JPH02307751A - Laminated film - Google Patents

Abstract

PURPOSE:To obtain a laminated film suitable as a packing film low in anisotropy and excellent in interlaminar adhesiveness and gas barrier properties by laminating a thermotropic liquid-crystalline polymer layer containing a filler and the same layer containing no filler. CONSTITUTION:A liquid-crystalline polymer is polyester consisting of a repeating unit I (structural formula I) and a repeating unit II (structural formula II) and contains about 10 - 90 mol.% of the unit I and about 10 - 90 mol.% of the unit II. As a filler, a substance usually added to a thermoplastic resin and a thermosetting resin, for example, a carbon fiber is contained in the liquid- crystalline polymer layer in an appropriate amount within a range not damaging extrusion moldability and film characteristics. When the filler-containing liquid- crystalline polymer is set to LCPCF and the liquid-crystalline polymer is set to LCP, polymer layers are laminated in a two-layer structure of LCPCF layer/ LCP layer, a three-layer structure of LCP layer/LCPCF layer/LCP layer or a multilayer structure composed of the repetition of the two-layer structure and the three-layer structure. LCPCF, LCP and, if necessary, a thermoplastic resin are respectively melted in an extruder and subjected to coextrusion mold ing to make it possible to prepare a laminated film.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a laminated film that includes a liquid crystalline polymer layer and is suitable as a packaging film or the like.

[Prior Art and Problems to be Solved by the Invention] In recent years, as the types of objects to be packaged have expanded, various packaging films have been developed depending on the purpose. For example, packaging films include high-strength films, high-elastic films, flexible films, adhesive films, transparent films, conductive films, light-shielding films, gas barrier films, heat-resistant films, chemical-resistant films, Composite films made by combining these materials are known. However, since the properties of the constituent polymers of these packaging films are significantly different, they are used differently depending on the application.
It is difficult to simultaneously improve multiple properties in one film.

On the other hand, liquid crystalline polymers, which belong to the field of engineering plastics, have excellent mechanical properties, dimensional stability, heat resistance, chemical stability, gas barrier properties, etc., as well as good electrical properties, so they meet various performance requirements. It is designated as Note L1 as a raw material polymer for films that satisfies the following. However, as is clear from the fact that highly elastic split fibers can be obtained by splitting liquid crystalline polymer films (see Japanese Patent Publication No. 60-42287), the orientation of liquid crystalline polymers is large and anisotropic. Therefore, the extrusion direction (hereinafter,
The strength in the direction perpendicular to the MD force direction (hereinafter referred to as the TD force direction), that is, the width direction of the film (hereinafter referred to as the TD force direction), is extremely weak.
Easy to crack along the extrusion direction.

Furthermore, even if a liquid crystalline polymer and another thermoplastic polymer are coextruded, the interlayer adhesive strength is generally low, making it difficult to form a composite. In view of the above points, in order to increase the interlayer adhesive strength, a liquid crystal polymer with a specific amount of glass fiber added,
A method for producing a multilayer sheet by coextruding a thermoplastic polymer other than a liquid crystalline polymer has been proposed (Japanese Patent Application Laid-Open No. 1983-1996).
-69323).

However, the multilayer film obtained by this method still has insufficient interlayer adhesive strength. Furthermore, since the liquid crystal polymer layer contains glass fibers, the properties of the liquid crystal polymer deteriorate. For example, when a filler such as glass fiber is added, microvoids are generated in the liquid crystalline polymer layer, and gas barrier properties are significantly impaired.

Therefore, an object of the present invention is to provide a laminated film that has low anisotropy, excellent interlayer adhesion and gas barrier properties, and is suitable for use as a packaging film, etc., while taking advantage of the excellent properties of liquid crystalline polymers.

[Structure of the Invention] The present invention provides a laminated film in which a zumotropic liquid crystalline polymer layer containing a filler and a thermotropic liquid crystalline polymer layer not containing a filler are laminated.
” This solves the second problem.

As used herein, the term "liquid crystalline polymer" refers to a thermotropic liquid crystalline polymer and a composition thereof that softens and flows when heated, becomes moldable, and does not exhibit an anisotropic melt phase having birefringence when melted.

Furthermore, the term "film" is used to include all relatively thin, substantially flat structures that are sometimes referred to as sheets or the like in the technical field.

Examples of the above-mentioned liquid crystalline polymers include polymers consisting of the following constituent components.

(1) One or more aromatic dicarboxylic acids and alicyclic dicarboxylic acids (2) One or more aromatic diols, alicyclic diols, and aliphatic diols (3) Aromatic hydroxycarboxylic acids (4) One or more aromatic thiol carboxylic acids (5) One or more aromatic dithiols, aromatic thiol phenols (6) Aromatic hydroxyamines, aromatic diamines Or two or more types.

The liquid crystalline polymer consisting of the above components includes i) polyester consisting of components (1) and (2), 11)
polyester consisting of component (3), 1ii) polyester consisting of component (1), (2) and (3), iv) polythiol ester consisting of component (4), ■) polyester consisting of component (1) and (3), 5) polythiol ester consisting of vi) polythiol ester consisting of constituent components (1), (4) and (5), vj i) polyester amide consisting of constituent components (1), (3) and (5) , vHi) components (1), (2), (3) and (5)
A combination of polyesteramide, etc. consisting of

Although not included in the above combination of components, such liquid crystalline polymers include aromatic polyazomethine,
A specific example is poly(nitrilo-2-methyl-1,4-
phenylenenitrilomethylidine-1,4-phenylenemethylidine), poly(nitrilo-2-chloro-1, 4=phenylenenitrilomethylidine-1,4-phenylenemethylidine).

Furthermore, such liquid crystalline polymers include polyester carbonate, which is not included in the scope of the above-mentioned combination of components. This polymer contains 4-oxybenzoyl units, dioquinphenyl units, dioxycarbonyl units, and terephthaloyl units in woody terms.

Examples of the aromatic dicarboxylic acids include terephthalic acid, 4.
4'-diphenyldicarboxylic acid, 4°4#-triphenyldicarboxylic acid, 2,6-naphthalene dicarboxylic acid, diphenyl ether-4°4'-dicarboxylic acid, diphenoxyethane-4°4'-dicarboxylic acid, diphenoxybutane -4゜47-dicarboxylic acid, diphenylethane-4
゜4'-dicarboxylic acid, isophthalic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenoxyethane-
3,3'-dicarboxylic acid, diphenylethane-3,3'
- Aromatic dicarboxylic acids such as dicarboxylic acid, naphthalene-1,6-dicarboxylic acid; alkyl, alkoxy or halogen substituted aromatic dicarboxylic acids, such as chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid, Examples include dimethyl terephthalic acid, ethyl terephthalic acid, methoxyterephthalic acid, and ethoxyterephthalic acid.

Examples of alicyclic dicarboxylic acids include alicyclic dicarboxylic acids such as trans-1°4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid.

Alkyl, alkoxy or halogen substituted alicyclic dicarboxylic acids, such as trans-1,4-(1-methyl)cyclohexanedicarboxylic acid, trans-1,4-(
1-chloro)cyclohexanedicarboxylic acid and the like.

Aromatic diols include hydroquinone, resorcinol, 4.4'-dihydroxydiphenyl, 4.4'-dihydroxytriphenyl, 2.6-naphthalenediol, 4.4'-dihydroxydiphenyl ether, bis(4-hydroxyphenoxy)ethane. , 3.3'-dihydroxydiphenyl, 3.3'-dihydroxydiphenyl ether, 1.6-naphthalenediol, 2,2
-bis(4-hydroxyphenyl)propane, ], ]1
-Aromatic diols such as methane, alkyl, alkoxy or halogen substituted aromatic diols, such as chlorohydroquinone, methylhydroquinone, 1-butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4- Examples include chlororesorcin and 4-methylresorcin.

Examples of alicyclic diols include trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4-cyclohexane dimetatool,
trans-1,3-cyclohexanediol, cis-1
, 2-cyclohexanediol, trans-1,3-cyclohexane dimetatool; alkyl, alkoxy or halogen substituted alicyclic diols, such as trans-1,4-(1-methyl)cyclohexane Diol, trans-1,4-(1-chloro)
Examples include cyclohexanediol.

As the aliphatic diol, ethylene glycol, 1.3
- Straight-chain or branched aliphatic diols such as propanediol, 1,4-butanediol, and neopentyl glycol are mentioned.

Examples of aromatic hydroxycarboxylic acids include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, and 6-hydroxybenzoic acid.
Aromatic hydroxycarphonic acids such as 2-naph I-technic acid and 6-hydroxy-1-naphthoic acid; alkyl, alkoxy or halogen-substituted aromatic hydroxycarboxylic acids,
For example, 3-methyl-4-hydroxybenzoic acid, 3,5
-dimethyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 3-methoxy-4-hydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzoic acid, 6-hydroquine-5-methyl- 2-naphthoic acid, 6-hydroxy-5-methoxy-2-naphthoic acid,
3-chloro-4-hydroxybenzoic acid, 2,3-dichloro-4-hydroxybenzoic acid, 3,5-dichloro-4-
Hydroxybenzoic acid, 2,5-dichloro-4-hydroquinebenzoic acid, 3-bromo-4-hydroxybenzoic acid, 6
Examples include -hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-5,7-dichloro-2-naphthoic acid, and the like.

-]〇- Examples of the aromatic mercaptocarboxylic acids include 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-2-naphthoic acid, and 7-mercapto-2-naphthoic acid.

Aromatic dithiols include benzene-1,4-dithiol, benzene-1,3-dithiol, naphthalene-2
, 6-dithiol, naphthalene-2,7-dithiol, and the like.

Examples of aromatic mercaptophenol include 4-mercaptophenol, 3-mercaptophenol, 2-mercaptophenol, and the like.

As aromatic hydroxyamine and aromatic diamine, 4
-Aminophenol, N-methyl-4-aminophenol, 1,4-phenylenediamine, N-methyl-1,4
- Phenylenediamine, N.

N'-dimethyl-1,4-phenylenediamine, 3-aminophenol, 3-methyl-4-aminophenol-2-chloro-4-aminophenol, 4-amino-1-
naphthol, 4-amino-4'-hydroxydiphenyl, 4-amino-4'-hydroxydiphenyl ether,
4-amino-4'-hydroxydiphenylmethane, 4-
Amino-4'-hydroxydiphenyl sulfide, 4゜4'-diaminophenyl sulfide (thiodianiline)
, 4.4'-diaminodiphenylsulfone, 2.5
-diaminotoluene, 4,4'-ethylene dianiline,
4.4'-diaminodiphenoxyethane, 4.4'-
Diaminodiphenylmethane (methylene dianiline),
4.4'-diaminodiphenyl ether (oxydianiline) and the like.

The polymers 1) to vii consisting of each of the above constituent components
Regarding i), depending on the constituent components, the composition ratio in the polymer, and the sequence distribution, some polymers do not have birefringence when melted, but the polymers used in the present invention are those that have birefringence when melted. Limited.

The liquid crystalline polymer used in the present invention can be produced by a conventionally known method.

Fully aromatic polymers preferably used in the present invention tend to be substantially insoluble in common solvents and are therefore unsuitable for solution processing. However, these polymers can be easily processed using conventional melt processing methods. It should be noted that particularly preferred fully aromatic polymers are somewhat soluble in pentafluorophenol.

The liquid crystalline polymer used in the present invention may have an appropriate molecular weight within a range that does not impair film-forming properties and the like. for example,
Suitable fully aromatic polyesters usually have a weight average molecular weight of about 2,000 to 200,000, preferably about 10
,000 to 50,000, particularly preferably about 20,00
0 to 25,000. Suitable fully aromatic polyesteramides also typically have a molecular weight of about 5,000 to 50,000
000, preferably about 10,000 to 30,000, such as 15,000 to 17,000. Molecular weight measurements can be performed by gel permeation chromatography as well as other standard measurements that do not involve melt formation of polymers, such as quantification of end groups by infrared spectroscopy on compression molded films. Alternatively, the molecular weight can be measured using a light scattering method using a pentafluorophenol solution.

The fully aromatic polyesteramide described above has at least about 2.0% concentration by weight when dissolved in pentafluorophenol at a temperature of 60°C. OdJ! /g, for example about 2.
0-10. The logarithmic viscosity (1, V,) in OdJ/g is generally indicated.

Particularly preferred polyesters forming an anisotropic melt phase are:
It contains naphthalene moieties such as 6-hydroxy-2-naphthoyl, 2.6-dihydroxynaphthalene, and 2,6-dicarboxynaphthalene in an amount of about 10 mole percent or more. Preferred polyesteramides are those containing repeating units of the above naphthalene moiety and a moiety consisting of 4-aminophenol or ], ]4-phenylenediami.

Specifically, the details are as follows.

(A) A polyester consisting essentially of the following repeating units I and (2) ]4 - This polyester contains about 10 to 90 mol % of units I and about 10 to 90 mol % of units (2).

- In embodiments, the unit I is about 65 to 85 mol% (e.g.
up to an amount of about 75 mole %). In other aspects,
The unit ■ is about 15 to 35 mol%, preferably about 20 to 30
Present in amounts as low as mole %. Further, at least a part of the hydrogen atoms bonded to the ring is substituted with a substituent selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a phenyl group, a substituted phenyl group, and a combination thereof. It's okay.

(B) A polyester consisting of the following repeating units (■, ■, and ■) in terms of wood quality.

This polyester contains about 30 to 70 mol % of units (■). The polyester preferably has about 40 units
~60 mol%, unit ■ about 20-30 mol% and unit ■
contains about 20 to 30 mol% of H. Further, at least -l of the hydrogen atoms bonded to the ring is substituted with a substituent selected from the group consisting of an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a phenyl group, a substituted phenyl group, and a combination thereof. It's okay.

(C) A polyester consisting of the following repeating units ■, ■, ■, and ■ in terms of wood; This polyester contains about 20 to 60 mole % of unit (2), about 5 to 35 mole percent of unit (2), about 5 to 18 mole percent of unit (2), and about 20 to 40 mole percent of unit (2). This polyester preferably contains about 35 to 45 mol % of units (2), about 15 to 25 mol % of units (2), about 10 to 15 mol % of units (2), and about 25 to 35 mol % of units (2). however,
The total molar concentration of units ■ and ■ is substantially equal to the molar concentration of unit ■. Furthermore, at least some of the hydrogen atoms bonded to the ring are a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a phenyl group, a substituted phenyl group, and a combination thereof. may be substituted with a substituent selected from. This fully aromatic polyester exhibits zero conversion to pentafluorophenol at a temperature of 60°C.
．． At least 2.0 when dissolved at a concentration of 3 W/V%
d''7g1, for example 2.0 to 1o, typically exhibiting an logarithmic viscosity of 0617g.

(D) A polyester consisting essentially of the following repeating units: ■, ■, ■, and ■.

General formula +0-Ar-〇masu ■ (In the formula, Ar contains at least one aromatic ring -18
= dioxyaryl unit represented by the general formula +C-Ar-C+ (in which Ar is the same as above). 20 to 40 mol%, unit ■ exceeding 10 mol% and up to about 50 mol%, unit ■ exceeding 5 mol% and up to about 30 mol%, and unit ■ exceeding 5 mol% and about 30 mol% Contain in the following amounts. This polyester preferably contains about 20 to 30 mol%, for example about 25 mol%, of units (2), about 25 to 40 mol%, for example, about 35 mol% of units (2), and about 15 to 25 mol% of units (2). , for example, about 2Q mol%, and about 15 to 25 units
It contains about 20 mol%, for example, about 20 mol%.

In addition, at least some of the hydrogen atoms bonded to the ring are
-19-' Substituted with a substituent selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a phenyl group, a substituted phenyl group, and a combination thereof. Good too.

The units ■ and ■ are symmetrically arranged on a divalent bond connecting these 41-positions to other units on both sides in the polymer main chain, or on one or more aromatic rings (for example, naphthalene). When present on a ring, it is preferable that they are symmetrical in the sense that they are arranged at para positions with respect to each other or on a diagonal ring. However, asymmetric units such as those derived from resorcinol and isophthalic acid can also be used.

The preferred dioxyaryl unit (2) is .The preferred dicarboxyaryl unit (2) is.

(E) Polyester consisting essentially of the following repeating units ■, ■, ■; dioxyaryl unit represented by the general formula +0-Ar-0+ ■ (wherein Ar is the same as above) general formula +C-Ar- C+ ■ Dicarboxyaryl unit represented by (wherein Ar is the same as above) This polyester contains approximately 10 to 90 mol% of units (■), 5 to 45 mol% of units (■), and 5 to 45 mol% of units (■). Contain in an amount of This polyester preferably contains about 20 to 80 mol % of units, about 10 to 40 mol % of units (2), and about 10 to 40 mol % of units (2). More preferably, the polyester contains about 60 to 80 mole % units I, about 10 to 20 mole % units ■, and about 10 to 20 mole % units ■. In addition, at least some of the hydrogen atoms bonded to the ring are selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halokene atom, a phenyl group, a substituted phenyl group, and a combination thereof. It may be substituted with selected substituents.

The preferred dioxyaryl unit (2) is and the preferred dicarboxyaryl unit (2) is.

(F) Polyester amide consisting essentially of the following repeating units 1, IX, X and unit represented by the general formula +0-Ar-0-)X (where Ar is the same as above; Y is O, NH or NR,
Z means NH or NR, and R has 1 to 1 carbon atoms.
This polyesteramide has a unit represented by the general formula +0-Ar-0 sho (in which A is the same as above). Approximately 10 to 90 mol%, unit ■ 5 to 45 mol%, unit X 5 to 45 mol%
, and the unit ■ in an amount of about 0 to 40 mol%. In addition, at least some of the hydrogen atoms bonded to the ring are selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a phenyl group, a substituted phenyl group, and a combination thereof. It may be substituted with selected substituents.

Preferred dicarboxyaryl units (2) are, preferred units (X) are, and preferred dioxyaryl units (2) are.

Furthermore, the polymer forming the anisotropic melt phase of the present invention includes:
Also included are polymers in which a portion of one polymer chain is composed of segments of a polymer that forms the above-mentioned anisotropic melt phase, and the remaining part is composed of segments of a thermoplastic resin that does not form an anisotropic melt phase.

The heat distortion temperature of the liquid crystalline polymer is usually 8° to 400°.
°C1 is preferably about 1.20 to 350 °C,
Excellent heat resistance. Especially heat distortion temperature 1.50~250°C
Liquid crystalline polymers are preferred because they have excellent film-forming properties. In addition, the liquid crystalline polymer film has a water vapor transmission rate of approximately 0.1 g/
m2 / 100 μm / 24 hours / atmospheric pressure or less, excellent moisture resistance, and oxygen gas and carbon dioxide gas permeability of 1.0c
c/m2, 25 μm, 24 hours, and atmospheric pressure, and has excellent gas barrier properties. Also, the temperature is 70'C and the relative humidity is 96
%, it only changes by about 0.003 to 0.02% even if left for 500 hours, and has excellent dimensional stability.

The laminated film of the present invention is composed of a liquid crystalline polymer layer containing a filler and a liquid crystalline polymer layer containing no filler.

The fillers include substances normally added to thermoplastic resins and thermosetting resins, such as inorganic fibers such as glass fibers, carbon fibers, metal fibers, ceramic fibers, boron fibers, and asbestos; organic fibers such as phenolic resin fibers. Calcium carbonate, barium sulfate, titanium oxide, highly dispersed silicic acid, alumina, aluminum hydroxide, silica, talc,
Powder substances such as kaolin, mica, glass flakes, glass pieces, silica sand, various metal powders, carbon black, organic or inorganic pigments, calcined gypsum; inorganic compounds such as silicon carbide, holon nitride and silicon nitride, whiskers and metal whiskers etc. are included. The above fillers may be used singly or in combination.

In order to improve the transparency of the liquid crystal polymer layer, fillers with a small difference in refractive index from the liquid crystal polymer, such as glass fiber, calcium carbonate, silica, talc, and organic pigments, are preferable. In addition, in fields that do not require transparency,
Fillers such as carbon fiber and carbon black can also be used. In addition, among the above-mentioned fillers, inorganic substances having excellent thermal stability are preferable.

The above filler can be contained in an appropriate amount in the liquid crystal polymer layer within a range that does not impair extrusion moldability and film properties.
It is usually about 1 to 60% by weight, preferably about 5 to 50% by weight, and more preferably about 10 to 40% by weight. If the filler content is less than 1% by weight, the anisotropy of the liquid crystalline polymer will be large, and if it exceeds 60% by weight, extrusion moldability will decrease.

Note that by adding a filler, the orientation and anisotropy of the liquid crystalline polymer are reduced, and while the mechanical strength in the TD force direction is increased, the gas barrier property is decreased.

Therefore, in the present invention, a liquid crystalline polymer layer containing no filler is laminated on at least one surface of the liquid crystalline polymer layer containing the filler.

The lamination form of the laminated film is not particularly limited as long as at least a liquid crystalline polymer layer containing a filler and a liquid crystalline polymer layer not containing a filler are laminated. For example, when the liquid crystalline polymer containing filler is LCPCF and the liquid crystalline polymer is LCP, the laminated form of the laminated film is a two-layer structure of LCPCF layer/LCP layer: LCP layer/LCPCF layer/LCP layer, LCP
Examples include a three-layer structure of CF layer/LCP layer/LCPCF layer, a multilayer structure consisting of repeating the above two-layer structure or three-layer structure, and a multilayer structure consisting of a combination of a two-layer structure and a three-layer structure. Further, another thermoplastic polymer layer may be laminated on at least one surface of the laminated film of the above form. Examples of the thermoplastic polymer include polyethylene, polypropylene, polybutylene, polybutadiene, polyisoprene, polyvinyl acetate,
Ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, ethylene-methacrylic ester copolymer, ionomer, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylic resin, ABS resin,
AS resin, BS resin, polyurethane, polyacetal,
Polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyacrylonitrile, polyvinyl alcohol, polyvinyl ether,
Examples include polyetherimide, polyamideimide, polyetheretherimide, polyetheretherketone, polyethersulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, and the like.

Among thermoplastic polymers, modified polyolefins and polyesters used as hot melt type I adhesives not only have excellent adhesion to the LCPCF layer and LCP layer, but also can ensure heat sealability or hot melt adhesiveness. Therefore, a laminated film on the surface of which the above-mentioned modified polyolefin or the like is laminated can be easily formed into a bag by pillow packaging, four-sided sealing, etc., and can be used as a variety of packaging films.

Examples of the modified polyolefin include carboxy-modified polyolefin, glycidyl-modified polyolefin,
Alkoxysilane-modified polyolefin, carboxy-modified ethylene-ethyl acrylate copolymer, glycidyl-modified ethylene-ethyl acrylate copolymer, alkoxysilane-modified ethylene-ethyl acrylate copolymer, carboxy-modified ethylene-vinyl acetate copolymer, glycidyl Examples include modified ethylene-vinyl acetate copolymers, alkoxysilane-modified ethylene-vinyl acetate copolymers, and the like. The above-mentioned polyester includes terephthalic acid as a main component, polyhydric carboxylic acids including adipic acid, sebacic acid, and isophthalic acid, ethylene glyco-29-yl, 1,4-butanediol, and especially ], ]4-butanediol. A polyester starting from is preferred. Among the polyhydric carboxylic acids, terephthalic acid is preferably present in an amount of 30 to 80 mol%.

In order to improve the thickness, gas barrier properties, mechanical strength, etc. of the laminated film in the above laminated form, LCP layer/LCPCF layer/L
A laminated film including a laminated form of CP layer is preferred. In addition, in order to prevent the surface layer of the liquid crystalline polymer film from peeling off due to the frictional force with the lip of the die tip during extrusion molding and reducing the surface smoothness, the LCPCF layer/LCP layer/
Laminated films of LCPCF layers are also preferred. In the laminated film having this laminated structure, the shearing force acting on the intermediate LCP layer can be suppressed, so that the anisotropy of the LCP layer is also reduced.

Note that when the LCPCF layer and the LCP layer are laminated, since each layer contains a liquid crystalline polymer, interlayer adhesion is extremely high. Furthermore, the LCP layer can ensure excellent gas barrier properties.

Note that the LCPCF layer and the LCP layer are made of (1) the above-mentioned thermoplastic resins and thermosetting resins that do not form an anisotropic melt phase;
It may contain at least one type of low-molecular organic compound. Further, the thermoplastic polymer layer may contain the filler mentioned above, the thermosetting resin mentioned above, or a low-molecular organic compound.

Examples of the thermosetting resin include phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, diallyl phthalate resin, and alkyd resin.

Examples of the low-molecular organic compounds include plasticizers, weather and light stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents,
Includes flame retardants, coloring agents such as dyes, foaming agents, divinyl compounds, crosslinking agents such as peroxides and vulcanizing agents, and low-molecular organic compounds used as lubricants to improve fluidity, etc. .

The thickness of each layer constituting the above-mentioned laminated film is not particularly limited as long as it does not impair properties such as gas barrier properties, but it is usually 1 to 1.
The thickness is preferably about 500 μm, preferably about 5 to 250 μm.

Note that the laminated film may be uniaxially or biaxially stretched to an appropriate magnification by a conventional stretching means such as roll stretching, belt stretching, tenter stretching, or tube stretching. In addition, the laminated film has corona discharge treatment, sputtering treatment,
Surface treatments such as high frequency treatment, flame treatment, chromic acid treatment, solvent etching treatment, undercoating treatment, etc., or a combination of these treatments may be performed.

The laminated film of the present invention is LCPCF and 5LCP.

If necessary, the thermoplastic resin can be manufactured by melting and extruding each of the thermoplastic resins using an extruder and coextruding the resins. Note that the coextrusion molding machine is not particularly limited as long as it is a device that can coextrude into multiple layers. Examples of coextrusion molding machines include a multi-manifold die, a feed block system (11) that combines a feed block and a single-layer die, and a feed block system (2) that combines a feed block and a multi-manifold die, and a Bain die manufactured by Cloeren Co., Ltd. Thus, an apparatus or the like that can perform coextrusion molding with different molding temperatures of the polymers forming each layer of the multilayer film can be used. In addition, feed blog is the Dow Company of the United States,
This is a device for laminating molten polymers in a coextrusion multilayer film production device sold by Egan Co., Cloeren Co., etc.

When a laminated film is produced by coextrusion molding in this manner, the interlayer adhesive strength between the LCPCF layer and the LCP layer can be significantly increased.

The laminated film of the present invention can be used as a film for individual packaging, interior packaging, exterior packaging, and bag making of various packaged items. For example, in addition to packaging materials for food such as retort foods and microwave foods, packaging materials for oil-based cooking materials, packaging materials for medicines, packaging materials for cosmetics, and aroma-retaining packaging materials for aromatic substances, for example, desks, It can be used for various purposes such as a protective film for laboratory tables, etc.

[Effects of the Invention] As described above, according to the laminated film of the present invention, a thermotropic liquid crystalline polymer layer containing a filler and a thermotropic liquid crystalline polymer layer not containing a filler are laminated, so that liquid crystallinity It takes advantage of the excellent properties of polymers, has low anisotropy, and has excellent interlayer adhesion and gas barrier properties.

[Examples] The present invention will be described in more detail below based on Examples.

Example 1 Pellets of a liquid crystalline polymer (manufactured by Polyplastic ■, trade name: Vectra A900, hereinafter referred to as LCP) consisting of polyester (A) composed of the repeating units ■ and ■, and 30% by weight of carbon fibers. Liquid crystalline polymer (made of polyplastic ■, product name Pecto A230, hereinafter referred to as L)
By extruding the chips (referred to as CP-CF) from a T-die using a feed block type extrusion molding machine,
LCP/LCP'-CF/LCP=10μm/30μm
A laminated film having a laminated structure of /10 μm was produced.

Example 2 An example was carried out using pellets of LCP and chips of a liquid crystalline polymer (manufactured by Polyplastic ■, trade name: Pecto A], 30, hereinafter referred to as LCP-GF) containing 30% glass fiber. Similarly to 1, LCP/LCP
- A laminated film having a laminated structure of GF/LCP=10 μm/30 μm/10 μm was produced.

Example 3 Using pellets of LCP and chips of a liquid crystalline polymer containing 25% by weight of graphite (manufactured by Polyplastic ■, trade name Pecto A625, hereinafter referred to as LCP-G), the same procedure as in Example 1 was carried out. , LCP/LCP-G/L
A laminated film having a laminated structure of CP-10 μIN/30 μm/10 μm was produced.

Example 4 LCP pellets and calcium carbonate (Kamishima Chemical Industry ■
LC containing 30% by weight of Calcease-P manufactured by
P (hereinafter referred to as LCP-C) chip, LCP/LCP-C/LCP=1 in the same manner as in Example 1.
(A laminated film having a laminated structure of 1 m/30 μm/10 μm was produced.

Example 5 LCP-CF/I-CP/LC was produced by extruding LCP pellets and LCP-CF chips from a T-die using a feedblock extruder.
A laminated film having a laminated structure of P-CF=15 μm/20 μm/15 μm was produced.

Example 6 Using LCP pellets and LCP-GF chips,
In the same manner as in Example 5, LCP-GF/LCP/LCP
-GF=15 μm/20 μm/] A laminated film having a laminated structure of 5 μm was produced.

Comparative Example I A single-layer LCP film having a thickness of 20 μm was produced by extruding LCP pellets through a T-die.

Comparative Example 2 Comparative Example 1 except that LCP-CF was used instead of LCP
A single layer film of LCP'-CF having a thickness of 50 μm was prepared in the same manner as above. In this example, since LCP-CF contains a filler and has low stretchability, the above film thickness was set.

Comparative Example 3 LCP pellets, polyethylene terephthalate pellets (intrinsic viscosity 0.65, hereinafter referred to as PET),
LC was prepared in the same manner as in Example 1 using LCP pellets.
A laminated film having a laminated structure of P/PET/LCP=20 μm/150 μm/20 μm was produced.

And MD of the film obtained in each example and comparative example
The tensile strength in the force and TI directions was measured, and the interlayer adhesion strength was measured by a 180° peel (T-peel) strength test. The tensile strength and interlayer adhesion strength were measured using Autograph (
(manufactured by Shimadzu Corporation) at a speed of 50 mm/min.

Further, gas permeability and water vapor permeability were measured under the following conditions.

Oxygen gas permeability: 98% nitrogen gas under conditions of temperature 23℃ and relative humidity 60%
, using a carrier gas consisting of 2% hydrogen gas, ASTM
I)-3985-81.

Water vapor permeability was measured using an infrared sensor according to ASTM F-372-73 under conditions of a temperature of 25° C. and a relative humidity of 9026, using air as a carrier gas.

The results are shown in the table.

(Hereinafter, blank space) -39= As is clear from the table, the film of Comparative Example 1 has extremely low strength in the TD force direction and is easily torn, and the film of Comparative Example 2 does not have sufficient gas barrier properties. Furthermore, the laminated film of Comparative Example 3 had extremely low interlayer adhesive strength. On the other hand, the laminated films of each example were excellent in MD force direction and TD force direction strength, interlayer adhesive strength, and gas barrier properties.

Patent applicant Daicel Chemical Industries, Ltd. Representative
Person Patent Attorney Hoe 1) Mitsuru Life -40-

Claims (1)

[Scope of Claims] 1. A laminated film characterized in that a thermotropic liquid crystalline polymer layer containing a filler and a thermotropic liquid crystalline polymer layer not containing a filler are laminated. 2. The laminated film according to claim 1, wherein a filler-free thermotropic liquid crystal polymer layer is laminated on both sides of the filler-containing thermotropic liquid crystal polymer layer.