JPS6189816A - Manufacture of laminated film - Google Patents

Abstract

PURPOSE:To realize film without impairing highly oriented state and losing high strength by a method wherein lamination is performed by melt-molding either one of polymers to be laminated to each other. CONSTITUTION:Thermoplastic polymer with film-forming properties is laminated through melt molding by ordinary laminated film forming method to prepared uniaxially oriented sheet of polymer, which produces anisotropic fused phase. Thus, first polymer, which shows anisotropic fused phase, takes charge of a major part of the strength in the direction of orientation. Second polymer or film-forming thermoplastic polymer takes charge of a major part of the strength in crosswise direction. Further, the second thermoplastic polymer also takes charge of film-forming properties. Consequently, the industrial continuous produc tion method of multi-layer laminating film is established.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides an industrially viable manufacturing method for continuously manufacturing a high-strength multilayer film containing at least one layer of a polymer that forms an anisotropic melt phase. related to.

[Conventional technology and its problems]

Polymers exhibiting an anisotropic melt phase known as thermotropic liquid crystal polymers are known to have extremely high strength in the orientation direction due to the anisotropy of their orientation.
The strength in the direction perpendicular to the orientation direction is significantly lower than that in the orientation direction, making it difficult to form into a film in a normal continuous process or limiting the usefulness of the film in many applications. .

BACKGROUND OF THE INVENTION Methods have been proposed for producing sheets or films made of thermotropic liquid crystal polymers that exhibit desirable properties in multiple directions. For example, JP-A-56-4626, JP-A-5
6-46727 and JP-A-55-161821 propose internal plasticization of the molecular structure and plasticization by blending plasticizers, etc., but rather the strength is reduced because the anisotropy is extremely reduced and melt molding is performed. It has the disadvantage of being sacrificed.

In addition, JP-A-58-31.718 proposes a multi-axially oriented laminate in which uniaxially oriented sheets of thermotropic liquid crystal polymer are laminated, and it is possible to achieve high strength by layering sheets with different axial directions. However, it is difficult and uneconomical to laminate two sheets in a continuous process so that their axes form a certain angle, and this method is not satisfactory as an industrial manufacturing method.

An object of the present invention is to solve the technical problem of forming a thermotropic liquid crystal polymer into a film while maintaining its characteristics of high orientation and high strength.

[Means for solving problems]

That is, the present invention provides a method for continuously producing a high-strength laminate film on an industrial scale, which comprises a polymer that forms an anisotropic melt phase and a thermoplastic polymer that has film-forming ability. The present invention relates to a method for producing a laminate film, which comprises melt-molding and laminating at least one of the polymers when producing a multilayer sheet and/or a multilayer film.

According to the present invention, the strength in the orientation direction is largely dependent on the first polymer exhibiting an anisotropic melt phase, and the strength in the transverse direction is largely dependent on the second polymer, which is a thermoplastic polymer capable of forming a film. Provided is a method capable of industrially and continuously producing a multilayer laminate film in which the second thermoplastic polymer is dependent on the second thermoplastic polymer and has film forming ability.

The polymer exhibiting an anisotropic melt phase used in the laminate film of the present invention is a thermoplastic melt-processable polymer composition that exhibits optical anisotropy when melted, and is generally classified as a thermodropink liquid crystal polymer. Ru.

Polymers that form such an anisotropic melt phase have a property in which polymer molecular chains are regularly arranged in parallel in a molten state. The state in which the molecules are arranged in this way is often called the liquid crystal state or the nematic phase of liquid crystal materials. Such polymers are generally elongated, oblate, and are made from monomers that are fairly rigid along the long axis of the molecule and have multiple chain extensions, usually in either coaxial or parallel relationships. Manufactured.

The nature of the anisotropic melt phase can be confirmed by conventional polarization testing using crossed polarizers. More specifically, the anisotropic melt phase can be confirmed using a Leitz polarization microscope. +i I
This can be carried out by observing a sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. The polymer is optically anisotropic. That is, it transmits light when examined between orthogonal polarizers.

If the sample is optically anisotropic, polarized light will pass through it even if it is at rest.

Constituent components of the polymer that forms the anisotropic melt phase as described above include: - Consisting of one or more of aromatic dicarboxylic acids and alicyclic dicarboxylic acids - Aromatic diols, alicyclic diols, and aliphatic diols ■ Consisting of one or more aromatic hydroxycarboxylic acids ■ Consisting of one or more aromatic thiol carboxylic acids ■ Consisting of aromatic dithiols, aromatic ol-phenols 1
Polyesters consisting of one or more of aromatic hydroxyamines and aromatic diamines, etc. Polyesters that form an anisotropic melt phase include polyesters consisting of ■)■ and ■■) Polyester consisting of only ■ Polyester consisting of ■) ■, ■ and ■ ■) Polythiol ester consisting only of ■ ■) Polythiol ester consisting of ■ and ■ ■) Polythiol ester consisting of ■ and ■ ■) ■ and ■ It is composed of a combination of polyester amide (■) consisting of ■), ■, polyester amide consisting of ■ and ■, etc.

Furthermore, although it is not included in the above range of combinations of ingredients,
Polymers that form an anisotropic melt phase include aromatic polyazomethines, and specific examples of such polymers include poly-2-methyl-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine. ) ; poly
trilo-2-methyl-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine); Can be mentioned.

Furthermore, although it is not included in the above range of combinations of ingredients,
Polyester carbonate is included as a polymer that forms an anisotropic melt phase. It may consist essentially of 1-oxybenzoyl units, dioxyphenyl units, dioxycarbonyl units and terephthaloyl units.

The compounds constituting the above-mentioned components I) to (2) are listed below.

Examples of aromatic dicarboxylic acids include terephthalic acid, 4.4'-diphenyldicarboxylic acid, 4.4'-1-diphenyldicarboxylic acid, 2.6-naphthalene dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, and diphenoxy Ethane-4,4'-dicarboxylic acid, diphenoxybutane-4,4'-dicarboxylic acid, diphenylethane-4,
4°-dicarboxylic acid, isophthalic acid, diphenyl ether-3,3'-dicarboxylic acid, diphenoxyethane-3
, 3'-dicarboxylic acid, diphenylethane-3,3'-
dicarboxylic acid, aromatic dicarboxylic acid such as naphthalene-1,6-dicarboxylic acid, or chloroterephthalic acid,
Examples include alkyl, alkoxy or halogen substituted products of the aromatic dicarboxylic acids such as dichloroterephthalic acid, bromo terephthalic acid, methyl terephthalic acid, 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, l,3-cyclohexanedicarboxylic acid, and trans-1,4-( 1
-methyl)cyclohexanedicarboxylic acid, trans-1
, 4-<1-chloro)cyclohexanedicarboxylic acid, etc.
Examples include alkyl, alkoxy, or halogen-substituted products of the above alicyclic dicarboxylic acids.

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, 1,6-1-phthalenediol, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis (
Aromatic diols such as 4-hydroxyphenyl)mecune, chlorohydroquinone, methylhydroquinone,
1-butylhydroquinone, phenylhydroquinone,
Methoxyhydroquinone, phenoxyhydroquinone:
Examples include alkyl, alkoxy or halogen substituted products of the above aromatic diols such as 4-chlorresorcin and 4-methylresorcin.

Examples of alicyclic diols include trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4-cyclohexane dimetatool,
Alicyclic diols such as cis-1,4-cyclohexane dimetatool, trans-1,3-cyclohexanediol, cis-L2-cyclohexanediol, trans-1,3-cyclohexane dimetatool, or trans-1,4- Examples include alkyl, alkoxy or halogen substituted products of the above alicyclic diols such as (1-methyl)cyclohexanediol and trans-1,4-(1-chloro)cyclohexanediol.

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

Examples of aromatic hydroxycarboxylic acids include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, and 6-hydroxybenzoic acid.
Aromatic hydroxycarboxylic acids such as 2-naphthoic acid and 6-hydroxy-1-naphthoic acid, or 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-hydroxy-5-methyl-2-naphthoic acid, 6-hydroxy-5-
Methoxy-2-naphthoic acid, 3-chloro-4-hydroxybenzoic acid, 2-chloro-4-hydroxybenzoic acid, 2
, 3-dichloro-4-hydroxybenzoic acid, 3,5-dichloro-4-hydroxybenzoic acid, 2,5-dichloro-
4-Hydroxybenzoic acid, 3-bromo-4=hydroxybenzoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-7=chloro-2-naphthoic acid, 6
Examples include alkyl, alkoxy or halogen substituted aromatic hydroxycarboxylic acids such as -hydroxy-5,7-dichloro-2-naphthoic acid.

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

Examples of the aromatic dithiol include benzene-1,4-dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol, and 2,7-naphthalene-dithiol.

Examples of aromatic mercaptophenol include 4-mercaptophenol, 3-mercaptophenol, 6-mercaptophenol, and 7-mercaptophenol.

Aromatic hydroxyamine, aromatic diamine is 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-diamino-1-toluene, 4,
4'-ethylene dianiline, 4,4'-diaminodiphenoxyethane, 4.4°-diaminodiphenylmethane (
methylene dianiline), 4,4'-diaminodiphenyl ether (oxydianiline), and the like.

The above-mentioned polymers (■) to (■) consisting of the above-mentioned components may or may not form an anisotropic melt phase depending on the constituent components, the composition ratio in the polymer, and the sea fence distribution, but they are used in the present invention. The polymers that can be used are limited to those that form an anisotropic melt phase among the above-mentioned polymers.

The polyesters of 1), n), and III) and the polyesteramide of ①), which are polymers forming an anisotropic melt phase suitable for use in the present invention, have functional groups that form the required repeating units by condensation. It can be produced by various ester formation methods that allow the organic monomer compounds that are present to react with each other. For example, the functional groups of these organic monomer compounds may be carboxylic acid groups, hydroxyl groups, ester groups, acyloxy groups, acid halides, amine groups, and the like. The above organic monomer compounds can be reacted without the presence of a heat exchange fluid by a melt acidolysis method. In this method, the monomers are first heated together to form a molten solution of the reactants. As the reaction continues, solid polymer particles will form large particles in the liquid. Vacuum may be applied to facilitate removal of by-product volatiles (eg, acetic acid or water) during the final stages of condensation.

Slurry polymerization techniques can also be employed to form fully aromatic polyesters suitable for use in the present invention. In this process, a solid product is obtained in suspension in a heat exchange medium.

Regardless of whether the above-mentioned melt acidolysis method or slurry polymerization method is employed, the organic monomer reactant for inducing the fully aromatic polyester is in a modified form (i.e., lower (as an acyl ester). The lower acyl group preferably has about 2 to 4 carbon atoms. Preferably, an acetate ester of such an organic monomer reactant is subjected to the reaction.

Furthermore, representative examples of catalysts that can optionally be used in either the melt acidolysis method or the slurry method include dialkyltin oxides (e.g., dibutyltin oxide), diaryltin oxides, titanium dioxide, antimony trioxide, alkoxytitanium silicates, titanium alkoxides. , alkali and alkaline earth metal salts of carboxylic acids (e.g. zinc acetate), Lewis (e.g. BFI), hydrogen halides (e.g.
Examples include gaseous acid catalysts such as HCI). The amount of catalyst used is generally about o, based on the total weight of monomer.
oot~1% by weight, especially about 0.01-0.2% by weight.

Fully aromatic polymers suitable for use in the present invention include:
fct tends to be virtually insoluble in solvents and therefore ? Not suitable for liquid processing.

However, as previously mentioned, these polymers can be readily processed using conventional melt processing methods. Particularly preferred fully aromatic polymers are somewhat tolerant of penta'7) leolophenols.

Fully aromatic polyesters suitable for use in the present invention generally have a weight average molecular weight of about 2.000 to 200.000.
, preferably about 10,000 to 50,000, particularly preferably about 20,000 to 25,000. On the other hand, suitable fully aromatic polyesteramides generally have a molecular weight of about 5,000 to 50,000, preferably about 10,000.
~30,000, for example 15,000 to 17,000. Such molecular weight measurements can be carried out by gel permeation chromatography as well as other standard methods of measuring polymers that do not involve solution formation, 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 polyesters and polyesteramides described above also yield 0.1% of pentafluorophenol at 60°C.
When dissolved at a weight percent concentration of at least about 2.0 d
i/g, for example about 2.0 to 10.0 di/g.

Particularly preferred anisotropic melt phase forming polyesters for use in the present invention include repeating units containing naphthalene moieties such as 6-hydroxy-2-naphthoyl, 2,6-dihydroxynaphthalene and 2,6-dicarboxynaphthalene. It contains about 10 mol% or more. Preferred polyesteramides are those containing repeating units of the naphthalene moiety described above and a moiety consisting of 4-aminophenol or 1,4-phenylenediamine. Specifically, the details are as follows.

+11 A polyester consisting essentially of the following repeating units (■) and (■).

The polyester contains about 10 to 90 mole percent of units I and about 1
Contains 0 to 90 mol % of units (■). In embodiments Unit I is present in an amount of about 65 to 85 mole %, preferably about 70 to 80 mole % (e.g., about 75 mole %). In another embodiment, the unit ■ is present in much lower concentrations of about 15-35 mole %, preferably about 20-30 mole %.

In addition, at least a portion of the hydrogen atoms bonded to the ring may optionally be selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and a combination thereof. It may be substituted with selected substituents.

(2) A polyester consisting essentially of the following repeating units I, ■ and ■.

This polyester contains about 30 to 70 mole % of units I. The polyester preferably has about 40 to 60
It contains about 20 to 30 mol % of units (2), about 20 to 30 mol % of units (2), and about 20 to 30 mol % of units (2). In addition, at least a portion of the hydrogen atoms bonded to the ring may optionally consist of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, or a combination thereof. It may be substituted with a substituent selected from the group.

(3) Polyester consisting essentially of the following repeating units r, n, ■ and ■: (wherein R means methyl, chloro, bromo or a combination thereof, and is a substituent for the hydrogen atom on the aromatic ring. ), and about 20 to 60 mol% of unit I,
It contains about 5 to 18 mol% 1 of unit (2), about 5 to 35 mol% of unit (2), and about 20 to 40 mol% of unit (2). The polyester preferably contains about 35 to 45 mole % units ■, about 10 to 15 mole % units ■, about 15 to 2
It contains 5 mol % of Ill at position 41 and about 25-35 mol % of units ■. However, the total molar concentration of units ■ and ■ is substantially equal to the molar concentration of unit ■.

In addition, at least some of the hydrogen atoms bonded to the ring are
Optionally, an alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
may be substituted with a substituent selected from the group consisting of an alkoxy group, halogen, phenyl, substituted phenyl, and combinations thereof. This fully aromatic polyester was dissolved in pentafluorophenol for 0.3 h at 60°C.
/νχ concentration of at least 2.0 dl/
For example, 2.0 to 10. OL: Logarithmic viscosity of 11/g is shown in part.

(4) Polyester consisting essentially of the following repeating units I, ■, ■, and ■: ■ General formula -EO-A r-0) (wherein, the total means a divalent group containing at least one aromatic ring a dioxyaryl unit represented by ), a dicarboxyaryl unit represented by (meaning a divalent group containing at least one aromatic ring), and about 20 to 40 mol% of the unit More than 10 mol% and not more than about 50 mol%, more than 5 mol% of the unit ■ and not more than about 30 mol%, and 5 mol% of the unit
30 mole % or less. The polyester preferably contains about 20 to 30 mole percent (e.g. about 25 mole percent).
mol %) of units I, about 25 to 40 mol % (e.g., about 35 mol %) of units ■, about 15 to 25 mol % (e.g., about 20 mol %) of units ■, and about 15 to 25 mol % of units (For example, about 20
Contains the unit ■ of mol %). In addition, at least some of the hydrogen atoms bonded to the ring may have 1 to 1 carbon atoms, depending on the case.
4 alkyl group, carbon 1i (((1 to 4 alkoxy groups, halogen, phenyl, substituted phenyl, and combinations thereof) may be substituted with a substituent selected from the group consisting of.

Units ■ and ■ have a symmetrical arrangement on one or more aromatic rings in which the divalent bonds connecting these units to other units on either side within the polymer backbone (e.g., on a naphthalene ring) When present, they are preferably symmetrical in the sense that they are arranged para 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 ■ is and the preferred dicarboxyaryl unit ■ is It is.

(5) Polyester consisting essentially of the following repeating units I, n and ■: ■ With the general formula (0-Ar-0) (wherein Ar means a divalent group containing at least one aromatic ring) dioxyaryl unit shown (meaning a divalent group containing at least one aromatic ring), and about 10 to 90 mol% of units (■) and 5 to 45 mol% of units (■) Contains 5 to 45 mole 1% of the unit (mol%). The polyester preferably has about 20 to 80
Mol% Unit 11 Contains about 10 to 40 mole percent of the 4'i-position ■, and about 10 to 40 mole percent of the unit ■. More preferably, the polyester has about 60 to 80 mole percent units (1), about 10 to 20 mole percent units (2), and about 10 to 2 mole percent units (2).
Contains 0 mol% of units ■. In addition, at least some of the hydrogen atoms bonded to the ring may have 1 to 1 carbon atoms, depending on the case.
It may be substituted with a substituent selected from the group consisting of an alkyl group having 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and a combination thereof.

The preferred dioxyaryl unit ■ is and the preferred dicarboxyaryl unit ■ is It is.

(6) Polyesteramide consisting essentially of the following repeating units I, ■, ■ and ■: II 11 ■ General formula IC-A-C (wherein A is a divalent group containing at least one aromatic ring) or divalent trans-cyclohexane group), ■ General formula -EY-Ar-Z
) (In the formula, Ar is a small amount (2 containing both one aromatic ring)
Valid group, Y is 0, NH or NR, Z is NH or NR
respectively, and R is an alkyl group having 1 to 6 carbon atoms,
or aryl group), ■ General formula I0-Ar
'-〇) (in the formula, the total ゛ means a divalent group containing at least one aromatic ring), and about 10 to 90 mol % of unit I and about 5 to 45 mol % of unit 2 %, about 5 to 45 mol % of the unit (■), and about 0 to 40 mol % of the unit (2). Also,
A group consisting of a small number of hydrogen atoms bonded to a ring (some of which may optionally include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, and a combination thereof) may be substituted with a substituent selected from.

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

Furthermore, the polymer forming the anisotropic melt phase of the present invention includes:
A part of one polymer chain is composed of polymer segments that form an anisotropic melt phase as explained above, and the remaining part is composed of thermoplastic resin segments that do not form an anisotropic melt phase. Also includes polymers.

The melt-processable polymer composition that forms an anisotropic melt phase used in the present invention includes: (1) other polymers that form an anisotropic melt phase, (2) thermoplastic resins that do not form an anisotropic melt phase, (2) It may contain one or more of the following: a thermosetting resin, (1) a low-molecular organic compound, and (2) an inorganic substance. Here, the polymer forming the anisotropic melt phase and the remaining portion in the composition may or may not be thermodynamically compatible.

Examples of the above thermoplastic resin (■) include polyethylene,
Polypropylene, polybutylene, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylic resin, ABS
Resin, AS resin, BS resin, polyurethane, silicone resin, fluorine resin, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, aromatic polyester, polyamide, polyacrylonitrile, polyvinyl alcohol, polyvinyl ether, polyetherimide, polyamideimide, polyetheretherimide, polyetheretherketone,
Includes polyether sulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, etc.

Examples of the thermosetting resin mentioned in (1) above include phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, and alkyd resins.

In addition, the low-molecular organic compounds mentioned in (2) above are, for example, substances added to general thermoplastic resins and thermosetting resins, such as plasticizers, antioxidants, ultraviolet absorbers, etc., weather-resistant and light-resistant stabilizers, and electrostatic stabilizers. Used as inhibitors, flame retardants, colorants such as dyes and pigments, blowing agents, crosslinking agents such as divinyl compounds, peroxides and vulcanizing agents, and lubricants to improve fluidity and mold release properties. This includes low-molecular-weight organic compounds.

Furthermore, the above-mentioned inorganic substances include, for example, substances added to general thermoplastic resins and thermosetting resins, such as general inorganic fibers such as glass fibers, carbon fibers, metal fibers, ceramic fibers, boron fibers, asbestos, etc. Powdered materials and carbonization such as calcium carbonate, highly dispersed silicic acid, alumina, aluminum hydroxide, talc powder, mica, glass flakes, glass peas, quartz powder, silica sand, various metal powders, carbon black, barium sulfate, calcined gypsum, etc. Inorganic compounds such as silicon, alumina, boron nitride and silicon nitride,
Includes whiskers, metal whiskers, etc.

In the polymer composition of the present invention exhibiting an anisotropic melt phase, the polymer chains are highly oriented even in a static state when melted, and the high orientation is further enhanced by the flow of the melt during melt molding. In order to show higher orientation in the laminated film.

Next, the film-formable thermoplastic polymer used in the laminate film of the present invention has a strength capable of reinforcing at least the strength in the transverse axis direction with respect to the orientation direction of the thermodropink liquid crystal polymer when the laminate film is formed. In addition, it is necessary that the polymer has excellent film forming ability by melt molding, and the following polymers are exemplified. Polyethylene, polypropylene, polybutylene, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, acrylic resin, ABS resin, AS resin, BS resin, polyurethane, silicone resin, fluorine resin, polycarbonate,
Polyethylene terephthalate, polybutylene terephthalate, aromatic polyester, polyamide, polyacrylonitrile, polyvinyl alcohol, polyvinyl ether, polyetheramide, polyamideimide, polyetheretherimide, polyetheretherketone, polyethersulfone, polysulfone, polyphenylene sulfide, ionomer , T.P.X.

and copolymers thereof.

Among these, polyamide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, aromatic polyester, polyether sulfone, polyether imide, polyether ether ketone, polyphenylene sulfide, and the like are preferred.

The method for forming the laminate film of the present invention includes various methods conventionally used for forming thermoplastic resin films, such as inflation processing, T-die film processing, calendering method, casting method, and stretching methods thereof. Conventional methods can be used in combination with. Further, when using a multilayer laminate in which at least one type is formed singly into a sheet or film in advance, ordinary laminating equipment and coating equipment can be used.

One preferred method of carrying out the present invention is to prepare a uniaxially oriented sheet of a polymer that forms an anisotropic melt phase, and to melt-form a thermoplastic polymer having film-forming ability on this sheet by the usual laminate film forming method as described above. There is a way to laminate it.

The individual sheets of polymer forming the anisotropic melt phase that make up such a laminate can be produced by any conventional method, including extrusion and melt stretching of the polymer through a suitably sized slit die under conditions of suitable temperature and pressure. Forming a sheet is the preferred manufacturing method. As used herein, the term "sheet" includes all of the various relatively thin, substantially flat structures that are sometimes referred to in the art as sheets, slabs, films, and the like. The thickness of the individual sheets constituting the laminate is not particularly limited, and depends on the intended use of the laminate; for example, the higher the required strength, the greater the need to use a thicker sheet.

Sheets produced in this manner exhibit a substantially uniaxial or unidirectional orientation.

The presence of such alignment or unidirectional orientation can be determined by measuring the tensile properties (i.e., tensile strength) of the sheet in both the machine (MD) and transverse (TD) directions according to American Standard Test Method ASTM D 882. can. C) Appropriate uniaxial orientation exists when the ratio of tensile strength in the H direction (extrusion direction) to the transverse direction exceeds about 2.0 (preferably within the range of about 2.0 to 100). . Particularly preferably, this ratio is within the range of about 10-50.

The temperature and pressure conditions under which the liquid crystal polymer can be extruded to form a sheet are not particularly limited in the present invention.
Those skilled in the art can readily determine these conditions. Generally, extrusion of thermotropic liquid crystal polymers is approximately 250-3
It can be carried out at a temperature in the range of 50° C. (depending on the melting temperature of the polymer) and under a pressure in the range of about 7.0 to 350 kg/cm 2 .

To ensure that the as-extruded sheet exhibits the desired uniaxial orientation, the extruded polymer melt is preferably subjected to a drawing step. The draw down ratio is generally greater than about 5.0. The stretched polymer is then cooled or quenched by appropriate means such as cooling rolls, air blowing, or water cooling.

According to the method of the present invention, a film can be formed using a lamination processing device such as a T-die extrusion type lamination processing device or a coating processing device on the high-strength, highly oriented sheet of thermotropic liquid crystal polymer thus obtained. The thermoplastic polymers having the following properties can be laminated together by melt molding. This process can easily be carried out continuously on an industrial scale.

Also, in this case, the sheets to be laminated can be heated above their melting temperature without significantly reducing the high degree of orientation exhibited by the polymers making up the sheets. Since such polymers retain their anisotropy even in the melt phase,
It is possible to avoid using adhesives or the like when joining the sheets together. However, if desired, an adhesive phase may be included as a third component.

In another preferred method of implementing the present invention, it is also possible to simultaneously melt-form and laminate both a polymer that forms an anisotropic melt phase and a thermoplastic polymer that has film-forming ability, and then stretch the polymer after the melt-forming. It is preferable to subject it to a process.

The mechanical properties of laminates produced according to the invention may also be further improved by subjecting them to heat treatment after their formation.

〔Example〕

Next, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

Examples 1 to 5 Thermotropic liquid crystal polymer pellets obtained by polymerizing 75 mol% of p-hydroxybenzoic acid and 25 mol% of 6-hydroxy-2-naphthoic acid were dried in advance at 140°C for 7 hours. This polymer was extruded at a speed of 2.72 m/min using a T-die type extruder, and a width of 8.15 cm was obtained.
A film with a thickness of 0.10 m/m was obtained. The melt drawdown ratio at this time was 14.3.

The obtained thermotropic liquid crystal polymer film was coated with polycarbonate (Lexan 8030 manufactured by Asahi Glass), nylon 12 (Diamid 441B manufactured by Daicel Chemical Industries), polyethylene terephthalate (manufactured by Toshi), and polybutylene terephthalate (Duranesox manufactured by Polyplastics).
, polyacrylate (Durel manufactured by Occidental) was laminated using a T-die extrusion type lamination device, and the width was 8.15cm, 0°15±0.05m/
A laminated film with a thickness of m was obtained.

The obtained laminate film was processed in the main axis direction (MD) and in the direction perpendicular to the main axis direction (TD) according to ASTM D 882.
The tensile strength was measured in two directions.

The results are shown in Table 1.

Example 6 A thermodropink liquid crystal polymer obtained by polymerizing 75 mol% of p-hydroxybenzoic acid and 25 mol% of 6-hydroxy-2'-naphthoic acid and a laminate film of polyethylene terephthalate were combined using a multilayer blown film device. Created by melt molding and similarly ASTM
The tensile properties were determined according to D 882. The results are shown in Table 2.

Example 7 A thermotropic liquid crystal polymer obtained in the same manner as in Example 6 and polyethylene terephthalate were melt-molded using a T-die multilayer extrusion device and a biaxial stretching device to obtain a biaxially stretched laminate film. Similarly, ΔSTM D
Tensile properties were measured according to 882. The results are shown in Table 2.

Table 1: Laminated film's drawstring sealing agent Table 2: Film preparation method and tensile strength procedure (Section of the official seal) January 8, 1985 1. Indication of the incident Patent application No. 1987-210587 2. Title of the invention Manufacturing method for laminate film 3, relationship with the case of the person making the amendment Patent applicant Polyplastics Co., Ltd. 4, agent 3 Nakai Building, Nihonbashi Yokoyama-cho, Chuo-ku, Tokyo 1-3 Column 6 for detailed explanation of the invention in the specification , Contents of amendment fil The following statement was added between lines 14 and 15 on page 17 of the specification: ``The polymer exhibiting an anisotropic melt phase used in the present invention is
Aromatic polyesters and aromatic polyesteramides are preferred, and polyesters partially containing aromatic polyesters and aromatic polyesteramides in the same molecular chain are also preferred examples.

Preferred examples of the compounds constituting them are naphthalene compounds such as 2,6-naphthalene dicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene and 6-hydroxyl 2-naphthoic acid, 4,4'-diphenyl Dicarboxylic acid, biphenyl compounds such as 4.4″-dihydroxybiphenyl, the following general formulas (1), (n)
or a compound represented by (I[[): (where X: alkylene (C+ to C4), alkylidene, -O-, -5O
A group selected from -1-5O□-1-8-, -co-
Z) 110-(n・1 to 4)) benzene compounds substituted at the rose position such as p-hydroxybenzoic acid, terephthalic acid, hydroquinone, p-aminophenol, and p-phenylenediamine, and their nuclear substituted benzenes compound (substituents selected from chlorine, bromine, methyl, phenyl, l-phenylethyl), isophthalic acid,
It is a meta-substituted benzene compound such as resorcinol.

A preferred example of the polyester partially containing the above-mentioned constituents in the same molecular chain is polyalkylene terephthalate, in which the alkyl group has 2 to 4 carbon atoms.

Among the above-mentioned components, a more preferred example is one containing one or more compounds selected from naphthalene compounds, biphenyl compounds, and para-substituted benzene compounds as an essential component. Among the p-substituted benzene compounds, p-hydroxybenzoic acid, methylhydroquinone and 1-phenylethylhydroquinone are particularly preferred examples.

The following are exemplified as specific combinations of constituent components.

(-Q-) (-CO,,-Q-0(C1l□)tO-Q-CO-)
(-0(C1l mountain 0-GO-J!:5-Co-) In the formula, Z is a substituent selected from -CL-Br+-CH3, and X is alkylene (01-C1), alkylidene,
It is a substituent selected from -O-, -5O-1-3O□-1-S-, and -CO-. (1) Same page 36, line 16 rt-----Good. ”
Add the following statement next to

Claims (1)

[Claims] 1. When producing multilayer sheets and multilayer films made of a polymer that forms an anisotropic melt phase and a thermoplastic polymer that has film-forming ability, at least one of the polymers is melt-molded and laminated. A method for producing a laminate film, characterized by: 2 A uniaxially oriented sheet of a polymer that forms an anisotropic melt phase is prepared, and a thermoplastic polymer having film-forming ability is melt-molded and laminated onto the sheet.
Manufacturing method described in section. 3. The manufacturing method according to claim 1, wherein both a polymer that forms an anisotropic melt phase and a thermoplastic polymer that has film-forming ability are simultaneously melt-molded and laminated. 4. The manufacturing method according to claim 3, in which biaxial stretching is performed after melt molding.