JPS6257459A - Thermoplastic polymer sheet - Google Patents

Abstract

PURPOSE:To provide a thermoplastic polymer sheet containing inorganic porous microcapsules including a thermoplastic polymer and a character-imparting agent, and having various excellent properties. CONSTITUTION:(A) A character-imparting agent such as electrically conductive metallic compound, organic dye, pigment, crosslinking agent, etc., is included in (B) a microcapsule having a spherical form with a diameter of 0.1-100mum, containing cavity 2 and made of a porous wall material (inorganic material such as calcium carbonate) having an average pore diameter of 10-600Angstrom and capable of including a liquid, solid or gas in the cavity in a freely releasable state. The inclusion is carried out by impregnating the component A in the microcapsule B in the case of an organic substance or by using the component A as a core substance in the production of microcapsule in the case of an inorganic substance. The capsule containing the character-imparting agent is added in the polymerization of (C) a thermoplastic polymer, preferably polyester, polyamide, etc., and the obtained polymer having a thermoplastic polymer content of 5-80vol% and containing microcapsules containing1-95vol% character- imparting agent is formed in the form of a sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a thermoplastic polymer sheet to which inorganic porous microcapsules containing at least a thermoplastic polymer and a property-imparting agent are added.

More specifically, the present invention uses a thermoplastic polymer and a property-imparting agent that includes (1) a conductive metal compound, (2) an organic dye, an organic pigment, (3) a crosslinking agent, (4) an ultrafine particle, and (5) an electrostatic charge. A thermoplastic polymer sheet containing inorganic porous microcapsules containing an inhibitor, (6) an ultraviolet absorber, (7) a liquid lubricant, (8) a heat stabilizer, and (9) a metal halide. It is something.

[Prior art]

Each type of the above-mentioned characteristic imparting agent will be described below.

! 1) In order to improve the electrostatic castability of a thermoplastic polymer film, Zns Mg, or a Mn compound and a phosphorus compound, as described in Japanese Patent Publication No. 56-15730,
As disclosed in JP-A-59-214618, a method has been proposed in which conductive metal compounds such as magnesium compounds, phosphorus compounds, and alkali metal compounds are added to lower the resistivity of molten polymers.

However, when a conductive metal compound is added, the added metal compound adheres to metal parts such as the cap, and streaks due to the cap tend to occur on the film surface.Also, when used as an insulator for a capacitor, the dielectric breakdown voltage increases. decreases,
It was impossible to improve both electrostatic castability and dielectric breakdown voltage.

(2) A polarizing film in which an organic dye is added to a thermoplastic polymer and the polymer molecules are oriented by stretching and the dye molecules are also oriented is disclosed in, for example, JP-A-57-84409.

However, in such a film, since the dye molecules are oriented, color unevenness cannot be avoided under polarized light, for example, reflected light.

(3) A method of manufacturing a translucent film by adding a crosslinking agent such as divinylbenzene to a thermoplastic polymer, melting it, extruding it, and stretching it is disclosed in JP-A-55-15899, for example.
Publication No. 7 G has been proposed.

However, since the crosslinking agent is directly added to the thermoplastic polymer, when it comes into contact with a high temperature metal such as a die during melt extrusion, gelation is promoted in the contact area and foreign matter is generated. Because of this, the crosslinking density is large;
There was a drawback that crosslinking unevenness was likely to occur.

(4) A method of adding inert inorganic fine particles to a thermoplastic polymer in order to improve the conductivity, transparency, and slipperiness of the thermopolymer film is disclosed, for example, in JP-A-56-92915. There is.

However, as the additive particles become finer, secondary aggregation of the fine particles tends to occur, and the surface of the film becomes rough due to the secondary agglomerated particles.

(5) In order to impart antistatic properties to thermoplastic polymer films, antistatic agents with low electrical resistance, that is, excellent conductivity of 101' ohms or less, have been directly added to thermoplastic polymers.

However, conventional antistatic films have the following drawbacks.

B. When the thermoplastic polymer is melt-extruded, a large amount of the added antistatic agent is scattered into the air, and the amount of antistatic agent in the thermoplastic polymer is drastically reduced, which not only significantly reduces the antistatic performance. The scattered antistatic agent adheres to the die lip, casting drum, etc., reducing productivity.

During melt-extrusion, the antistatic agent comes into direct contact with the high-temperature metal wall, which tends to cause thermal decomposition and gelation, resulting in foreign matter, fish eyes, etc. occurring in the film, resulting in film defects. .

C. The transparent antistatic agent has ionic conductivity and therefore has strong hygroscopicity. For this reason, if a molten sheet containing an antistatic agent is placed directly into water, the antistatic agent will dissolve into the water and not only will it contaminate the water, but the resulting thermoplastic polymer sheet will also lose almost all of its antistatic properties. Resulting in.

Second, when the obtained thermoplastic polymer sheet is used in applications where repeated wear and friction occur, the antistatic performance is easily lost at the point where the number of repetitions is high.

(6) In order to improve the weather resistance of thermoplastic polymer films, for example, Japanese Patent Publication No. 57-6740 and Japanese Patent Publication No. 60-60
It is known to add organic weathering agents such as benzophenone, benzotriazole, and phenyl salicylate to thermoplastic polymers as described in Japanese Patent Publication No. 25457, and antimony compounds as disclosed in Japanese Patent Publication No. 59-49938. There is.

However, in addition to the above-mentioned drawbacks (5), 40 mouths, there was a drawback that the weather resistance effect disappeared within a relatively short period of 1 to 2 years.

(7) In order to improve the surface smoothness of thermoplastic polymer films, adding silicone oil is recommended.
This method is known from Japanese Patent Publication No. 48898 and Japanese Patent Publication No. 14372/1983.

However, such liquid lubricants often bleed out, resulting in poor film adhesion, poor dispersibility of the liquid lubricant, and increased film surface roughness.Furthermore, the liquid lubricant thermally deteriorates during melt extrusion, resulting in smoke generation. There were drawbacks.

(8) In order to improve the thermal stability of thermoplastic polymers at high temperatures, the addition of various organic thermal stabilizers has already been proposed. (Special Publication No. 37-12371, Publication No. 12373-1973, and Publication No. 44-735
However, in addition to the drawback of (5) 41 above, the heat stabilizer scatters during melt extrusion over a long period of time, leading to deterioration of the polymer and at the same time reducing the heat stabilizing effect.
Addition of a large amount of heat stabilizer has the drawback of deteriorating the physical properties and productivity of the polymer.

(9) The addition of metal halides to improve the gas barrier properties, moldability, and stretchability of thermoplastic polymer films is already known, for example, in JP-A-57-185349.

However, the addition of metal halides greatly reduces the flexibility and transparency of the film, and although water caused by the hygroscopicity of metal halides is effective in improving film stretchability, it has poor gas barrier properties. In addition, metal halides absorb water during melt extrusion of the polymer, leading to decomposition and foaming of the polymer, making it difficult to handle the resulting polymer chips and films. There were drawbacks such as.

[Purpose of the invention]

The present invention solves the above-mentioned conventional drawbacks (1) an ultra-thin capacitor film with excellent static charge application properties and electrical insulation properties;
(2) Films for general packaging and covering of photosensitive layers;
(3) Heat-shrinkable films and capacitors, cable insulators, (4) and (7) magnetic recording base films, (5) general industrial/packaging sheets, (6) weather-resistant sheets, (7) capacitors The object of the present invention is to provide a film for food packaging and electrical insulation materials, (8) a heat-resistant film, and (9) a film for food packaging and molding that has excellent gas barrier properties and mechanical properties.

[Structure of the invention]

The thermoplastic polymer sheet of the present invention that achieves the above objects is
It is characterized by adding to a thermoplastic polymer inorganic porous microcapsules encapsulating a thermoplastic polymer at a filling rate of 5 to 80% by volume and a characteristic imparting agent at a filling rate of 1 to 95% by volume. It is.

The thermoplastic polymer in the present invention exhibits desired flow upon heating, and is primarily a linear polymer in chemical structure.

Typical examples include polyolefins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polybutadiene, polystyrene, and polymethylpentene, polyethylene terephthalate, and polyethylene α,β-bis(2-chlorophenoxy)ethane4. .4
′Dicarboxylate, polybutylene terephthalate,
Polyesters such as polyethylene naphthalate and polycarbonate, halogenated polymers such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, and polyvinyl fluoride, polyhexamethylene adipate (nylon 66), and polyε-caprolactam. (Nylon 6), Nylon 6■0, etc., as well as vinyl polymers such as polyacrylonitrile and polyvinyl alcohol, polyacetals, polyethersulfones, polyetherketones, polyphenylene ethers, polysulfones, polyphenylene sulfides, and copolymers thereof. These include combinations and mixtures, and in the case of the present invention, polyester, polyphenylsulfide, polyamide, polysulfone, and polyvinylidene fluoride are particularly preferred.

In addition, the inorganic porous microcapsules (hereinafter simply referred to as microcapsules) used in the present invention are minute particles with a diameter of 0.1 μm to 100 μm.
As shown in Figure 1, the wall material l is a porous, spherical container with an average pore size of 10 to 600, and has a hollow part 2 inside, in which liquid, solid, or gas can be stored. Freely include and
It can be released.

As a typical manufacturing method, for example, Japanese Patent Publication No. 54-625
Publication No. 1, Special Publication No. 57-55454, Special Publication No. 55
"Interfacial reaction method" described in No.-43404 etc.
In other words, it is a method of preparing inorganic powder by an aqueous solution precipitation reaction, but in the preparation process, a water-in-oil type (W1
Type 0) can be manufactured by adjusting hollow, spherical, and porous inorganic powder particles using an emulsion.

The inorganic wall material that makes up the microcapsules is
Alkaline earth metal carbonates such as calcium carbonate, barium carbonate, and magnesium carbonate; alkaline earth metal silicates such as calcium silicate, barium silicate, and magnesium silicate;
Alkaline earth metal phosphates such as calcium phosphate, barium phosphate, magnesium phosphate, calcium sulfate,
Alkaline earth metal sulfates such as barium sulfate and magnesium sulfate, metal oxides such as silicic anhydride, aluminum oxide, zinc oxide, iron oxide, titanium oxide, tin oxide, antimony oxide, cobalt oxide, nickel oxide, and manganese oxide, water Metal hydroxides such as iron oxide, nickel hydroxide, aluminum hydroxide, calcium hydroxide, and chromium hydroxide; metal silicates such as zinc silicate, aluminum silicate, and silicate steel;
Typical examples include metal carbonates such as zinc carbonate, aluminum carbonate, cobalt carbonate, nickel carbonate, and basic copper carbonate.

The size of the microcapsules is variable in the range of 0.05 to 80 μm, and in the case of the present invention, in particular O,1 to 108 μm.
Spherical particles with a sharp average particle size distribution are preferable because they have good compatibility with thermoplastic polymers and good distribution.

The pore diameter of the capsule particle surface was measured by the BIiT method and was 20
600 people, but in the case of the present invention, 20 to 10
A distribution having a main pore size in the range of 0.000 to 0.000000000000 is preferred.

Of course, a completely spherical shape is preferable in terms of dispersibility, fluidity, slipperiness, smoothness, abrasion resistance, etc.

Because they are microspheres and porous with pores, their particle surface area is extremely large (100 to 1000 m / g when measured by the BET method, and their apparent specific gravity is also small. The thickness is about 0.1 to 0.4.

In addition, the thickness of the wall of this microcapsule is also 0.01~
It can be freely changed to about 5 μm, and this is caused by deformation due to external force.
It is determined not only by mechanical properties such as fracture, but also by the release characteristics of the inclusions to the outside.

Methods for encapsulating the property-imparting agent used in the present invention in such microcapsules include an impregnation method and a suspension method, but in the case of the present invention, the impregnation method is preferable in terms of productivity, quality, etc.

Furthermore, as a method for encapsulating the thermoplastic polymer in microcapsules, it is most preferable to add the microcapsules encapsulating the above-mentioned property imparting agent at the time of polymerization of the thermoplastic polymer.

The amount of thermoplastic polymer encapsulated in the microcapsules needs to be 5 to 80% by volume, preferably 10 to 40% by volume. If the ratio is less than the above, voids may occur between the thermoplastic polymer and the microcapsules,
Not only does it make it difficult for the property-imparting agent to bleed out into the thermoplastic polymer and its surface through the pores of the microcapsules, but it also prevents the property-imparting agent from scattering into the air during the melt-extrusion process and changing the appearance of the film due to thermal decomposition and gelation. It has the disadvantage that foreign objects and streaks occur frequently, which significantly reduces the product value. The upper limit volume fraction of the thermoplastic polymer in the microcapsules is preferably 40% by volume when the property-imparting agent is an organic compound, and 80% by volume when the property-imparting agent is an inorganic compound. This is the upper limit of the content required to exhibit the effect of the property-imparting agent.

It is clear that the microcapsules may contain less than 20 volumes of void space in addition to the thermoplastic polymer and the characterization agent.

Next, the characteristic imparting agent encapsulated in the microcapsules of the present invention and the amount added to the capsules encapsulating the same will be explained.

+l) Conductive metal oxide As the conductive metal oxide, antimony oxide, indium oxide, stannic oxide, mixtures thereof, etc. are preferably used, and the amount of such metal oxide contained in the microcapsules is determined by the filling amount. The amount of microcapsules encapsulating these metal oxides added to the thermoplastic polymer is 0.001 to 5.0% by weight.

If the amount of metal oxides included is less than 3% by volume, the conductive properties will be insufficient and the resistivity of the molten polymer will not decrease, and if the amount of included metal oxides exceeds 80% by volume, the diameter of the microcapsules will increase and the film will be damaged. This causes deterioration of the electrical characteristics of the

Furthermore, if the amount of metal oxide-containing microcapsules added to the thermoplastic polymer is less than 0.001% by weight, conductivity will be insufficient as described above, and if it exceeds 5.0% by weight, the electrical insulation properties of the film will deteriorate. do.

(2) Organic dyes, organic pigments The types of organic dyes and organic pigments are not particularly limited, and examples of organic dyes include anthraquinone, azo, styryl,
Examples include azomethine series and azomethine series.

In addition, examples of organic pigments include azo pigments, atin pigments, copper phthalocyanine pigments, quinacridone pigments, perinone pigments,
Examples include mordant dye pigments.

The amount of such organic dyes and organic pigments to be encapsulated in microcapsules is not particularly limited, but the filling rate is 20 to 95.
The higher the volume %, the clearer the color, which is preferable.

The amount of capsules added to the thermoplastic polymer can be arbitrarily selected depending on the color shading, gloss level, etc., but it is usually 0.
．． 001 to 30% by weight is preferable.

(3) Crosslinking agent The crosslinking agent may be any agent as long as it has a group capable of covalent bonding by reacting with the thermoplastic polymer,
For example, examples of the compound (A) having two or more aliphatic unsaturated bonds in the molecule include divinylbenzene and divinylfulphone.

Alternatively, a copolymer of the above compound (A) and a monovinyl compound (B) having only one aliphatic unsaturated bond in the molecule may be used, and the compound (B) may include acrylic acid, methacrylic acid, and their methyl or glycidyl esters, maleic anhydride and its alkyl derivatives, vinyl glycidyl ether, vinyl acetate, vinylbenzene derivatives, and the like.

One or more types of each of the compounds (A) and (B) can be used, but ethylene or styrene may be further added thereto for copolymerization.

The amount of such crosslinking agent encapsulated in the microcapsules is preferably about 10 to 95% by volume.

In addition, the amount of microcapsules containing a crosslinking agent is
Depending on the degree of crosslinking, it is about 0.001 to 5% by weight.

(4) Fine particles Examples of fine particles include silicon-containing fine particles such as silicon oxide, mica, talc, kaolin, and zirconium silicate, zinc oxide, calcium carbonate, calcium sulfate, barium carbonate, barium sulfate, barium phosphate, magnesium phosphate, and sulfuric acid. Group 2 metal oxides such as strontium,
Examples include salt, aluminum oxide, zirconium oxide, trim oxide, and carbon black, but from the viewpoint of transparency of the thermoplastic polymer, silicon oxide and aluminum oxide are preferable, and silicon oxide is particularly preferable.

Such fine particles are obtained by uniformly dispersing aggregated particles with a particle size of 300 to 2000 mμ in a dispersion medium to obtain primary particles with a particle size of 20 to 200 mμ, encapsulating them in microcapsules in the dispersion medium, and then adding them to a thermoplastic polymer. , distributed.

Primary particles are encapsulated and covered in microcapsules to prevent secondary aggregation.

The amount of primary particles encapsulated in microcapsules is about 3 to 80% by volume, preferably about 5 to 40% by volume, and the amount of microcapsules encapsulating primary particles added to the thermoplastic polymer may vary depending on the purpose. Varies from 0.001 to 10% by weight
That's about it.

(5) Antistatic agent Antistatic agents are added to prevent static electricity on the film, and in the case of the present invention, antistatic agents are added to prevent the film from becoming static. Anything that makes it opaque is not preferred.

In the case of the present invention, it has a lipophilic group and a hydrophilic group, and has an appropriate 1 (LB
Compounds with guanidine derivatives, phosphate-containing anionic activators, anionic activators such as sulfonic acids, cationic activators such as polyamide amines, quaternary ammonium salts, pyridinium salts, polyoxyethylene alkylphenols and alkyl phenols, etc. These include polyethylene glycol nonionic surfactants such as midoethers, morpholine derivatives, imidacillin derivatives, amphoteric surfactants such as betaines and amino acids, and mixtures thereof.

Typical antistatic products include "Armostat" 10 (tertiary amine type Nilion oil), "Electro Stripper" EA (cationic type: Kao Atlas side), and "Resistat" 113 (ester type nonionic system:
Daiichi Kogyo Seiyaku Co., Ltd.), "Sunstat" 2515 (ampholytic type: Sanyo Chemical Co., Ltd.), and "Antex" C200 (quaternary ammonium salt type: Toho Chemical Co., Ltd.).

In the case of the present invention, antistatic properties are excellent, but those with poor productivity are particularly effective, and such antistatic agents are liquid at room temperature as shown above.

The amount of antistatic agent encapsulated in the microcapsules can be as small as 1% by volume to as high as 95% by volume. Considering this, a content of about 5 to 70% by volume is excellent.

Further, the amount of microcapsules containing the antistatic agent added is 0.001 to 40% by weight, preferably 0.0% by weight.
A content of 1 to 15% by weight is excellent in terms of operability, productivity, and quality.

Usually, antistatic properties have surface specific resistance (I
QII ohm・cm or less, preferably 10” ohm・c
m or less.

(6) Ultraviolet absorber The ultraviolet absorber used in the present invention is ideally one that completely absorbs wavelengths of 270 to 400 μm, but a thermoplastic polymer to which microcapsules containing the ultraviolet absorber are added is preferable. It may be one that absorbs only the light of the wavelength to be absorbed.

Examples of such ultraviolet absorbers include conventionally known benzophenone-based agents, such as Mark'LA51 (Adeka Argus), "5eesorb" (Shiraishi Calcium), "Uvxnul" 400, and "Uvinul".
"D-500 (Sintra Chemical), "υn1sorb"1
00 (Kyodo Yakuhin), benzotriazole series, e.g. “T
inuvin”P or 326 (Geigy), “υ5
olvin”Vs (7-KColorCorp), suenyl salicylate series, e.g. “5ee-sorb” 2
01 (colored stone calcium), “Lightsorber”
5alo (Dow Chemical Company), etc., and the types are not particularly limited, but FD
A-approved is preferred.

The amount of the ultraviolet absorber encapsulated in the microcapsules is 1 to 95% by volume, and the amount of the capsules added to the thermoplastic polymer is 0.001 to 20% by weight.

(7) Liquid lubricant The liquid lubricant used is not particularly limited, but for example, organic lubricants such as methylalkylpolysiloxane and diphenylpolysiloxane such as dimethylpolysiloxane, methylphenylpolysiloxane, methylbutylpolysiloxane, and methylbutylpolysiloxane are used. Examples include waxes such as polysiloxane and carnauba wax.

The amount of liquid lubricant encapsulated in the microcapsules is a filling rate of 1 to 95% by volume, and the amount of the microcapsules added to the thermoplastic polymer is 0.0001 to 10% by volume.
Weight%.

(8) Heat stabilizer The heat stabilizer used in the present invention includes inorganic salts such as lead sulfate, lead sulfite, lead silicate, lead carbonate, etc., such as "Stabinex" TCA (Mizusawa Chemical), lead stearate, and salicylic acid. Lead soaps such as "TVS" C5-8 (Nitto Kagaku), cadmium soaps such as cadmium stearate, cadmium laurate, cadmium benzoate, etc., such as "Shinakalet" (Shinyo Kako), "Mark" 702
(Adeka Argus), zinc stearate, zinc octylate and other zinc soaps, such as "TMT"-103 (Tokyo Fine Chemical), stearate bar! Barium soap such as Noum, barium octylate, e.g. Mina Chikara Red B5-
10 (Shinyou Kako), and dibutyltin laurate-based soaps such as "TN"-5B (Sakai Chemical Industry), "
TVS″N2000 (Nitto Chemical) can be mentioned.

The amount of such heat stabilizer to be encapsulated in microcapsules is
The filling rate is 1 to 95% by volume, and the amount of the microcapsules added to the thermoplastic polymer is 0.0001 to 5% by weight.

(9) Metal halide The metal halide in the present invention refers to a compound consisting of the following elements.

In other words, metals are groups Ia to ■a of the periodic table of elements, and groups Ib to r.
It is an element arbitrarily selected from the Vb group, and halogen is an element arbitrarily selected from the ■b group of the periodic table of elements.

Among these, preferred are those having the following characteristics.

That is, (a) Among the metals constituting the metal halide, the first ionization potential of at least one metal is 10 eV or less.

(b) When the metals constituting the metal halide consist only of Group Ia, the ionic crystal radius of at least one metal is 0.9 Å or less.

Representative examples of metal halides used in the present invention include those shown below, but are not limited thereto.

a. Magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, strontium chloride.

b, lithium chloride, lithium bromide, lithium iodide.

C6 cobalt chloride, copper chloride, zinc chloride, cobalt bromide,
Zinc bromide, nickel chloride.

d, beryllium chloride, lanthanum chloride, cerium chloride, molybdenum chloride, chromium chloride.

e, copper bromide, manganese chloride.

f, calcium potassium chloride, sodium aluminum chloride, sodium magnesium chloride; when two or more types of metal halides are used, they can be used in any combination.

The amount of the metal halide encapsulated in the microcapsules is 10 to 80% by volume, and the amount of the capsules added to the thermoplastic polymer is 0.1 to 25% by weight.

Furthermore, the porosity within the microcapsules is preferably 20% by volume or less.

Next, a method for manufacturing the thermoplastic polymer sheet of the present invention will be described, but the present invention is not necessarily limited thereto.

The characteristic imparting agent is the above (2), (3), (5) to (9).
In the case of organic compounds such as ), the compound is used as is, or a property-imparting agent is dissolved in a solvent, impregnated and infiltrated into microcapsules, and the solvent is evaporated. On the other hand, when the property-imparting agent is an inorganic compound like (11, (41),
In the microcapsule manufacturing process, the characterization agent is suspended as a core material to grow the microcapsules.

Next, at an arbitrary step during polymerization of the thermoplastic polymer, microcapsules encapsulating a property-imparting agent are added and polymerized.

The thus obtained microcapsule-containing thermoplastic polymer containing one or more property-imparting agents may be used alone, or may be blended with a microcapsule-containing thermoplastic polymer containing another property-imparting agent, or Add optional property-imparting agents and other additives, feed the extruder using a conventional method, melt at a temperature higher than the melting point of the polymer, extrude it into a sheet from a die, and place it on a casting drum or belt in a suitable manner. Cast by cooling and solidifying using methods such as air knife method, electrostatic application method, press roll method, etc.
Form into a sheet.

It is clear that stretching and rolling in the longitudinal and transverse directions, as well as heat treatment, embossing, calendering, surface treatment, etc., may be carried out as necessary.

The thickness of the sheet thus obtained is not particularly limited;
mn+ or less, preferably 0.5 mm or less, more preferably 190 μm or less, depending on the use, 50 μm or less
m or less is preferable.

In the case of the sheet of the present invention, the effect of the present invention is remarkable when high-pressure extrusion and high-temperature, high-magnification stretching conditions are used such that the concentration distribution of microcapsules in the cross-sectional direction of the sheet is higher than the concentration in the center of the additive sheet layer. become.

〔Effect of the invention〕

Next, the functions and effects of the present invention will be described for each type of property-imparting agent encapsulated in the inorganic porous microcapsules.

(1) Conductive metal oxide Since the metal oxide is encapsulated in microcapsules and added to the thermoplastic polymer while being guarded by the microcapsules and thermoplastic polymer, this polymer is melt-extruded into a sheet. When melting, metal oxides do not adhere to the metal walls of the die, etc., and the specific resistance during melting is lowered, giving the thermoplastic polymer sheet high electrostatic castability and high insulation properties. Can be done.

Further, even when the sheet is used as an insulator for an oil-insulated capacitor, the dielectric breakdown voltage does not decrease, and it is possible to achieve both electrostatic application castability and dielectric breakdown voltage.

This was not possible with conventional methods of directly adding conductive metal oxides to thermoplastic polymers.

Furthermore, it is possible to impart electrostatic castability to ultra-thin films, and this is particularly effective when the thickness at the time of casting is 20 to 80 μm.

Moreover, there is no unevenness in film thickness, and productivity can be improved.

Therefore, the sheet of the present invention can be suitably used as an ultra-thin insulator for a capacitor.

(2) Organic dyes and organic pigments (a) Organic dyes and pigments with poor thermal stability are encapsulated in inorganic hollow microcapsules with excellent heat resistance. Pigments do not come into direct contact with each other, making thermal decomposition and gelation less likely.

There is also less scattering of organic dyes and pigments from the mouth, the mouth outlet, and the sheet surface.

Therefore, a sheet with a smooth surface and a rear surface free from coloration and foreign matter can be obtained.

C. Since organic dyes and pigments are encapsulated in microcapsules, dye and pigment molecules do not become oriented during film stretching, thereby preventing color unevenness under polarized light.

Therefore, a sheet-like product with a deep feeling and no uneven color is provided, and is particularly preferably used for general industrial applications.

(3) Crosslinking agent In addition to the same effects as in (2), (a), and (2) above, a uniform distribution of crosslinking is provided even if the crosslinking density is low due to the uniform distribution of microcapsules.

Therefore, the thermoplastic polymer can be expected to have a rubber-like elastic effect, and since the crosslinking points are formed by chemical bonds between the thermoplastic polymer and the crosslinking agent with inorganic particles,
Molecular chain movement is inhibited, and scratch resistance and wear resistance can also be improved.

In other words, it prevents the polymer from flowing near the melting point of the thermoplastic polymer, so it is expected to be used as a heat-shrinkable film for packaging, and it prevents oil from swelling in oil in oil-insulated capacitors and OF cables. , for capacitors, and as a cable insulation material.

(4) Inorganic Fine Particles Since the particles are finely dispersed down to the primary particles and encapsulated in microcapsules, secondary aggregation is prevented.

Therefore, coarse graining and roughness of the film surface due to secondary aggregation are prevented, and it is preferably used in applications where surface roughness is small, such as packaging, base films for magnetic recording media such as floppy disks, and general industrial applications.

(5) Antistatic agent Not only does it have the same effect as (2), (a), and (a) above, but it also makes it possible to obtain a sheet with a smooth surface and a smooth surface that does not contain any coloring or foreign matter.

In addition, the obtained sheet contains an antistatic agent pre-douded through the pores of the porous microcapsules.
New antistatic agent is constantly supplied to the surface, and it exhibits excellent antistatic properties even after repeated use over a long period of time.

C. Even when cast in water during melt extrusion, not only does the water in the aquarium not become contaminated, but the resulting sheet also has excellent antistatic properties.

20 Even if the surface of the sheet is subjected to strong corona discharge treatment in order to improve surface adhesion, there is no blocking or deterioration of slipperiness, and the sheet has excellent slipperiness and adhesion.

E. It also has excellent abrasion resistance, and the porous microcapsules on the sheet surface do not easily fall off from the sheet even in infinitely repeated operations.

When used as a base film for magnetic recording media,
When an additive with an average particle size of 1 μm or less, which is smaller than the average particle size of inorganic porous microcapsules, is used as an additive for sheet slipperiness, the antistatic performance and slipperiness after repeated friction tests are improved. A particularly remarkable effect on surface smoothness is observed.

(6) Ultraviolet absorber In addition to the effects of (2) (a) and (2) above, it has a good appearance with no coloring or foreign matter.

The following effects can be achieved.

C1: A sheet with good appearance and no coloring or foreign matter can be obtained.

2. Deterioration of film due to ultraviolet rays usually starts from the surface layer of the film.

That is, in the case of the present invention, the ultraviolet absorber is released from the microcapsules in the surface layer, and weather resistance is imparted for a long period of time.

When a UV absorber is added directly to a thermoplastic polymer as in the past, the UV absorber in the middle layer of the film does not migrate to the surface layer after the effect of the UV absorber in the surface layer of the film disappears. It cannot withstand long-term use.

Therefore, the sheet with excellent weather resistance of the present invention is preferably used for general industrial purposes, agricultural sheets, and heat ray absorbing sheets.

(7) Liquid lubricant In addition to the effects of (2) (a) and (b) above, it is possible to achieve both film adhesion and slipperiness.

In other words, the decrease in film adhesion caused by the addition of an oily lubricant is due to the direct addition of an oily lubricant to the polymer.
This is because a large amount of lubricant bleeds out in the initial stage.

However, in the present invention, since the lubricant is encapsulated in microcapsules, the lubricant bleeds out only at the protrusions formed by the microcapsule particles, and there is no lubricant anywhere other than the protrusions, which impairs the adhesiveness of the film. can be improved.

In addition, since the film slips mainly on the protrusions, it is possible to improve the slipperiness, and the long-term bleed-out of the lubricant maintains the slipperiness over a long period of time, especially at high temperatures. can be improved.

Therefore, it can be suitably used as a base film for magnetic tape.

(8) Heat stabilizer The same effects as in (2) A and A above can be obtained, and a film with a good appearance that maintains long-term thermal stability can be obtained, and its use in -S industrial applications is preferable. .

(9) Metal halide Since the metal halide is guarded by microcapsules, the hygroscopicity of the metal halide is inhibited, and an easily slippery sheet without the generation of voids due to water is provided.

That is, compared to the case of direct addition of a metal halide, handling during extrusion and film formation is easier, and productivity can be improved.

At the same time, it is possible to improve gas barrier properties as a function inherent to metal halides.

Therefore, according to the present invention, both slipperiness and gas barrier properties can be achieved.

Moreover, the absence of voids also improves mechanical and optical properties, making such sheets preferably used for packaging applications.

The measurement method used in this specification will be described below.

A. Breakdown voltage (BDV) AC voltage (60Hz) is applied to the capacitor element at 100 Hz per second.
The voltage was applied at a rising rate of V, and the reading on the voltmeter at the time of complete breakdown (permanent breakdown) was taken as the dielectric breakdown voltage of the capacitor.

Further, the capacitance of the capacitor element was 0.5 μF.

Less than 100v × 100~130v△ 131~160V 0 Over 160V ◎ B, center line average roughness: Ra (μm) Measured according to JIS-80601-1976.

From the roughness curve, extract a part of measurement length l in the direction of its center line, take the center line of this part as the X axis, the vertical direction as the Y axis, and set the roughness curve as Y=f (x), then Ra was calculated using the following formula.

Ra=1/f o r (x) dx Note that a cutoff value of 0.25 mm was used.

C1 maximum roughness Rt (μm) represents the distance between the largest peak and the deepest valley within the measurement length of the roughness curve.

D, intrinsic viscosity [η] Measured according to ASTM 04601.

Unit: dl/g Dan-to-to-saku-go-rito Measured according to ASTM D-1894-63.

μs<1.0 0 1.0≦μ, ≦3.0 to 3.0<μ, × F, rotation U'' value Using JIS C2330 equipment for measuring volume resistivity, guard bridge and counter electrode The resistance value generated between the main electrode and the guard electrode was measured by replacing the terminals.

1. At 25℃ and 65RHχ, the outer diameter of the film was 20III
180 to lφ 5US27 fixed rod (surface roughness 0.3S)
℃ winding speed of 95w+m/sec, load 50g/8
+++n+ width was applied and the vehicle was run repeatedly 100 times.

Capturing images of H1 average particle size particles using a scanning electron microscope,
The number average diameter φn is obtained by connecting the light density produced by the particles to an image analyzer (for example, Q T M2O3, manufactured by Nippon Regulator) and performing the following numerical processing.

Σdn/Σn=φn However, n is the number and d is the actual pore diameter.

1, Ys 01cDt F#' (S rMs method) 5~
This is a method in which an ion beam with an energy of about 15 KeV is applied to the sample surface, and secondary ions generated from the sample are subjected to mass spectrometry by sputtering.
This is the only surface analysis method that can handle the concentration range.

J, surface (BET method) (e.g., J, ^-, Chem, Soc,, 38.22
19 (1916). ) Adsorb nitrogen molecules onto the particle surface, measure the amount of adsorption, calculate the volume of adsorbed gas when the entire surface is covered with a monomolecular adsorption layer using the following formula (1), and calculate this by one nitrogen molecule. The number of molecules was determined by dividing by the volume of . This number of molecules and the following formula (2
) The specific surface area was obtained by multiplying by the volume σ occupied by one adsorbed molecule on the surface.

V = VmCP/(Ps-P) (1+ (C-1)
P/Ps ) (1) where Vm is the volume of adsorbed molecules when the entire surface is covered with single molecule adsorption, ■ is the pressure p
The volume of adsorbed gas at , P indicates the pressure, Ps is the saturated vapor pressure, and C is a constant.

σ= 1.091 (M/NP)
+2) Here, σ is the area occupied by one adsorbed molecule on the surface, M is the molecular weight, N is Avogadro's number, and p is the density of the adsorbed molecule layer on the surface.

BET using K-Toyoko Pressure Shimabara Seisakusho (manufactured by Digisoap 2500)
It is determined by analyzing the sorption isotherm curve using the BJH method.

Dan-! The film was dissolved in a good solvent of Mouse polymer at room temperature with stirring, and the added inert fine particles were separated by centrifugal sedimentation.

The separated inert fine particles were heated under a vacuum of 1 Qtorr at 100
After sufficiently drying at a temperature of ℃, the separated inert fine particles 1
gr was heated at 800°C for 14 hours in an air atmosphere based on the ash content test of JIS C2330, and the weight B (unit: gr) of the isolated inert fine particles obtained at this time was measured at 25°C and 5
Measurement was performed under an atmosphere of 0% RH. Furthermore, the total pore volume A (unit: cc) of the isolated inert fine particles was determined by the permeation method shown below.

The density (g/cc) of the polymer was determined from these values using the following formula (11).

Note that the method for determining the total pore volume (cc) using the above-mentioned infiltration method is to dissolve a certain amount C (gr) of isolated inert fine particle sample in a solvent (
After boiling in carbon tetrachloride at a temperature of 76 to 78° C. for 5 hours, only the particle sample is separated by centrifugal sedimentation. then 60
Dry with hot air at ~70°C for 30 minutes, and then
Measure D(gr).

From these values, the total pore volume was determined using the following formula (2).

The above-mentioned separated inert fine particles E
(gr) is the weight F (gr
), find the void volume (cc), then calculate the total void volume (cc).
Find the ratio to cc).

M. The separated inert fine particles obtained in the process of measuring the porosity of microcapsules are immersed in a good solvent for the property-imparting agent and thermoplastic polymer, and boiled at the boiling point of the solvent for a sufficiently long time to form microcapsules. Extract the characterization agent and thermoplastic polymer from the capsule. The content volume ratio is calculated from the extract by gas chromatography, and the filling rate of the thermoplastic polymer is given by (100−porosity)×volume ratio of the thermoplastic polymer in the microcapsule.

The filling rate of the characteristic imparting agent is determined by (100 - porosity - filling rate of thermolabile polymer).

The content of the microcapsules is determined based on the JIS C2330 ash content test method by heating sample A (gr) in an air atmosphere at 800°C for 4 hours and calculating the weight fjtB (gr) of the film-activated fine particles obtained by - ×100(%)
Find it according to.

Examples of the present invention will be described below.

〔Example〕

Example 1.2 and Comparative Examples 1 to 3 Porous spherical microcapsules containing a conductive metal oxide had an average particle size of 0.7 μm, a pore diameter of 30 μm, a specific surface area of 550 m1g, and an apparent specific gravity of 0.37 g/ cc spherical porous hollow silica S-1 (manufactured by Meiki Yushi) was used to encapsulate 30% by volume of tin oxide as a conductive metal oxide.

These microcapsules were added to the polymerization stage of polyethylene terephthalate to form a spherical porous hollow silica containing conductive metal oxide and polyethylene terephthalate (polyethylene terephthalate filling rate: 70%) at 0.05%.
Polyethylene terephthalate containing % by weight (hereinafter referred to as
(abbreviated as PET) (intrinsic viscosity [η) = 0.65, diethylene glycol 0.3 mol% copolymerization) was polymerized.

After drying the obtained PET at 180°C for 2 hours, it was fed to an extruder and melted at 285°C, then 100Kg/c
Mirror-finished chrome plating that was discharged from the mouthpiece by applying a filtration pressure of a1 or higher and maintained at 30°C while applying an electrostatic charge.
A non-oriented sheet was obtained by casting onto a roll.

This sheet was stretched 3.9 times in the machine direction at 95°C, then 4.1 times in the transverse direction at 98°C, and then heat-set for 3 seconds at 215°C while allowing 5% relaxation in the transverse direction. .

The thickness of the biaxially oriented film thus obtained was 2 μm, and the properties of this film are shown in Table 1. In addition, as comparative examples, a case where a conductive metal oxide was not added and a case where a conductive metal oxide was directly added were shown.

(Margins below this page) As is clear from Table 1, according to the present invention, a film with excellent electrostatic castability for extremely thin objects can be obtained, and this film has both electrostatic castability and dielectric breakdown voltage ( B
It is clear that it is also superior in terms of DV).

Example 3, Comparative Example 4 In Example 1, disperse dye Sumikalon Orange 13
(manufactured by Sumitomo Chemical) in microcapsules containing 85% PET by volume.
This microcapsule is made of PET.
A PET film was produced in the same manner as in Example 1, except that 0.05% by weight was added.

Note that the film thickness was 75 μm.

Table 2 below shows the results of a comparison between the properties of the obtained PET film and the properties obtained when the dye was directly added to PET.

Table 2 In Table 2, ■ is 300n under orthogonal Nicols.
It shows the light transmittance from m to 1500 nm, and ■ shows the light transmittance at a parallel value.

As is clear from Table 2, the film of the present invention has a remarkable effect of preventing color unevenness under polarized light.

Example 4, Comparative Example 5 Microcapsules with an average particle size of 5 μm filled with 65% by volume of divinylbenzene, 25% by volume of polypropylene, and 10% by volume of porosity as crosslinking agents were prepared using polypropylene (
Melt flow index ldl/g, stereoregularity index II = 99.5%) was added by 1.5% by weight.The melt was extruded from an extruder using a conventional method and cooled in close contact on a cast roll equipped with a Prosroll. Solidified. The cast sheet was stretched 5 times on a longitudinal stretching roll heated to 130°C, and then stretched 10 times in a horizontal stretching tenter heated to 158°C.
After the double stretching, the film was thermally solidified at 165° C. without being relaxed by 5% in the transverse direction to obtain a biaxially stretched polypropylene film with a thickness of 90 μm.

On the other hand, Example 4 except that 0.05% by weight of divinylbenzene was directly added to the polypropylene as Comparative Example 5.
A two-wheel stretched polypropylene film having a thickness of 90 μm was obtained in exactly the same manner as above.

The degree of crosslinking in Table 3 is expressed by the weight % of the dissolved residue based on the film after dissolving the film in n-peptane.

The degree of swelling represents the rate of increase in film thickness after 48 hours of immersion in a dodecylbenzene solution at 80°C.

As described above, it can be seen that by encapsulating the crosslinking agent in microcapsules, the film is not colored and the swelling of the obtained film is small, which is excellent.

Example 5, Comparative Example 6 A PET film was obtained in the same manner as in Example 1, except that 5% by weight of microcapsules filled with 40% by volume of carbon black and 60% by volume of PET were added to PET. Note that the film thickness was 75 μm.

Table 4 shows the results of comparison with Comparative Example 6 in which 2% by weight of carbon black was added directly to the PUT.

From Table 4, it is clear that direct addition of carbon blank leads to secondary aggregation, resulting in rough film surfaces, dropouts, and a decrease in light-shielding properties.

The light shielding property was evaluated as ◯ if the transmittance of light at 900 nm was less than 30%, △ if it was 30 to 60%, and × if it was more than 60%.

Example 6 As an antistatic agent, Sanstatsu) 721 (cationic quaternary ammonium salt, liquid at room temperature, manufactured by Sanyo Chemical) was used at 9
2% by volume, 0.50% by weight of microcapsules encapsulating 8% by volume of PET, and 0% by weight of colloidal silica with an average particle size of 160μm (manufactured by Nippon Shokubai Kasei Co., Ltd.) with an average particle size of 120μm.
．． PE was prepared in the same manner as in Example 1 except that 2% by weight was added.
A T film was produced.

However, the stretching conditions are as follows: 120°C in the longitudinal direction of the PET sheet.
The resulting biaxial The thickness of the oriented film was 9 μm.

The properties of the obtained film are shown in Table 5.

(Margins below this page) Table 5 As is clear from Table 5, it has excellent antistatic properties and slip properties even after repeated running tests, and the antistatic properties are even better after running. It shows the value.

Comparative Example 7 Instead of the spherical porous hollow silica containing an antistatic agent used in Example 6, Aerosil ATT (average particle size 0.7μ
Using PET containing 0.05% by weight of M1 (manufactured by Degutsusa) and 0.5% by weight of the same antistatic agent as in Example 6, it was biaxially stretched in the same manner as in Example 6 to a thickness of 9 μm.
A film of m was obtained.

The quality of the obtained film is shown in Table 5 above, and it can be seen that not only the surface characteristic value but also the coefficient of friction deteriorated significantly after repeated running, making it impossible to use it as a base film for magnetic tape.

Of course, during the film-forming process, the antistatic agent in this film is heavily scattered, and gelled substances are mixed in, resulting in coloring of the entire film, which is poor in both appearance and quality.

Example 7 A biaxially oriented film with a thickness of 9 μm was obtained in the same manner as in Example 7, except that the longitudinal stretching conditions in Example 6 were changed to 3.3 times stretching at 87° C.

As is clear from Table 5, it is found to be inferior to Example 6 in antistatic effect and slipperiness effect after the running test.

In order to investigate these causes, we used a secondary ion mass spectrometer (SIMS) device to measure the concentration distribution of inorganic additive 5i02 in the cross-sectional direction, and calculated the thickness from the film surface layer where the maximum concentration occurs and the concentration. I asked for it. The results are shown in Table 6.

Table 6 From Table 6, it can be seen that the concentration distribution of the additive in the cross-sectional direction varies depending on the conditions of the film forming process, resulting in a difference in quality.

Example 8 The same procedure was carried out except that the solid antistatic agent Erion A-34 (cationic diameter quaternary ammonium salt, paste form, manufactured by Sanyo Chemical) was used instead of the liquid antistatic agent used in Example 6. A film was formed under exactly the same conditions as in Example 6.

As shown in Table 5 above, the antistatic effect of the obtained film is slightly inferior even before running, depending on the type of additive, and the antistatic properties are only slightly deteriorated after running.

Comparative Example 14.15 Instead of using the microcapsules encapsulating the mixture of antistatic agent and PET used in Example 6, when only the antistatic agent was encapsulated in the microcapsules (Comparative Example 14)
), 0.5 directly to PET without using microcapsules.
The effect of the present invention was examined by comparing the case where the amount of chlorine was added by weight% (Comparative Example 7) with Example 6.

Thus, it can be seen that it is necessary to contain at least 8% by volume of a polymer having substantially the same composition as the thermoplastic polymer added to the microcapsules.

Example 9, Comparative Example 8 Benzotriazole-based Tinu was used as an ultraviolet absorber.
Vin 326 (manufactured by Geigi) at 70% by volume, pEr
A film with a thickness of 100 μm was produced in the same manner as in Example 1, except that 5% by weight of microcapsules filled with 30% by volume of the following were added.

However, the film stretching conditions were 120°C in the longitudinal direction and 1.
The film was stretched 7 times, 2.9 times at 95°C, then 4.0 times in the transverse direction at 98°C, and heat set at 190°C for 5 seconds while allowing 5.0% relaxation.

The thickness of the obtained film was 100 μm.

Further, Comparative Example 8 showed a case where the material was directly added to PET without being encapsulated in microcapsules.

Film properties are shown in Table 8.

From Table 8, it is clear that long-term weather resistance is improved by encapsulating the ultraviolet absorber in microcapsules.

Long-term weather resistance means that the elongation at break of the film after being exposed outdoors for 2 years is ○ if it has a retention rate of more than 50% compared to the untreated film, and △ if it is 50 to 30%. 3
Those less than 0% were marked as x.

Example IO and Comparative Example 9 Microcapsules filled with 95% by volume of silicone oil 511200 (viscosity 50CP) and 5% by volume of PET were
．． PE was added in the same manner as in Example 1 except that 01% by weight was added.
A T film was produced.

However, the stretching conditions were 115°C in the longitudinal direction, 1.6 times, 9
It was stretched 3.0 times at 5°C, then 4.0 times in the transverse direction at 95°C, and heat set at 195°C for 3 seconds while giving 5% relaxation.

The thickness of the obtained film was 9 μm.

Further, Comparative Example 9 showed a case where silicone oil was directly added.

Film properties are shown in Table 9.

Table 9 Table 9 shows that since the silicone oil is gradually released from the microcapsules, the difference in slipperiness (μS) before and after running is small, the surface condition is good, and there is a large difference in adhesive strength compared to the comparative example. It turns out that there is.

Example 11 and Comparative Example 10 60% by volume of zinc-based metal soap TMT-103 (Tokyo Fine Chemicals) and 40% by volume of PET as heat stabilizers
A PET film was obtained in the same manner as in Example 1, except that 0.1% by weight of the encapsulated microcapsules was added.

The stretching conditions were the same as in Example 10, and the film thickness was 2.
It was 5 μm.

Film quality is shown in Table 10.

Even if the film of the present invention is used in two ways at 150″C [η
] There was no decrease in

On the other hand, when metal soap is directly added to PET (Comparative Example 1
Example 12 and Comparative Examples 11 to 13 in which a large decrease in [η] was observed Li was used as a metal halide to improve gas barrier properties.
A 15 μm thick film was produced in the same manner as in Example 1, except that 5% by weight of microcapsules containing 60% by volume of ck and 40% by volume of nylon 6 was added to nylon 6 (relative viscosity 3.2). However, the stretching conditions were 3 times stretching at 80°C in the machine direction, 3 times stretching at 85°C in the horizontal direction, and 3 times stretching at 85°C in the transverse direction.
Heat fixation was performed for 5 seconds while giving 7% relaxation.

In addition, as a comparative example, a case where a metal chloride was directly added was shown.

The properties of the obtained film are shown in Table 11.

Oxygen barrier property means that the oxygen permeability measured according to JIS is less than 2 (cc/day 1) per 15 μm, ○, 2 to 10 (cc/day m'), Δ, 1
Anything over 0 (cc/day d) is multiplied.

As is clear from Table 11, by encapsulating metal chlorides in microcapsules, moisture absorption of chips is suppressed, handling becomes easier, productivity is improved, and gas barrier properties, stretching, and slipping properties are improved. It also improves.

[Brief explanation of drawings]

FIG. 1 is an enlarged schematic cross-sectional view of an inorganic porous microcapsule used in the present invention. ■...Wall material, 2...Hollow part.

Claims (1)

[Claims] Thermoplastic polymer characterized by adding inorganic porous microcapsules encapsulating a thermoplastic polymer at a filling rate of 5 to 80% by volume and a property imparting agent at a filling rate of 1 to 95% by volume. Plastic polymer sheet.