the laminated film is a layer comprising the resin composition according to any one of claims 1 to 7. 10. The resin film according to claim 8, wherein the resin film is stretched in at least one direction.