JP2000327805A - Resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve barrier properties without causing discoloration and spoiling transparency by setting the ratio of a swellable laminar silicate salt having a diameter of a circle, having an equivalent area to that of the salt, of a specific value or less among swellable laminar silicate salts contained in a resin film to a specific value or more. SOLUTION: There is provided a resin film formed from a resin composition comprising 100 pts.wt. of a polyester resin and/or a polycarbonate resin having incorporated therein 0.001-12 pts.wt. of a swellable laminar silicate salt containing at least 30 wt.% of that having a diameter of a circle, having an equivalent area thereto, of not more than 2,000 Å in such an amount that the number of particles dispersed is at least 40/100 μm2. The aspect ratio of the swellable laminar silicate salt in the resin film is 10-300 and the average thickness of the layer is not more than 300 Å. As the swellable laminar silicate salt can be employed montmorillonite, bentonite or the like. This resin composition is obtained by preparing a swellable laminar silicate salt-water dispersion containing the swellable laminar silicate salt and water, mixing this dispersion with a polymerizable prepolymer such as a polyester resin or the like and then polymerizing the polymerizable prepolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin film containing a polyester resin and / or a polycarbonate resin and a swellable layered silicate.

[0002]

2. Description of the Related Art Polyester resin films such as polyethylene terephthalate and polyethylene naphthalate and polycarbonate resin films such as bisphenol A-type aromatic polycarbonate have mechanical strength, dimensional stability, cold / heat resistance, high rigidity, workability, and transparency. Because it has excellent characteristics such as properties in a well-balanced manner, it is widely used as an industrial material for magnetic materials, electric materials and the like.
In recent years, other than industrial materials, as packaging film materials,
Development of barrier material applications such as food and beverage packaging materials, medical sterile packaging materials, and pharmaceutical packaging materials is desired. However, polyester resin films and polycarbonate resin films are practically insufficient as barrier materials for oxygen gas barrier applications, and various studies for improvement have been attempted.

For example, a method of covering the surface with vinylidene chloride (PVDC) (so-called K-coated product) and a method of depositing a special silicon oxide or alumina can be used. However, chlorine-containing materials such as K-coated products are being shunned in recent years due to increasing interest in environmental issues and the problem of toxic gas generation during combustion. In addition, the method of depositing silicon oxide or alumina has problems in terms of cost, such as loss of transparency, which is a feature of the film, and high cost.

As another attempt, studies have been made to specify the proportions of a polyethylene isophthalate copolymer, terephthalic acid / isophthalic acid and ethylene glycol / diethylene glycol, but this is not at a practically satisfactory level.

[0005] As another attempt, a resin composite containing a resin matrix and a layered particle having an average layer thickness of about 50 ° or less and a maximum layer thickness of about 100 ° or less is combined with an organometallic compound such as a silane compound. Invention on Materials (Patent Document WO 95/06090 (199)
No. 5), U.S. Pat. No. 5,514,734, International Publication No. 93 /
04118 pamphlet (1993), International Publication No. 93
/ 11190 pamphlet (1993)). Specifically, the water vapor permeability of a nylon 6-based composite material film composed of montmorillonite and nylon 6 bonded with isocyanatopropyltriethoxysilane and the like to which caprolactam has been copolymerized is improved. I have. However, depending on the production conditions of the resin composite material, coloring of the film due to the organometallic compound may occur, which may cause problems in appearance and transparency.

[0006]

Accordingly, there is substantially provided a technique for improving the barrier properties of a polyester resin film or a polycarbonate resin film without worrying about coloring and without impairing the inherent properties such as transparency. At present, it has not been done, and an object of the present invention is to solve such a problem.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an untreated swellable layered silicate which is not treated with an organometallic compound or the like is used, and a large number of thin plate-like unit layers are originally laminated. Separating and cleaving the layer from the swellable layered silicate particles existing in the form of agglomerates at the μm level, subdivided into a very large number of ultra-fine Å level plate-like particles, The inventors have found that the above objects can be achieved by independently and / or uniformly dispersing the components in a polycarbonate resin, and have completed the present invention.

That is, a first aspect of the present invention is a resin film containing a polyester resin and / or a polycarbonate resin and a swellable phyllosilicate, wherein the swellable phyllosilicate contained in the resin film is contained. The present invention relates to a resin film in which a ratio of a swellable layered silicate having an equivalent area circle diameter [D] of 2000 ° or less is 30% or more.

As a preferred embodiment, the present invention relates to the resin film described above, wherein the average value of the equivalent area circle diameter [D] of the swellable layered silicate is 3000 ° or less.

A second aspect of the present invention is a polyester resin and / or
Or a resin film containing a polycarbonate resin and a swellable layered silicate, wherein the average value of the equivalent area circular diameter [D] of the swellable layered silicate in the resin film is 3
000 ° or less.

A third aspect of the present invention is a polyester resin and / or
Or a resin film containing a polycarbonate resin and a swellable layered silicate, wherein the number of particles dispersed in an area of 100 μm ^{2 of the} resin film per unit ratio of the swellable layered silicate [N] It relates to a resin film having a value of 40 or more.

As a preferred embodiment, in any one of the resin films described above, the average aspect ratio (layer length / layer thickness ratio) of the swellable layered silicate in the resin film.
Is 10 to 300.

As a further preferred embodiment, the present invention relates to any one of the resin films described above, wherein the maximum thickness of the swellable layered silicate is 1000 ° or less.

As a further preferred embodiment, the present invention relates to any one of the above resin films, wherein the average thickness of the swellable layered silicate is 300 ° or less.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester resin used in the present invention refers to an acid component containing a dicarboxylic acid compound and / or an ester-forming derivative of dicarboxylic acid as a main component, and a diol compound and / or an ester-forming compound of a diol compound. It is a conventionally known arbitrary polyester resin obtained by a reaction with a diol component containing a derivative as a main component.

The term "main component" means that the proportion of each in the acid component or diol component is 80% or more, and more preferably 90% or more, and the upper limit is 100%.

Among the above dicarboxylic acid compounds, aromatic dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4 ' −
Examples thereof include diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, and 4,4'-diphenyl isopropylidene dicarboxylic acid. Substitutes thereof (for example, methyl isophthalic acid and the like) Alkyl group-substituted products) and derivatives (eg, alkyl ester compounds such as dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate) can also be used. Also, p-oxybenzoic acid and p
Oxy acids such as -hydroxyethoxybenzoic acid and their ester-forming derivatives may also be used. Two or more of these monomers may be used as a mixture. If the amount is small enough not to impair the properties of the obtained polyester resin composition, one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecane diacid, sebacic acid and the like are mixed with these aromatic dicarboxylic acids. Can be used.

Among the above-mentioned acid components, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and the like, in view of the crystallinity, strength and mechanical properties of the obtained polyester resin. Ester-forming derivatives are preferred.

Among the above diol compounds, the glycol compounds include aliphatic glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol and the like, and 1,4-cyclohexanedimethanol and the like. Alicyclic glycols, aromatic diols such as 1,4-phenylenedioxydimethanol, and the following general formula (1):

[0020]

Embedded image (Wherein -A- is -O-, -S-, -SO-, -SO
_2- , -CO-, an alkylene group having 1 to 20 carbon atoms or an alkylidene group having 6 to 20 carbon atoms, R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ and R ⁸ are each a hydrogen atom, a halogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms, which may be different from each other. ), For example, 2,2-bis (4-hydroxyphenyl) propane ("bisphenol A"), bis (4-hydroxyphenyl) methane, 1,1-bis (4'-hydroxyphenyl) Ethane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (“bisphenol TMC”), bis (4-hydroxyphenyl) cyclohexylmethane,
2,2-bis (4'-hydroxy-3,5'-dibromophenyl) propane, bis (4-hydroxy-3,5-
Dichlorophenyl) methane, bis (4-hydroxy-
3,5-dimethylphenyl) methane, 2,2-bis (4'-hydroxy-3 ', 5'-dimethylphenyl)
Propane, 1,1-bis (4'-hydroxyphenyl)
-1-phenylethane, 4,4'-dihydroxydiphenyl ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethylphenyl) ) Sulfone, 4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide, and the like, and substituted substances and derivatives thereof can also be used. Also, cyclic esters such as ε-caprolactone may be used. Two or more of these may be used in combination. Furthermore, if the amount is small enough not to significantly reduce the mechanical properties of the polyester resin, long-chain diol compounds (eg, polyethylene glycol, polytetramethylene glycol), and alkylene oxide addition polymers of bisphenols (eg, , An ethylene oxide addition polymer of bisphenol A) and the like.

Among the above-mentioned diol components, ethylene glycol, butylene glycol, and the like are considered from the viewpoints of handleability and strength and mechanical properties of the obtained polyester resin.
1,4-cyclohexanedimethanol and 2,2-bis (4-hydroxyphenyl) propane are preferred.

Specific examples of the polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, neopentyl terephthalate, polyethylene isophthalate, polyethylene naphthalate,
Polybutylene naphthalate, polyhexamethylene naphthalate, polyarylate obtained from the reaction of terephthalic acid and 2,2-bis (4-hydroxyphenyl) propane ("bisphenol A") (for example, manufactured by Unitika Ltd.)
(Trade name: U polymer), polyarylate obtained from the reaction of isophthalic acid and 2,2-bis (4-hydroxyphenyl) propane (for example, manufactured by DuPont, trade name: Arylon), a mixture of terephthalic acid and isophthalic acid, and Polyarylate obtained from the reaction of 2,2-bis (4-hydroxyphenyl) propane, a mixture of terephthalic acid and isophthalic acid, and 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4-hydroxy A polyarylate obtained from the reaction of a mixture of phenyl) -3,3,5-trimethylcyclohexane, a mixture of isophthalic acid and 2,5-naphthalenedicarboxylic acid and 2,2
Polyarylate obtained from the reaction of -bis (4-hydroxyphenyl) propane, a mixture of isophthalic acid and 2,5-naphthalenedicarboxylic acid and 2,2-bis (4-
Polyarylate obtained from the reaction of a mixture of (hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane. Further, a copolymerized polyester produced by using two or more kinds of acid components and / or diol components used for producing these resins may be mentioned.

The above-mentioned polyester resins can be used alone or in combination of two or more of those having different compositions or components and / or having different intrinsic viscosities.

Among the polyester resins, polyethylene terephthalate, polybutylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, polyethylene naphthalate, and terephthalic acid and / or isophthalic acid are preferred in view of strength, mechanical properties, cost, and the like. And a polyarylate obtained by a reaction using bisphenol A is preferred.

The molecular weight of the polyester resin is such that the intrinsic viscosity measured at 25 ° C. using a phenol / tetrachloroethane (5/5 weight ratio) mixed solvent is 0.3 to 2.0 (dl).
/ G) is desirable. When the intrinsic viscosity is 0.3 (dl /
If it is less than g), the mechanical properties and impact resistance of the obtained film are low, and if it is more than 2.0 (dl / g), the fluidity during film formation is reduced.

The polycarbonate resin used in the present invention is not particularly limited, and any conventionally known polycarbonate resin obtained by a reaction between a bisphenol compound and phosgene or a reaction between a bisphenol compound and a diester carbonate can be used.

As the bisphenol compound, in addition to the compound represented by the above general formula (1), a polymer obtained by copolymerizing a bisphenol having a benzotriazole group in order to enhance flame retardancy can be used. Substitutes and derivatives of these bisphenol compounds can also be used. These bisphenol compounds may be used alone or in combination of two or more.

Examples of the carbonic acid diester compound include bisalkyl carbonates such as dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate and di-n-butyl carbonate, diphenyl carbonate, bis (2,4-
Dichlorophenyl) carbonate, bis (2,4,6-
Trichlorophenyl) carbonate, bis (2-nitrophenyl) carbonate, bis (2-cyanophenyl)
Bisaryl carbonates such as carbonate, bis (4-methylphenyl) carbonate, bis (3-methylphenyl) carbonate, and dinaphthyl carbonate are exemplified.

Specific examples of the polycarbonate resin include:
2,2-bis (4-hydroxyphenyl) propane type polycarbonate resin, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane type polycarbonate, 1,1-bis (4-hydroxyphenyl) cyclohexane type Polycarbonate, 4,4′-dihydroxyphenyl ether type polycarbonate, 4,4′-dihydroxydiphenyl sulfide type polycarbonate,
4'-dihydroxydiphenylsulfone type polycarbonate, bis (4-hydroxyphenyl) ketone type polycarbonate, 1,4-bis (4-hydroxyphenylsulfonyl) benzene, and the like. They may be used alone or in combination of two or more.

The above-mentioned polycarbonate resins may be used alone, or two or more of those having different constituent components and ratios and / or different molecular weights may be used in combination.

Among the above polycarbonate resins, bisphenol A is preferred in view of strength, mechanical properties and cost.
Mold polycarbonate is preferred.

The polycarbonate (PC) resin has a viscosity average molecular weight (Mv) of 10,000 to 200,000,
Preferably it is 20000-120,000. When the viscosity average molecular weight is less than 10,000, the strength of the obtained resin film tends to decrease, and
If it is larger, there is a tendency that a problem occurs in processability such as fluidity during solution casting.

The viscosity-average molecular weight was determined by measuring the intrinsic viscosity of a chloroform solution of a polycarbonate resin at a measurement temperature of 25 ° C. by using Mark-Houk-Sakurada.
(ink-Sakurada). The various coefficients of the above formula are described in Polymer Handbook, Third Revised Edition, Willie (1989) (Poly
mer Handbook 3rd Ed. Wille
y, 1989), pp. 7-23.

The swellable layered silicate used in the present invention is mainly formed of a tetrahedral sheet of silicon oxide and an octahedral sheet of metal hydroxide. Examples of the swellable layered silicate include smectite clay and swellable mica. No.

The smectite group clay is represented by the following general formula (2): X _0.2 to _0.6 Y ₂ to ₃ Z ₄ O ₁₀ (OH) ₂ .nH ₂ O (2) (where X is K, Na, 1 / 2Ca and 1 / 2Mg
At least one member selected from the group consisting of
e, Mn, Ni, Zn, Li, Al, and at least one member selected from the group consisting of Cr, and Z is at least one member selected from the group consisting of Si and Al. Note that H ₂ O represents a water molecule bonded to an interlayer ion, and n varies remarkably depending on the interlayer ion and the relative humidity. Specific examples of the smectite group clay include, for example, montmorillonite,
Examples include beidellite, nontronite, saponite, iron saponite, hectorite, sauconite, stevensite, bentonite, and the like, and substituted substances, derivatives, and mixtures thereof. The distance between the bottom surfaces of the smectite group clay in the initial aggregation state is about 10 to 1
7 °, and the average particle size of the smectite group clay in the agglomerated state is approximately 1000-1,000,000 °.

The swellable mica is represented by the following general formula (3): X _0.5 to _1.0 Y ₂ to ₃ (Z ₄ O ₁₀ ) (F, OH) ₂ (3) (where X is Li, Na, At least one member selected from the group consisting of K, Rb, Ca, Ba, and Sr;
g, one or more selected from the group consisting of Fe, Ni, Mn, Al, and Li, and Z is Si, Ge, Al, F
at least one selected from the group consisting of e and B. )
And natural or synthetic. These are substances having the property of swelling in water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. For example, lithium-type teniolite, sodium-type teniolite, lithium-type Examples thereof include silicon mica, sodium tetrasilicic mica, and the like, and substituted substances, derivatives, and mixtures thereof. The distance between the bottom surfaces of the swellable mica in the initial aggregation state is approximately 10 to 17
Å, and the average particle size of the swellable mica in the aggregated state is about 10
It is 00 to 1,000,000 °.

Some of the above-mentioned swellable mica have a structure similar to that of vermiculite, and such a vermiculite equivalent can be used. The said vermiculite such equivalent has three octahedral type and dioctahedral the following general formula (4): (Mg, Fe , Al) 2 ~ 3 (Si 4-x Al x) O 10 (OH) 2 (M ⁺ , M ²⁺ _1/2 ) _x · nH ₂ O (4) (where M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x = 0.6 to 0.6) 9, n =
3.5 to 5). In the initial state of aggregation of the vermiculite-equivalent product, the distance between the bottom surfaces is approximately 10 to 17 °, and the average particle size in the aggregated state is approximately 1000 to 5,000,000 °.

The crystal structure of the swellable layered silicate is desirably high in purity, which is regularly stacked in the c-axis direction. However, a so-called mixed-layer mineral in which the crystal cycle is disturbed and a plurality of types of crystal structures are mixed is also used. Can be used.

The swellable layered silicate may be used alone or in combination of two or more. Among these, montmorillonite, bentonite, hectorite and swellable mica with sodium ions between layers,
It is preferable from the viewpoint of easy availability, dispersibility in the obtained resin film, and effect of improving the physical properties of the resin film.

In the present invention, there is no need to treat the swellable layered silicate with a swelling agent such as an organometallic compound such as a silane compound or an organic onium salt, so that there is no fear of coloring due to these.

In the resin film of the present invention, the compounding amount of the swellable layered silicate with respect to 100 parts by weight of the resin component composed of the polyester resin and / or the polycarbonate resin is 0.001 to 12 parts by weight, preferably 0.003 to 12 parts by weight. 1
0 parts by weight, more preferably 0.005 to 8 parts by weight. If the amount of the swellable layered silicate is less than 0.001 part by weight, the effect of improving the barrier properties may not be sufficient, and if it exceeds 12 parts by weight, transparency and surface properties may be impaired.

The ash content of the resin film derived from the swellable layered silicate is typically 0.001 to 10% by weight, preferably 0.003 to 8% by weight, more preferably 0.005 to 10% by weight. It is prepared to be 6% by weight. If the ash content is less than 0.001 part by weight, the effect of improving the barrier properties may not be sufficient, and if it exceeds 10% by weight, the transparency and surface properties may be impaired.

The form of the swellable phyllosilicate dispersed in the resin film of the present invention is the same as that of the swellable phyllosilicate before blending, because the swellable phyllosilicate has a large number of layers laminated and formed. Completely different from the structure. That is, the swellable layered silicate layer is cleaved and fragmented independently of each other. As a result, the swellable phyllosilicate is dispersed in a very fine and independent lamellar form in the resin film, and the number thereof is significantly increased as compared with the swellable phyllosilicate before compounding. The dispersion state of such a thin plate-like swellable phyllosilicate is as follows: equivalent area circle diameter [D], number of dispersed particles [N], aspect ratio (ratio of layer length / layer thickness), average layer thickness , Maximum layer thickness.

First, the equivalent area circular diameter [D] has an area equal to the area on the image of each swellable layered silicate dispersed in various shapes in an image obtained by a microscope or the like. Defined as the diameter of the circle. In this case, among the swellable phyllosilicates dispersed in the resin film, the ratio of the number of swellable phyllosilicates having an equivalent area circle diameter [D] of 2000 ° or less is 30% or more, and preferably 40% or more. % Or more, more preferably 50% or more, and particularly preferably 60% or more. Equivalent area circle diameter [D] is 200
If the ratio of 0 ° or less is less than 30%, the effect of improving the mechanical properties and gas barrier properties of the resin film may be insufficient. The average value of the equivalent area circle diameter [D] of the swellable layered silicate in the resin film of the present invention is 300.
0 ° or less, preferably 2500 ° or less, more preferably 2000 ° or less. If the average value of the equivalent area circle diameter [D] is more than 3000 °, the effect of improving the mechanical properties and gas barrier properties of the resin film may not be sufficient, and the surface properties and transparency may be impaired. Although there is no particular lower limit, the effect hardly changes when the angle is less than about 100 °.

The equivalent area circle diameter [D] is measured by selecting an arbitrary region containing 100 or more swellable layered silicate layers on an image taken using a microscope or the like, and using an image processing device or the like. Can be quantified by image formation using a computer and computer processing.

When the number [N] of dispersed particles is defined as the number of dispersed particles per unit weight ratio of the swellable phyllosilicate in an area of 100 μm ² of the resin film,
The [N] value of the swellable layered silicate in the resin film is 4
It is 0 or more, preferably 45 or more, more preferably 50 or more, and particularly preferably 60 or more. There is no particular upper limit, but if the [N] value exceeds about 1000, the effect will not change any more.
There is no need to make it larger. The [N] value can be obtained, for example, as follows. That is, the resin film is cut into an ultrathin section having a thickness of about 50 μm to 100 μm, and the number of particles of the swellable layered silicate present in an arbitrary region having an area of 100 μm ² is determined on an image obtained by photographing the section with a TEM or the like. By the weight ratio of the swellable phyllosilicate used. Alternatively, on the TEM image, an arbitrary region (area is measured) in which 100 or more particles are present is selected, and the number of particles present in the region is determined by the weight ratio of the swellable layered silicate used. Then, a value converted to the area of 100 μm ² may be used as the [N] value. Therefore, the [N] value can be quantified by using a TEM photograph or the like of the resin film. The weight ratio of the swellable layered silicate may be the ash content of the resin film derived from the swellable layered silicate.

When the average aspect ratio is defined as the average value of the ratio of the layer length / layer thickness of the swellable phyllosilicate dispersed in the resin, the swellable phyllosilicate in the resin film is defined as an average value. The average aspect ratio is from 10 to 300, preferably from 15 to 300. More preferably, it is 20 to 300. If the average aspect ratio is less than 10, the effect of improving the mechanical properties and gas barrier properties of the obtained resin film may not be sufficiently obtained. Further, even if it is larger than 300, the effect does not change any more, so that it is not necessary to make the average aspect ratio larger than 300.

When the average layer thickness is defined as the average value of the layer thickness of the swellable layered silicate dispersed in a thin plate shape,
The upper limit of the average layer thickness of the swellable phyllosilicate in the resin film is 300 ° or less, preferably 250 ° or less, more preferably 200 ° or less. Average layer thickness is 3
If it is larger than 00 °, the effect of improving the mechanical properties and gas barrier properties of the obtained resin film may not be sufficiently obtained. Although the lower limit of the average layer thickness is not particularly limited,
Greater than Å.

When the maximum layer thickness is defined as the maximum value of the layer thickness of the swellable layered silicate dispersed in a thin plate shape in the resin film, the upper limit of the maximum layer thickness of the swellable layered silicate is defined. Is 1000 ° or less, preferably 850 ° or less, more preferably 700 ° or less. If the maximum layer thickness is more than 1000 °, the transparency and surface properties of the obtained resin film may be impaired. Although the lower limit of the maximum layer thickness of the swellable layered silicate is not particularly limited, it is 10 °.
Greater than.

The layer thickness and the layer length can be determined from an image obtained by using a microscope or the like to obtain a film obtained by heating and melting a resin film and then performing hot press molding or stretch molding.

That is, an ultrathin section having a thickness of about 50 μm to 100 μm is cut out in a direction perpendicular to the plane direction of the film prepared by the above method, and the section is cut out by a transmission electron microscope or the like to about 40 to 100,000 times. It can be determined by observing at the above high magnification. The measurement is performed by placing an arbitrary region containing 100 or more swellable phyllosilicates on an elephant of a transmission electron microscope obtained by the above method, forming an image with an image processing device or the like, and performing computer processing. Can be quantified. Alternatively, it can also be obtained by measuring using a ruler or the like.

The method for producing the resin film of the present invention is not particularly limited. For example, a swellable layered silicate in which a swellable layered silicate is uniformly and finely dispersed in a thin plate beforehand in a polyester resin and / or a polycarbonate resin. It is obtained by producing a resin-containing resin and then forming it into a film.

The method for producing a swellable layered silicate-containing polyester resin in which the swellable layered silicate is uniformly and finely dispersed in a thin plate shape includes, for example, (A) a swellable layered silicate containing water and water. Preparing a silicate-water dispersion;
A method including (B) a step of mixing a polymerizable prepolymer of a polyester resin with the swellable layered silicate-water dispersion, and (C) a step of polymerizing the polymerizable prepolymer are preferable.

Regarding the above step (A), the method for preparing the swellable layered silicate-water dispersion is not particularly limited, and for example, is performed using a conventionally known wet stirrer. Examples of the wet stirrer include a high-speed stirrer in which a stirring blade rotates at a high speed and stirs, a wet mill for wet-milling a sample in a gap between a rotor and a stator at a high shear rate, and a mechanical method using a hard medium. Examples include wet crushers and wet crushers that collide a sample at a high speed with a jet nozzle or the like. In order to perform mixing efficiently, the rotation speed of stirring is 500 rpm or more, or a shear rate of 300 (1 / s) or more is applied. The upper limit of the number of revolutions is 25000 rp
m, and the upper limit of the shear rate is 500000 (1 / s).
It is. There is a tendency that the effect does not change even if the stirring is performed at a value larger than the upper limit, so that it is not necessary to perform the stirring at a value larger than the upper limit.

The swellable layered silicate-water dispersion contains, if necessary, a polar solvent compatible with water at an arbitrary ratio. Examples of the polar solvent include alcohols such as methanol, ethanol and isopropanol; glycols such as ethylene glycol, propylene glycol and 1,4-butanediol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran. And amide compounds such as dimethylformamide, and other solvents such as dimethylsulfoxide and 2-pyrrolidone. These polar solvents may be used alone or in combination of two or more.

By preparing the swellable phyllosilicate-water dispersion by the above-mentioned method, the initial layered / aggregated structure of the swellable phyllosilicate disappears, and the interval between the layers expands to form a so-called swelling state. It becomes. In the present specification, the initial bottom surface interval of the swellable layered silicate is the bottom surface interval of the particulate swellable layered silicate in which unit layers are stacked and aggregated before being added to the dispersion medium. Intended for something.

As the step (B), a step of mixing the polymerizable prepolymer of a polyester resin and the swellable layered silicate-water dispersion may be performed.

Here, the polymerizable prepolymer of the polyester resin means at least one selected from polymerizable monomers of the polyester resin and low-polymerized polymers.

The polymerizable monomer includes an acid component mainly composed of a dicarboxylic acid compound and / or an ester-forming derivative of dicarboxylic acid, and a diol component mainly composed of a diol compound and / or an ester-forming derivative of a diol compound. However, since it has already been described in detail, it is omitted here.

The low-polymerized polyester resin is a condensate obtained by the reaction of the above-mentioned polymerizable monomer and is a swellable layered silicate-water dispersion containing a swellable layered silicate in a molten state. Has a molecular weight such that the melt viscosity is such that it can be sufficiently uniformly dispersed. From the viewpoint of the uniform dispersibility of the swellable layered silicate-water dispersion, the logarithmic viscosity of the low-polymerized polymer is less than 0.4 (dl / g), preferably 0.35 (dl / g) or less. And more preferably 0.30 (dl / g) or less.

The method for obtaining the above-mentioned polymer having a low degree of polymerization is not particularly limited. Examples of such a method include a method of esterifying an aromatic dicarboxylic acid with a diol compound,
Examples of the method generally used include a method of transesterifying an aromatic dicarboxylic acid alkyl ester and a diol compound. As described above, in addition to the method of obtaining an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol compound or an ester-forming derivative thereof by a condensation reaction, part or all of a polyester resin is depolymerized with a diol compound. The method of obtaining is also mentioned. That is, for example, a method of heating a mixture of a polyester resin and a diol compound as a raw material and depolymerizing in a temperature range from about 150 ° C. to a melting point of the polyester resin, or a method in which the polyester resin as a raw material is previously heated to the melting point of the polyester resin or more. And a method in which a diol compound is added thereto and depolymerized while stirring. In this case, when a plurality of diol compounds are copolymerized into a copolymerized polyester resin, a diol compound having a structure different from the diol component constituting the polyester resin can be added and used for depolymerization. As the diol compound used for the depolymerization of the polyester resin, one or more of the same diol compounds as the various diol compounds used as the polymerizable monomer of the polyester resin are used. The catalyst required for the reaction to obtain a low-polymer polyester is a transesterification catalyst, and one or more of metal oxides, carbonates, acetates, and alcoholates can be used. In the method obtained by depolymerization of the polyester resin, the catalyst required for the reaction is usually already contained in the polyester resin as the starting material, but if necessary, the above-mentioned transesterification catalyst is newly added and used. You can do it.

The method for mixing the swellable layered silicate-water dispersion and the polymerizable prepolymer of the polyester resin is not particularly limited. As such a method, for example, a polymerizable prepolymer of a polyester resin is made into a molten state and / or a solution, and then a swellable layered silicate-water dispersion is added, mixed, and deaerated using a liquid addition device or the like. And the like.

The timing of mixing is not particularly limited, and mixing can be performed at any stage. For example, during storage / preparation of a polymerizable monomer of a polyester resin (in a monomer preparation tank, etc.), during transesterification reaction of the above polymerizable monomer (in a transesterification tank), when condensation polymerization of an ester exchange product to give a high molecular weight. (In a polymerization tank, etc.). The mixing speed may be, for example, a method of batch-mixing a polymerizable prepolymer of a polyester resin in a molten state or a solution and a swellable layered silicate-water dispersion, or a method of continuously mixing a swellable layered silicate-water dispersion. And the method of adding sequentially or sequentially. In such a case, the rate of addition of the swellable layered silicate-water dispersion is not particularly limited, but is based on 100 parts by weight of the polymerizable prepolymer of the polyester resin. 0.01 to 10.0 parts by weight /
Min, preferably from 0.03 to 8.0 parts by weight / minute, more preferably from 0.05 to 6.0 parts by weight / minute, continuously or sequentially. The temperature of the system during mixing is not particularly limited,
For example, if the polymerizable prepolymer of the polyester resin is in a molten state, the melting point is equal to or higher than the melting point, and
0 ° C., more preferably 80 ° C. to 250 ° C.,
More preferably, the temperature is from 80C to 200C. It is not necessary to keep the mixing temperature constant within the above temperature range. Therefore,
The temperature fluctuation width is not particularly limited, but is preferably 100 ° C.
Or less, more preferably 80 ° C. or less, and still more preferably 50 ° C. or less.

As described above, mixing can be performed by various methods.
At the time of mixing, the polymerizable prepolymer of the polyester resin is preferably in a molten state, which is preferable in terms of productivity, handling of the system, and solvent-free because it is solvent-free, in terms of safety, environment, and hygiene. The method of adding the body continuously and sequentially is preferable from the viewpoint of improving the dispersibility of the swellable layered silicate and improving the physical properties of the obtained resin composition.

As the step (C), a step of increasing the molecular weight of the polymerizable prepolymer of the polyester resin may be performed. The method for increasing the molecular weight is not particularly limited, and can be achieved by a generally-used polymerization method of a polyester resin. Examples of such a method include a melt polycondensation method and a solid phase polymerization method.

In the case where another diol component is copolymerized with the resin component, a desired diol compound is added and mixed at any time during the melt polycondensation reaction, and then the melt polycondensation reaction or the solid phase polymerization is carried out. Is obtained by The catalyst necessary for the reaction is used by adding one or more of metal oxides, carbonates, acetates, and alcoholates as necessary.

The molecular weight after increasing the molecular weight was determined using a phenol / tetrachloroethane (5/5 weight ratio) mixed solvent.
The logarithmic viscosity measured at 25 ° C is 0.3 to 2.0 (dl /
g), preferably from 0.30 to 1.8 (dl / g), more preferably from 0.30 to 1.5 (dl / g), and still more preferably from 0.30 to 1.2 (dl / g). (Dl / g). If the logarithmic viscosity is less than 0.3 (dl / g), the mechanical properties are low. If the logarithmic viscosity is more than 2.0 (dl / g), the molding fluidity tends to decrease due to the high melt viscosity.

The method for producing a swellable layered silicate-containing polycarbonate resin in which the swellable layered silicate is uniformly finely dispersed in a thin plate shape is described in, for example, (D) Swelling layered silicate containing water and water. (E) mixing the polymerizable prepolymer of the polycarbonate resin with the swellable layered silicate-water dispersion, and (F) mixing the swellable layered silicate-water dispersion. It is preferable to produce by a method including a step of polymerizing a polymerizable prepolymer.

The step (D) is the same as the above step (A), and will not be described here.

As the step (E), a step of mixing the swellable layered silicate-water dispersion and a polymerizable prepolymer of a polycarbonate resin is performed. Here, the polymerizable prepolymer of the polycarbonate resin means at least one selected from a polymerizable monomer and a low polymer.

The polymerizable monomers of the polycarbonate resin include bisphenols and carbonates, but they have already been described in detail and will not be described here.

The low-polymer of the polycarbonate resin is a condensate obtained by the reaction of the above-mentioned polymerizable monomer, and is a swellable layered silicate in a molten state.
It means one having a molecular weight that gives a melt viscosity of such an extent that the water dispersion can be sufficiently uniformly dispersed.

The method for obtaining the above-mentioned low-polymer is not particularly limited, and any of an interfacial polymerization method, a pyridine method, and a transesterification method can be adopted. Among them, a low-polymer obtained by a transesterification method is preferable. The low polymer can also be obtained by depolymerizing a polycarbonate resin.

The method of mixing the swellable layered silicate-water dispersion and the polymerizable prepolymer is the same as that in the above step (B), and will not be described here.

As the above step (F), a step of increasing the molecular weight of the polymerizable prepolymer of the polycarbonate resin can be performed. The polymerization method is not particularly limited, and can be usually performed by a generally performed polymerization method of a polycarbonate resin.
From the viewpoint of operability and the like, the transesterification method is preferably employed.
In the transesterification method, a bisphenol compound is added to a mixture containing a carbonic acid diester compound, and the system is heated from about 280 to about 300 ° C. with sufficient stirring to perform a transesterification reaction in a molten state. Examples of the catalyst required for the transesterification method include simple metals / oxides of alkali metals or alkaline earth metals, hydroxides, amide compounds, alcoholates, phenolates, Sb ₂ O ₃ , ZnO, PbO,
One or more kinds of organic titanium compounds, quaternary ammonium salts and the like can be added and used.

The weight average molecular weight Mw measured at 40 ° C. by gel permeation chromatography (GPC) using a tetrahydrofuran (THF) solvent was converted into a monomolecular weight dispersed polystyrene in terms of the molecular weight after the increase in molecular weight.
15,000 to 80,000, preferably 30,000
~ 70,000.

The method for forming a film of the swellable silicate-containing resin obtained by the above method is not particularly limited, and examples thereof include a stretching method, a T-die extrusion method and a solution casting method.

The resin film of the present invention may include a polyester carbonate resin, if necessary, as long as the mechanical properties, transparency and surface properties of the film are not impaired.
Transparent thermoplastic resin such as polysulfone resin and polyphenylene ether resin, polybutadiene, butadiene
Styrene copolymer, natural rubber, chlorinated butyl rubber, α-
An elastomer such as an olefin copolymer can be added. The elastomer may be modified with an unsaturated carboxylic acid compound such as maleic anhydride or an unsaturated epoxy compound such as glycidyl methacrylate for the purpose of obtaining an affinity with the matrix resin.

Further, a lubricant, an antioxidant, a heat stabilizer, a weathering agent,
An additive such as an antistatic agent may be blended.

The resin film of the present invention can be laminated with any other film containing no swellable layered silicate to form a laminated film.

The method for producing the laminated film is not particularly limited. For example, a method of bonding the resin film of the present invention to another film with an adhesive or the like, and the method of flowing the resin film of the present invention on another film. A method of forming by a casting method, and conversely, a method of forming another film on a resin film of the present invention by a casting method, and the like.

In the resin film of the present invention, since the swellable layered silicate is very fine and thinly dispersed in a plate shape, the barrier property can be improved without impairing the transparency. .

The resin film obtained by the present invention is used as a packaging material for food and beverages, a medical packaging material, a medical packaging material, and also as an industrial material such as a magnetic material application, an electric material application, and an insulating material. it can.

[0084]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

Main raw materials used in Examples and Comparative Examples are shown below. Unless otherwise specified, the raw materials were not purified. -Bishydroxyethyl terephthalate: NISSO-BHET of Nisso Maruzen Chemical Co., Ltd. was used (hereinafter referred to as B
HET). -Dimethyl 2,6-naphthalenedicarboxylate: Wako first-class product manufactured by Wako Pure Chemical Industries, Ltd. was used (hereinafter referred to as NDC). -Dimethyl carbonate: Dimethyl carbonate from Wako Pure Chemical Industries, Ltd. was used (hereinafter referred to as DMC). Bisphenol A: Bisphenol A of Mitsui Chemicals, Inc. was used (hereinafter referred to as BPA). Swellable phyllosilicate: Lucentite SWN from Corp Chemical Co., Ltd. (synthetic hectorite, bottom spacing = 13)
Å, hereafter referred to as SWN) and Wenger HVP (Bentonite, bottom spacing = 13Å) from Toyshun Yoko Co., Ltd.
Wenger HVP) was used. The evaluation methods in Examples and Comparative Examples are summarized below. (Measurement of dispersion state) Ultrathin sections having a thickness of 50 to 100 µm were used. Transmission electron microscope (JEOL JEM-1200
Using EX), the dispersion state of the swellable layered silicate was observed and photographed at an acceleration voltage of 80 kV and a magnification of 40,000 to 1,000,000 times. T
In the EM photograph, an arbitrary region where 100 or more dispersed particles exist is selected, and the layer thickness, the layer length, the number of particles ([N]
Value), the equivalent area circle diameter [D] is measured by hand using a ruler with a scale, or an image analyzer P by Interquest.
It was measured by processing using IASIII.

The average aspect ratio was a number average value of the ratio between the layer length and the layer thickness of each swellable layered silicate. [N] value was measured as follows. First, on the TEM image, the number of particles of the swellable phyllosilicate existing in the selected region is determined. Separately, the ash content of the resin composition derived from the swellable phyllosilicate is measured. The value obtained by dividing the number of particles by the ash content and converting the result to an area of 100 μm ² was defined as the [N] value.

The average layer thickness was the number average of the individual swellable layered silicate layer thicknesses, and the maximum layer thickness was the maximum value among the individual swellable layered silicate layer thicknesses.

When the dispersed particles are large and observation with a TEM is inappropriate, the [N] value can be determined using an optical microscope (optical microscope BH-2 manufactured by Olympus Optical Co., Ltd.) in the same manner as described above. I asked. However, if necessary, the sample was melted at 250 to 300 ° C. using a LINKAM hot stage THM600, and the state of the dispersed particles was measured in the molten state.

The aspect ratio of the dispersed particles that are not dispersed in a plate shape was a value of major axis / minor axis. Here, the long diameter is intended to be the long side of the rectangle assuming a rectangle having the smallest area among rectangles circumscribing the target particle in a microscope image or the like. Further, the minor axis is intended to mean the short side of the minimum rectangle.

The equivalent area circle diameter [D] was measured by processing using an image analyzer PIASIII manufactured by Interquest. (Film Thickness) The film thickness of the film was measured using an electromagnetic thickness meter (SP-1100D) manufactured by Sanko Electronics Research Laboratory Co., Ltd. (Tensile properties) According to JIS K7127, at 25 ° C., a tensile speed of a resin film having a thickness of about 100 μm is 50 μm.
The tensile modulus at 0 mm / s was measured. The larger the value of the tensile modulus, the better. (Center line average roughness) Surface roughness meter of Tokyo Seimitsu Co., Ltd .; su
The center line average roughness was measured using rfcom1500A. The center line average roughness is preferable because the smaller the value, the smoother the value. (Transparency) The transparency of the resin film was evaluated in terms of haze (haze value). The haze of the film was measured according to JIS K7105 using a haze measuring device of Nippon Denshoku Industries Co., Ltd .; The smaller the value of the haze, the more transparent it is preferable. (Oxygen permeability) Nissan Sangyo Co., Ltd. oxygen permeability measuring device O
Using XTRAN, the oxygen permeability of the resin film having a thickness of about 25 μm was measured according to JIS K7126. The smaller the oxygen permeability is, the better the barrier property is. (Moisture permeability) Nissan Sangyo Co., Ltd. moisture permeability measurement device PERMA
It was measured according to JIS K7126 using TRAN. The smaller the value of the moisture permeability is, the better the barrier property is. (Ash content) The ash content of the resin film derived from the swellable layered silicate (or the swellable layered silicate) is determined by JISK
It measured according to 7052. (Production Example 1) 4000 g of ion-exchanged water and 120 g of SW
N was 5,000 rpm using a wet mill (Nippon Seiki Co., Ltd.).
m and stirring for 20 minutes to obtain a swellable layered silicate-water dispersion containing about 3% by weight of SWN.

3300 g of BHET was charged into the reactor,
The mixture was melted while stirring at 140 ° C. under a stream of dry nitrogen.
Then keep the system at 130-180 ° C and
BHET and the swellable layered silicate-water dispersion were mixed by gradually adding the swellable layered silicate-water dispersion while stirring at pm. The rate of addition is about 2000 g / hour. The evaporating water was drained out of the system.

After completion of the addition of the swellable layered silicate-water dispersion, the temperature of the system was gradually raised. The temperature in the system is about 220 ~
After confirming that about 70 to 80% of water in the added swellable layered silicate-water dispersion had flowed out of the system, 5.0 g of a hindered phenol-based stabilizer (Asahi ADK STAB AO60 (hereinafter referred to as AO60) and 0.5 g of antimony trioxide (Sb ₂ O ₃ ) were added, and the system was further heated to 280 ° C. After the temperature was raised, the system was decompressed (0.5-5.0 torr) and melt-polycondensed to obtain a swellable layered silicate-containing polyester resin a-1.
I got The amounts of the raw materials used are shown in Table 1 (the same applies to Production Examples 2 to 6).

[0093]

[Table 1] (Production Example 2) The amount of ion-exchanged water was set to 1300 g, and SW
A swellable layered silicate-containing polyester resin a-2 was obtained in the same manner as in Production Example 1 except that 120 g of Wengel HVP was used instead of N. However, the addition rate of the swellable layered silicate-water dispersion was about 1200 g / hour. (Production Example 3) A mixed solvent of 750 g of ion-exchanged water and 250 g of methanol and 120 g of HVP were mixed for 5000 r using a high-speed stirrer homogenizer (Nippon Seiki Co., Ltd.).
pm, and mixed for 15 minutes. Then, 550 g of ion-exchanged water was added, and the mixture was further stirred at 5000 rpm for 25 minutes to obtain a swellable layered silicate-water dispersion. Using the swellable layered silicate-water dispersion, a swellable layered silicate-containing polyester resin a-3 was obtained in the same manner as in Example 1. However, the addition rate of the swellable layered silicate-water dispersion was about 1400 g / hour. (Production Example 4) A swellable layered silicate-water dispersion was prepared in the same manner as in Production Example 1.

In a reactor, 2500 g of NDC, 1600
g of EG, 5.0 g of AO60 and 0.6 g of Ti (O
Bu) ₄ was charged, and the mixture was stirred at a reaction temperature of about 190 ° C. for about 3 hours to transesterify NDC and EG. Then 23
While maintaining the temperature at 0 to 250 ° C and stirring at 100 to 180 rpm, the swellable layered silicate-water dispersion was added and mixed.
The rate of addition was about 1600 g / hour.

After completion of the addition, the temperature of the system was gradually increased. After confirming that the temperature in the system reached about 220 to 240 ° C. and that about 70 to 80% of the water in the added swellable layered silicate-water dispersion had flowed out of the system, 0.5 g of the water was added. Sb ₂ O ₃ was charged, and the system was further heated to 280 ° C. After the temperature was raised, the system was decompressed (0.5 to 5.0 torr) and subjected to melt polycondensation to obtain a swellable layered silicate-containing polyester resin a-4. (Production Example 5) The amount of ion-exchanged water was set to 1800 g, and SW
A swellable layered silicate-containing polyester resin a-5 was obtained in the same manner as in Production Example 4 except that 120 g of Wengel HVP was used instead of N. However, the addition rate of the swellable layered silicate-water dispersion was about 1400 g / hour. (Production Example 6) 1300 g of ion-exchanged water and 120 g of H
The VP was stirred and mixed at 5,000 rpm for 20 minutes using a wet mill to obtain a swellable layered silicate-water dispersion containing about 8.5 wt% of HVP.

In a reactor, 2250 g of BPA, 2000 g
Of DMC, 19 g of dibutyltin oxide,
By reacting at a temperature of 160 ° C. under a pressure of 7 kg / cm ^{2 in} a nitrogen atmosphere, bismethyl carbonate of DPA was prepared. Then, while vigorously stirring the system at 180 rpm, the above-mentioned swellable layered silicate-water dispersion was gradually added to mix the bismethyl carbonate of BPA with the swellable layered silicate-water dispersion. . The rate of addition was about 900 g / hour. The evaporating water was drained out of the system.

Then, at a reaction temperature of 230 ° C. to 240 ° C.,
By performing melt polycondensation at a pressure of not more than torr, a swellable layered silicate-containing polycarbonate resin a-6 was obtained. (Production Example 7) 3300 g of BHET was charged into a reactor,
The mixture was melted while stirring at 140 ° C. under a stream of dry nitrogen.
When the temperature in the system reaches about 220 to 240 ° C, 5.
0 g of AO60 and 0.5 g of Sb2O3 were added and 28
The temperature was raised to 0 ° C. After the temperature was raised, the pressure was reduced (0.5 to 5.0 torr).
r) and melt polycondensation to obtain polyethylene terephthalate resin b-1. The amounts of raw materials used are shown in Table 2 (Production Example 7).
To 13).

[0098]

[Table 2] (Production Example 8) 2500 g of polyethylene terephthalate resin (obtained in the same manner as in Production Example 7), 120 g of SWN and 5.0 g of AO60 were subjected to a twin-screw extruder (LABOTEX30, manufactured by Nippon Steel Corporation). , Temperature 250 ~
Melt kneading under the conditions of 270 ° C. and 100 rpm,
Composition b-2 was obtained. (Production Example 9) 1500 g of EG and 120 g of SWN were mixed by stirring at 5000 rpm for 20 minutes using a wet mill.

3300 g of BHET was charged into the reactor,
The mixture was melted while stirring at 140 ° C. under a stream of dry nitrogen.
Then keep the system at 130-180 ° C and
The mixture was added while stirring at pm. After the addition was completed, the temperature was raised to about 220 to 240 ° C., and then 5.0 g of AO
60 and 0.5 g of Sb ₂ O ₃ were added, and the temperature was raised to 280 ° C. After the temperature was raised, the composition was melt-polycondensed under reduced pressure (0.5 to 5.0 torr) to obtain a composition b-3. (Production Example 10) 2500 g of NDC, 160
0 g EG, 5.0 g AO60 and 0.6 g Ti
(OBu) ₄ was added, and the mixture was stirred at a reaction temperature of about 190 ° C. for about 3 hours. When the temperature in the system reached about 220 to 240 ° C., 0.5 g of Sb ₂ O ₃ was added, and the temperature was raised to 280 ° C. After the temperature is raised, the polyethylene naphthalate resin b is subjected to melt polycondensation by reducing the pressure (0.5 to 5.0 torr).
-4 was obtained. (Production Example 11) 2500 g of polyethylene naphthalate resin (obtained in the same manner as in Production Example 10) and 120 g
Was melt-kneaded in the same manner as in Production Example 8 to obtain a composition b-5. (Production Example 12) In a reactor, 2250 g of BPA, 2000
g of DMC and 19 g of dibutyltin oxide were charged and reacted at a temperature of 160 ° C. under a pressure of 7 kg / cm ^{2 in} a nitrogen atmosphere to prepare bismethyl carbonate of DPA. Next, the reaction temperature is 230 ° C to 240 ° C.
Polycarbonate resin b-6 was obtained by melt polycondensation at 1 ° C. or lower at 1 ° C. (Production Example 13) 2500 g of polycarbonate resin (obtained in the same manner as in Production Example 12) and 120 g of SWN
And 5.0 g of AO60 in a twin-screw extruder (LABOTEX30, manufactured by Nippon Steel Corporation) at a temperature of 270-30.
The composition was melt-kneaded at 0 ° C. and a rotation speed of 100 rpm to obtain a composition b-7. (Examples 1 to 5) Swellable layered silicate-containing resin (a-1)
~ A-5) was dried (130 ° C, 5 hours), and then extruded at 280 ° C with an extruder having a T-die, and rapidly solidified to obtain an amorphous sheet. The obtained sheet is
3. Between the heating roll and the cooling roll, at 80 ° C in the longitudinal direction.
The film was stretched by a factor of 7 and a factor of 3.8 in the transverse direction at 95 ° C. Then, by performing a heat treatment on the stretched film at 200 ° C.
A resin film containing a swellable layered silicate was obtained and evaluated. The evaluation results are shown in Table 3 for Examples 1 to 3, and for Examples 4 and 4.
5 is shown in Table 4.

[0100]

[Table 3]

[0101]

[Table 4] Example 6 200 g of swellable silicate-containing resin a-6 was sufficiently dissolved in 1000 g of methylene chloride. The methylene chloride solution was cast on a substrate, and the solvent was dried at room temperature to 70 ° C. After drying, the film was peeled off from the substrate, and further subjected to 5 minutes at 100 ° C., 15 minutes at 130 ° C., and 1 minute at 150 ° C.
By performing heat treatment under the condition of 5 minutes, a resin film containing a swellable layered silicate was obtained. Evaluation is Example 1
The same was done. Table 5 shows the evaluation results.

[0102]

[Table 5] (Comparative Examples 1 to 5) In the same manner as in Example 1, Production Examples 7 to
The resin (b-1 to b-5) obtained in 11 was formed into a film and evaluated. The results are shown in Table 3 for Comparative Examples 1 to 3, and Table 4 for Comparative Examples 4 and 5.

In the comparative example, simply dispersing SWN with particles of μm level did not improve the barrier property at all and further impaired the transparency. (Comparative Examples 6 and 7) Production Example 1 by the same method as in Example 6.
The resins b-6 and b-7 obtained in 2, 13 were formed into films and evaluated. The results are shown in Table 5.

In the comparative example, simply dispersing SWN with particles of μm level did not improve the barrier property at all and further impaired the transparency.

[0105]

As described in detail above, an untreated swellable layered silicate which is not treated with an organometallic compound or the like is used, and a number of thin plate-like unit layers are originally laminated to form aggregates. The layer is separated and cleaved from the particles of the swellable phyllosilicate at the level of μm, and is subdivided into a very large number of extremely small Å-level plate-like particles, which are individually formed in a polyester resin and / or a polycarbonate resin. A resin film containing a polyester resin and / or a polycarbonate resin and a microlamellar swellable phyllosilicate obtained by independently and uniformly dispersing is free from the risk of coloring and has the inherent characteristics such as transparency. The barrier properties can be improved without impairing.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA43 AA45 AA46 AA48 AA50 AB26 AB30 AD06 AF08 AF30 AH04 AH12 AH14 BC01 4J002 CF001 CF041 CF051 CF061 CF071 CF081 CF161 CG001 CG011 CG021 DJ006 DJ056 FA016 GB01GG01GG01Q01

Claims (7)

[Claims] 1. A resin film containing a polyester resin and / or a polycarbonate resin and a swellable layered silicate, wherein the equivalent area circular diameter [D] of the swellable layered silicate contained in the resin film ] Is 2000Å
A resin film, wherein the ratio of the following swellable layered silicate is 30% or more. 2. A resin film containing a polyester resin and / or a polycarbonate resin and a swellable layered silicate, wherein the average of the equivalent area circle diameters [D] of the swellable layered silicate in the resin film. A polyester resin composition having a value of 3000 ° or less. 3. The resin film according to claim 1, wherein the average value of the equivalent area circle diameter [D] of the swellable layered silicate is 3000 ° or less. 4. A resin film containing a polyester resin and / or a polycarbonate resin and a swellable layered silicate, wherein the resin film is dispersed in an area of 100 μm ² per unit ratio of the swellable layered silicate. A resin film having an [N] value defined by the number of particles of 40 or more. 5. An average aspect ratio (layer length / layer thickness ratio) of a swellable layered silicate in a resin film is 10 to 300.
The resin film according to claim 1, 2, 3, or 4, wherein 6. The maximum layer thickness of the swellable layered silicate is 100.
The resin film according to claim 1, wherein the angle is 0 ° or less. 7. The swellable phyllosilicate has an average layer thickness of 300.
樹脂 The resin film according to claim 1, 2, 3, 4, 5, or 6, wherein