JPH0289617A - Film and method and apparatus for manufacturing thereof - Google Patents

Abstract

PURPOSE:To make even liquid crystalline polymer keep the intrinsic strength of the polymer and give the polymer excellent tear resistance by a method wherein the polymer of film is orientated in extrusion direction and, at the same time, one polymer among polymers at the front and rear layer parts of the film is orientated in the direction different from the extrusion direction. CONSTITUTION:Film is manufactured by T-die technique or by extruding polymer having film-forming properties such as crystalline polymer or the like through the slit of a T-die, which is connected to an extruder. A manifold 3, to which molten resin is fed and which is led to a slit 4, is formed in a die main body 2 consisting of the T-die 1. At both sides of the slit 4, a pivotable endless belt 6, which acts as a pivoting means 5 for making shearing stress act on molten polymer in the direction normal to the extrusion direction of the molten polymer by abutting against the molten polymer, is provided at the tip of the T-die 1. As the pivoting means is pivoted, shearing stress acts on the molten polymer, resulting in orientating the polymer in the direction different from the extrusion direction.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a film, a method for producing the same, and a film production apparatus, and more specifically, the present invention relates to a film, a method for producing the same, and a film production apparatus. The present invention relates to films, their manufacturing methods, and film manufacturing equipment.

[Prior Art and Problems to be Solved by the Invention] Liquid crystalline polymers are materials with excellent heat resistance, dimensional stability, and mechanical strength. However, in film molding, melt extrusion is extremely difficult due to the highly oriented molecular chains that characterize liquid crystalline polymers. Films with mechanical properties that can be put to practical use have not yet been obtained.In particular, because the molecular chains are highly oriented, the anisotropy is strong, the strength in the width direction of the film is extremely low, and the durability is poor. Tear strength is poor.

Therefore, liquid crystalline polymer films or sheets with reduced anisotropy and their production methods have been proposed, but it is difficult to industrially produce uniform films with crushed characteristics with good reproducibility. 0 For example, JP-A-55-
No. 161824 discloses a method for preparing a highly polymerized polyester containing ρ oxybenzoic acid residues, hydroquinone residues, and isophthalic acid residues, and discloses a method for preparing a highly polymerized polyester containing ρ oxybenzoic acid residues, hydroquinone residues, and isophthalic acid residues, and JP-A-56-4626 and JP-A No. 56-46727 discloses a polyester film comprising the same components as those mentioned above and a method for producing the same. In all of these techniques, anisotropy is reduced by plasticizing the liquid crystalline polymer itself, which serves as a raw material. However, in these films, etc., the reduction in anisotropy is extremely large, and there is a problem that the strength originally possessed by the liquid crystalline polymer is sacrificed.

In addition, as a method for obtaining a film without anisotropy while maintaining the original strength of liquid crystalline polymers, JP-A No. 52-10
Japanese Patent No. 9578 proposes an 81-layer multiaxially oriented film in which a plurality of films in which liquid crystalline polymers are uniaxially oriented are laminated so as to intersect at an angle of 30° or more. However, in films manufactured by conventional extrusion molding methods, the orientation direction coincides with the film take-off direction, making it difficult to laminate multiple films with their orientation directions intersecting at a constant angle in a continuous process. .

In particular, it is extremely difficult to continuously produce long and thin products industrially, and it is not economical, so it is not satisfactory as an industrial manufacturing method.

Improvements to extrusion molding machines are also being considered. For example, in JP-A No. 58-59818, a heatable plate-shaped porous body is installed inside the die in order to reduce the anisotropy of the film by generating turbulent flow in the die and disturbing the orientation. A method has been proposed. However, with this method, not only does the equipment become extremely complex, but experiments have shown that the shear rate within the porous body inside the die is too high, resulting in extremely poor workability and operability, making it impractical for industrial use. It's not a typical method.

On the other hand, as a method for improving tear resistance by limiting molding conditions, Japanese Patent Application Laid-Open No. 56-467287 discloses that the film is stretched at a stretching ratio of 2 to 50 times in the take-off direction and in the width direction by an inflation method. A method of manufacturing a biaxially oriented film by increasing the magnification from 1.2 to 20 times has been proposed. However, when using this method, increasing the stretching ratio in the width direction in order to obtain sufficient strength in the width direction not only reduces the thickness accuracy of the film, but also causes the film to become threaded during blowing, resulting in poor workability. There is a problem that operability is not sufficient.

An object of the present invention is to provide a film that maintains the inherent strength of a liquid crystal polymer, has tear resistance, etc., and can be used for practical purposes.

Another object of the present invention is to industrially and economically obtain a film that maintains the inherent strength of a liquid crystal polymer, has excellent tearability, etc., and is usable for practical use through a continuous process. An object of the present invention is to provide a film manufacturing method and a film manufacturing apparatus that can perform the following steps.

[Structure of the Invention] As a result of intensive research, the present inventors discovered that the above object can be achieved by a film having a specific orientation structure, leading to the present invention.

That is, the present invention provides a polymer film formed by a T-die method, in which the polymer of the film is oriented in the extrusion direction, and the polymer of at least one of the front and back layer parts of the film is oriented in the above-mentioned manner. The above problem is solved by a film oriented in a direction different from the extrusion direction.

According to the film having the above structure, the polymer is oriented in the extrusion direction, and the polymer in at least one of the front and back layer parts of the film is continuously oriented in a direction different from the extrusion direction. It has no anisotropy and can exhibit the inherent strength of the polymer not only in the extrusion direction but also in a direction perpendicular to the extrusion direction.

The present invention also provides a method for manufacturing a film by melt-extruding a polymer film through a slit of a T-die, wherein in the slit portion of the T-die, the polymer of at least one of the front and back layer portions of the molten polymer is The above-mentioned problem is solved by a method for manufacturing a film in which melt extrusion is performed while applying shear stress in a direction perpendicular to the extrusion direction.

According to the method for producing a film having the above configuration, in the slit portion of the T-die, shear stress is applied to the polymer of at least one of the front and back layer portions of the molten polymer in the rotational direction perpendicular to the extrusion direction. The polymer in at least one of the front and back layer parts of the film can be oriented in a direction different from the extrusion direction.

Furthermore, the present invention provides an extruder equipped with an extruder R for melting and extruding a polymer having film-forming ability, and a slit communicating with the extrusion mechanism of this extruder to form a slit through which the molten polymer is extruded. A film manufacturing apparatus having a T-die, wherein at least one side of the slit is provided with a rotating means that contacts the molten polymer and applies shear stress in a direction perpendicular to the extrusion direction of the molten polymer. This film manufacturing apparatus solves the above problems.

According to this film manufacturing apparatus, at least one side of the slit is provided with a rotating means that contacts the molten polymer and applies shear stress in a direction perpendicular to the extrusion direction of the molten polymer. As the moving means rotates, shear stress is applied to the molten polymer, and the polymer can be oriented in a direction different from the extrusion direction.

In this specification, the term "liquid crystalline polymer" refers to a thermotropic liquid crystalline polymer composition that becomes moldable by softening and flowing upon heating and exhibits an anisotropic melt phase having birefringence when melted.

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

Examples of the above-mentioned liquid crystalline polymers include polymers made 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) One or more aromatic hydroxycarboxylic acids or two or more types (4) one or more aromatic thiol carboxylic acids (5) one or more aromatic dithiols, aromatic thiol phenols (6) one or more aromatic hydroxyamines, aromatic diamines More than a species.

The liquid crystalline polymer consisting of the above components includes:) polyester consisting of components (1) and (2); 1) polyester consisting of component (3); ii) polyester consisting of component 411 (
Polyester consisting of 1), (2) and (3)■) Polythiol ester consisting of component (4)■)
Polythiol ester consisting of constituent components (1) and (5) vi) Polythiol ester consisting of constituent components (1), (4) and (5) vi i) Constituent components (1), (3) and (5) polyester amide consisting of (iii) constituent components (1), (2), (3) and (5)
) is selected as a combination of polyesteramide, etc.

Furthermore, although not included in the scope of the above-mentioned combinations of ingredients, such liquid crystalline polymers include aromatic polyazomethines;
Specific examples include trilo-2-methyl-1,4-phenylenenitriloethyridine-14-phenylenemethylidine) for poly, and trilo-2-methyl-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine for poly. )
, and polytrilow (2-chloro-1°4-phenylenenitrilomethylidine-1,4-phenylenemethylidine).

Further, although not included within the scope of the above-mentioned component combinations, such liquid crystalline polymers include polyester carbonates. It may consist essentially of 4-ogicibenzoyl units, dioxyphenyl units, dioxycarbonyl units and terephthaloyl units.

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゜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 derivatives of the above-mentioned aromatic dicarboxylic acids such as dichloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid, dimethylterephthalic acid, ethylterephthalic 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, or trans-1,4-( 1
-methyl)cyclohexanedicarboxylic acid, trans-1
, 4-(1-chloro)cyclohexanedicarboxylic acid and the like, alkyl, alkoxy or halogen substituted products of the above alicyclic dicarboxylic acids, and the like can be mentioned.

Aromatic diols include hydroquinone, resorcinol, 4.4′-dihydroxydiphenyl, 4.4″-dihydroxytriphenyl, 2,6 naphthalene diol, 4
, 4'-dihydroxydiphenyl ether, bis(4-
hydroxyphenoxy)ethane, 3.3'-dihydroxydiphenyl, 3.3'-dihydroxydiphenyl ether, 16-naphthalenediol, 2.2-bis(4-hydroxyphenyl)propane, 1.1-bis(4-hydroxyphenyl) Alkyl, alkoxy or halogen substitution of aromatic diols such as methane, or the above aromatic diols such as chlorohydroquinone, methylhydroquinone, 1-butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4-chlororesorcinol, 4-methylresorcinol, etc. Examples include the body.

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

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 hydroxycarboxylic acids such as 2-naphthoic acid, 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, 2.3-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
Examples include alkyl, alkoxy or halogen-substituted aromatic hydroxycarboxylic acids such as naphthoic acid, 6-droxy-7-chloro-2-naphthoic acid, and 6-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.

Aromatic dithiols include benzene-1,4-dithiol, benzene-1,3-dithiol, naphthalene-2,
Examples include 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-aminephenol, 1,4-phenylenediamine, N-methyl-1,4
- Phenylenediamine, N.

N-dimethyl-1,4-phenylenediamine, 3-aminephenol, 3-methyl-4-aminephenol,
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'-ethylenedianiline, 4.4
'-Diamino diphenoxyethane, 4.4'-diaminodiphenylmethane (methylene dianiline), 4.4'-
Examples include diaminodiphenyl ether (oxydianiline).

The above polymers i) 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 Siegen distribution, there are some that do not have birefringence when melted, but the polymers used in the present invention are those that exhibit an anisotropic melt phase among the above polymers. limited to.

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

Fully aromatic polymers suitable for use in the present invention tend to be substantially insoluble in common solvents and are therefore unsuitable for solution processing. However, as previously mentioned, these polymers can be easily processed using conventional melt processing techniques. Particularly preferred fully aromatic polymers are somewhat soluble in pentafluorophenol.

The fully aromatic polyester suitably used in the present invention may have an appropriate molecular weight, but generally has a weight average molecular weight of about 2,000 to 200,000, preferably about 1
0,000 to 50,000, particularly preferably about 20,0
00 to 25,000. On the other hand, suitable fully aromatic polyesteramides may have any suitable molecular weight, but generally have a molecular weight of about s,ooo to 50,000, preferably about 10,000 to 30,000, e.g.
000 to 17.000 is determined by gel permeation chromatography as well as other standard measurements that do not involve melt formation of polymers, e.g. quantification of end groups by infrared spectroscopy on compression molded films. This can be done by doing this. The molecular weight can also be measured using a light scattering method using a pentafluorophenol solution.

The fully aromatic polyester amide described above, when dissolved in pentafluorophenol at a weight percent concentration at a temperature of 60° C., is at least about 2.0 dJ/g, such as about 2.0 to 1
0. The logarithmic viscosity (1, V, ) in OdJ/g is generally indicated.

Particularly preferred polyesters forming an anisotropic melt phase are:
It contains about 10 mol% or more of naphthalene moiety-containing units such as 6-hydroxy-2-naphthoyl, 2.6-dihydroxynaphthalene and 2,6-dicarboxynaphthalene. Preferred polyesteramides include the above-mentioned naphthalene moieties and 4-aminophenol or 1,4-
It contains a repeating unit with a moiety consisting of fluorinated diamine. Specifically, the details are as follows.

(1) A polyester consisting essentially of the following repeating units (1) and (2);

-a, the unit work is approximately 65 to 85 mol% (for example,
up to an amount of about 75 mole %). In the pond aspect,
The unit ■ is about 15 to 35 mol%, preferably about 20 to 30
Present in amounts as low as mole %. In addition, at least a part of the hydrogen atoms bonded to the ring may have 1 to 1 carbon atoms.
4, alkoxy groups, halogen atoms, phenyl groups, substituted phenyl groups, and combinations thereof.

(2) Polyester consisting essentially of the following repeating units ■, ■, and 1v: This polyester contains about 10 to 90 mo of units ■ (hereinafter referred to as
Margin) This polyester contains about 30 to 70 mol % of the unit (■). The polyester preferably has about 40 units
~60 mol%, about 20-30 mol% of units ■ and units I
Contains about 20 to 30 mol% of V. In addition, at least a part of the hydrogen atoms bonded to the ring may have 1 carbon number
-4 may be substituted with a substituent selected from the group consisting of an alkoxy group, a halogen atom, a phenyl group, a substituted phenyl group, and a combination thereof.

(3) A polyester consisting essentially of the following repeating units ■, ILV and Vl; (wherein R means a methyl group, chloro, bromo or a combination thereof, and is a substituent for the hydrogen atom on the aromatic ring) This polyester contains approximately 20 to 60 mol% of unit ■, approximately 5 to 35 mol% of unit IV, and approximately 5 to 18 mol% of unit V.
Contains about 20 to 40 mol% of units (1) and (2). This polyester preferably contains about 35 to 45 mol% of units
Approximately 15 to 25 mol % of unit IV and approximately 10.0 mol % of unit V. ~1
5 mol % and about 25 to 35 mol % of units (■). However, the total molar concentration of units (■) and V is substantially equal to the molar concentration of units (2), and at least a portion of the hydrogen atoms bonded to the ring may optionally be an alkyl group having 1 to 4 carbon atoms, Optionally 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,
The fully aromatic polyester, when dissolved in pentafluorophenol at a concentration of 0.3% W/V at a temperature of 60°C, has a concentration of at least 2.0 d/g, e.g.
．． Logarithmic viscosity in OdJ/g is generally indicated.

(4) Polyester consisting essentially of the following repeating units I, ■, ■, and ■; general formula +0-Ar-0+ ■ (wherein Ar means a divalent group containing at least one aromatic ring) dicarboxyaryl unit represented by the dioxyaryl unit (in the formula, Ar is the same as above). % or less, unit
more than 5 mol% and less than about 30 mol%, and the unit ■ is 5
It is contained in an amount of more than 30 mol %, but not more than about 30 mol %. 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 20 mol%, and about 15 to 2 units
It contains 5 mol%, for example about 20 mol%.

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, a halogen atom, a phenyl group, a substituted phenyl group, and a combination thereof.

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 main chain are arranged symmetrically (e.g., naphthalene rings). Symmetrical units are preferably symmetrical in the sense that they are disposed para to each other or diagonally when present, except for asymmetric units such as those derived from resorcinol and isophthalic acid. Can be used.

The preferred dioxyaryl unit Vl is , and the preferred dicarboxyaryl unit 2 is .

(5) Polyester essentially consisting of the following repeating units I, ■, ■; dioxyaryl unit represented by the general formula +0-Ar-0÷■ (wherein Ar is the same as above) (wherein Ar is the same as above) (same as above) This polyester contains about 10 to 90 mol % of the unit, 5 to 45 mol % of the unit (2), and 5 to 45 mol % of the unit (2). This polyester preferably contains about 20 to 80 mol % of units (2), about 10 to 40 mol % of units (2), and about 10 to 40 mol % of units (2). More preferably, the polyester has about 60 to 80 mole percent of units
, about 10 to 20 mol % of units (2), and about 10 to 20 mol % of units (2). At least a portion of the hydrogen atoms bonded to the ring may optionally be an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom,
It may be substituted with a 'Il substituent selected from the group consisting of phenyl, substituted phenyl, and combinations thereof.

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

(6) Polyester amide consisting essentially of the following repeating units ■, IX, a unit represented by the general formula +0-Ar-0+)-X (meaning a divalent trans-cyclohexane group) (where Ar is the same as above, Y is 0, NH or NR,
Z means NH or NR, and R has 1 to 1 carbon atoms.
4 (means an alkyl group or aryl group); dioxyaryl unit represented by the general formula +0-Ar-0+ (wherein Ar is the same as above); -90 mol%, unit (1) contains 5 to 45 mol% of unit (X), 5 to 45 mol% of unit (X), and approximately 0 to 40 mol% of unit (2). In addition, at least a portion of the hydrogen atoms bonded to the ring may optionally be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having IN 4 carbon atoms, a halogen atom, a phenyl group, a substituted phenyl group, or a combination thereof. It may be substituted with a substituent selected from.

Preferred dicarboxyaryl units IX are , preferred units X are , and preferred dioxyaryl units I 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, a low-molecular organic compound, and an inorganic substance; the polymer that forms the anisotropic melt phase in the composition and the remaining portion are They may 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, silibone resin, fluororesin, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, aromatic polyester, polyamide, polyacrylonitrile,
Included are polyvinyl alcohol, polyvinyl ether, polyetherimide, polyamideimide, polyetheretherimide, polyetheretherketone, polyethersulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, and the like.

Examples of the thermosetting resin (2) above include phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, and the like.

Examples of the low-molecular-weight organic compounds mentioned in (1) above include substances normally added to thermoplastic resins and thermosetting resins, such as plasticizers, weather and light stabilizers such as antioxidants and ultraviolet absorbers, and antistatic agents. , flame retardants, colorants such as dyes and pigments, blowing agents, divinyl compounds, crosslinking agents such as peroxides and vulcanizing agents, and low-carbon compounds used as lubricants to improve fluidity and mold release properties. Includes molecular organic compounds. Furthermore, the above inorganic substances include, for example, substances normally added to thermoplastic resins and thermosetting resins, such as general inorganic fibers such as glass fibers, carbon fibers, metal fibers, ceramic fibers, boron fibers, and asbestos; Powder substances such as calcium, 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, and silica carbonate. It includes inorganic compounds such as boron nitride and silicon nitride, whiskers, and metal whiskers.

Note that the present invention can be applied to polymers other than liquid crystalline polymers having anisotropy and polymers constituting films conventionally manufactured by the T-die method; Preference is given to application to films consisting of polymers and compositions thereof.

The polymer film of the present invention is formed by the T-die method, and the polymer constituting the film is oriented in the extrusion direction. The T-die method is a method of manufacturing a film by melt-extruding a polymer having film-forming ability such as a liquid crystalline polymer using an extruder, and extruding the molten polymer through a slit of a T-die connected to the extruder. Molten polymers, particularly liquid crystalline polymers with high orientation, are oriented in the extrusion direction as they are extruded.

In order to eliminate the anisotropy of liquid crystalline polymers and develop the inherent strength of the polymer, the polymer in at least one of the front and back layers of the film is oriented in a direction different from the extrusion direction. . Of the polymers constituting the film, it is sufficient that the polymers in at least the front and back layers are oriented, and the polymers may be oriented in a direction different from the extrusion direction not only in the front and back layer parts of the film but also throughout the film. good.

The orientation direction of the polymer may be different from the extrusion direction, but in order to develop high mechanical strength, it is preferable to orient the polymer in a direction perpendicular to the extrusion direction. Or, since the polymer in the back layer is oriented in a direction different from the extrusion direction, even if the film is made of a liquid crystalline polymer, there is no anisotropy and the tear resistance is high.

The film of the present invention can be manufactured as follows. That is, when melt-extruding a polymer film from a T-die connected to an extruder, shear stress is applied to the polymer in at least one of the front and back layers of the molten polymer in a direction perpendicular to the extrusion direction at the slit section. Just let it work.

Below, the method for manufacturing a film of the present invention will be explained based on the accompanying drawings.

FIG. 1 is a longitudinal sectional view showing an embodiment of the T-die connected to an extruder, and FIG. 2 is a cross-sectional view of the T-die shown in FIG. 1.

The die body (2) constituting the T-die (1) has a manifold (3) to which molten resin extruded in a molten state from an extruder (not shown) of an extruder (not shown) is supplied. This manifold (3) extends to a slit (4) which is a discharge port for the molten polymer, and forms a lip at the tip of the T-die (1).

Rotating means (5) are provided on both sides of the slit (4) to contact the molten polymer and apply shear stress in a direction perpendicular to the extrusion direction of the molten polymer. More specifically, as shown in FIG. 2, the rotating means (5) is composed of an endless belt (6) that is rotatable at the tip of the T-die (1). (6) has a slit (
4) is formed. In addition, on both sides of the die side plate (8), there is a rotary drive shaft (7) that slides on the endless belt (6) under tension and transmits rotational force, and
) is provided with a rotational drive source (not shown) for rotating.

According to the film manufacturing apparatus having the above structure, the rotational force of the rotational drive source is transferred to the endless belt (6) through the rotational drive shaft (the blade).
Therefore, shear stress can be applied to the molten polymer at the slit (4) in a direction perpendicular to the extrusion direction.

Note that the rotating means (5) is not limited to the endless belt (6), and may be any member that comes into contact with the molten polymer and applies shear stress in the above-mentioned direction.

Further, the extruder for melt extrusion molding is not particularly limited, but a conventionally known extruder used for extrusion molding of thermoplastic resins is preferably used.

In the film manufacturing apparatus described above, tooth-shaped uneven parts may be formed on the outer surface of the endless belt (6). The endless belt (6) has a rotary drive shaft having a gear that meshes with the uneven portion, and a rotary drive source that rotates the rotary drive shaft having this gear.
) may be rotated in a predetermined direction.

FIG. 3 is a sectional view showing another embodiment of the T-die in the film manufacturing apparatus of the present invention, and the die body (12) constituting the T-die (11) has a manifold formed in the same manner as above. ing. Also, in this example, the slit (14
) section is formed by the opposing surfaces of a pair of endless belts (16a and 16b), and each endless belt (1
6a and 16b are rotated by a rotation drive source (not shown) via rotation drive shafts (17a and 17b) provided on both sides of the die side plate (18), respectively.

According to the film manufacturing apparatus having the above configuration, the slits (14
) section is formed by the facing surface of the endless belt (16a) (16b) that does not come into sliding contact with the rotational drive shaft (17aH17b), so that the film manufacturing apparatus is -, The slit (14) portion can be formed with higher precision. Further, by rotating at least one of the pair of endless belts (16a) and (16b), the slit (14
), shear stress can be applied to the polymer in at least one of the front and back layer parts of the molten polymer in a direction perpendicular to the extrusion direction. The pair of endless belts (168H16b) may rotate in the same direction or may rotate in different directions.

In addition, the film ffi! shown in FIG. ! In the manufacturing apparatus, the pair of endless belts (16aH16b) is not necessarily required, and it is sufficient that at least one of the endless belts is provided.

In addition, sealing members may be provided on both sides of the T-die (11 (11)) to prevent the molten polymer from leaking to the sides of the T-tie (11 (11)) as the endless belt (61f16aH16b) rotates. .

The shape and structure of the T-die (ilm) are not particularly limited,
It is sufficient that the slits (6), (16a, and 16b) have rotating means such as an endless belt that rotates the molten polymer in a direction perpendicular to the extrusion direction.

The area where the rotational shearing force is applied by the endless belt is not limited to the tip of the T-die, but may be any area where the polymer in the front and back layers of the obtained film can be oriented in a direction different from the extrusion direction, but preferably is from the tip of the T-die, more preferably from the tip of the lip. The preferred width of the dress belt is about 10 to 80 nm.

The drive mechanism such as the rotary drive shaft for driving the endless belt may be provided on both sides of the T-die as shown in the figure, but is preferably provided internally within the T-die.

The extrusion temperature of liquid crystalline polymer, etc. is equal to or higher than the flow start temperature of the polymer.For example, in the case of liquid crystalline polymer, 2
Temperature of 00-400°C, preferably 260-330°
The temperature is C. Note that the flow start temperature referred to here is
This is the lowest temperature at which liquid crystalline polymers can melt and flow.

It is also preferable that an endless belt temperature control device is provided. When controlling the temperature of an endless belt, the preferable temperature of the endless belt is between 10°C and +10°C below the resin temperature.
The temperature is about 20°C, more preferably +5 to the resin temperature.
+10°C. Note that the method of the temperature control device is not particularly limited, and various heating and temperature control methods such as a heater may be employed.

The material of the endless belt described above may be a metal used for general T-dies and metal belts, or may be a heat-resistant and corrosion-resistant metal if necessary, but is not limited to metal. do not have.

A process of forming a liquid crystalline polymer film having preferable characteristics using the film manufacturing apparatus as described above will be described below.

The endless belt can rotate in a direction perpendicular to the film extrusion direction, that is, the take-up direction. When the liquid crystalline polymer melt passes through the endless belt section, the shear stress generated by the rotation of the endless belt causes the liquid crystalline polymer melt to flow in a direction perpendicular to the film pulling direction, causing the liquid crystalline polymer to be pulled. A continuous layer is formed that is oriented in a direction perpendicular to the cutting direction. Then, as the liquid crystalline polymer flows in the discharge direction, that is, the extrusion direction within the T-die, the molecular chains are oriented in the direction in which the film is taken off. The orientation of the molecular chains in the direction perpendicular to the pulling direction of is induced. Therefore, it is presumed that the liquid crystalline polymer film obtained by the present invention has molecular chains biaxially oriented in each direction within the film plane, has isodirectional physical properties, and has excellent tear resistance. Ru.

Note that the ratio of the shear rate between the film take-up direction and the direction orthogonal to the direction is not particularly limited, and can be set as appropriate depending on the desired film characteristics.
The ratio is preferably 1.0:0.2 to 5.0, and the rotational speed of the endless belt can be appropriately set depending on the desired properties of the film. In addition, by controlling the flow rate (extrusion rate) of the liquid crystalline polymer in the die and the gap between the slits, the shear stress in each direction can be changed, and the orientation direction of the polymer constituting the film can be adjusted to the desired direction. Can be set. The flow rate (extrusion rate) of the liquid crystalline polymer in the die and the gap between the slits can be freely selected depending on the properties of the intended film, and are not particularly limited.

In addition, the polymer film extruded as above is
The film may be uniaxially or biaxially stretched by a conventionally used stretching method, such as a tenter method or a multistage stretching method. Further, if necessary, surface treatment such as corona discharge treatment or heat treatment may be performed.

In the above film, the thickness and width of the film are not particularly limited.

Among the films of the present invention, the liquid crystalline polymer film is
It has high strength and high elastic modulus, and has excellent heat resistance, chemical stability, electrical properties, dimensional stability, gas barrier properties, etc., and does not have the extreme anisotropy that was a drawback of conventional liquid crystal polymer films. It has well-balanced mechanical properties and significantly improved tear resistance. Furthermore, even liquid crystalline polymer films have good appearance and thickness accuracy, and have good workability and operability during extrusion molding, making them suitable for industrial production methods. The film of the present invention can be used in electrical applications such as video tapes, cassette tapes, floppy disks, flexible printed circuit boards, speaker diaphragms, capacitor dielectrics, and motor dielectric films, microfilms, thermal transfer printer tapes, and movie films. It can be preferably used for , barrier materials, sheet molding materials, etc.

[Effects of the Invention] As described above, according to the film of the present invention, the polymer of the film is oriented in the extrusion direction, and the polymer of at least one of the front and back layer parts of the film is
Since it is oriented in a direction different from the above-mentioned extrusion direction, even if it is a liquid crystal polymer, it maintains the strength inherent in the polymer, has excellent tear resistance, etc., and has excellent properties in practical use.

Further, according to the film manufacturing method of the present invention, in the slit portion of the T-die, while applying shear stress to the polymer of at least one of the front and back layer portions of the molten polymer in a direction perpendicular to the extrusion direction, Since it is melt-extruded, it is possible to industrially and economically obtain a practical vine film having the above-mentioned excellent properties in a continuous process.

Furthermore, according to the film manufacturing apparatus of the present invention, the rotating means contacts the molten polymer and applies shear stress to at least one side of the slit of the T-die in a direction orthogonal to the extrusion direction of the molten polymer. , it is possible to industrially and economically obtain a film having the above-mentioned excellent properties in a continuous process.

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

Example A T-die shown in FIGS. 1 and 2 was used as a film manufacturing apparatus. A pellet of liquid crystalline polymer (manufactured by Polyplastics ■, trade name Vectra A900) was heated to 150°C in advance.
Dry at a temperature of 8 hours.

Then, as a T die, a die with a slit width of 400 mm, a lip gap of 0.3 mm, and a metal endless belt of width 30 mm was used at a position of 3° from the tip of the lip, and was heated at a temperature of 280 °C. Extruded.

At that time, the rotary drive shaft rotates the endless belt 4m/
The film was drawn off at a speed of 8 m/min. The obtained film has a tensile strength of 3850 h/n in the pulling direction and in a direction perpendicular to the pulling direction, respectively.
It was 2.3300 h/2, and had excellent tear resistance, and was transparent with a smooth surface and good gloss.

Comparative Example The liquid crystalline polymer used in the example was extruded from a conventional T-die at a temperature of 280°C, and the film was taken off at a speed of 12 m/min. The tensile strength of the obtained film in the pulling direction and in the direction perpendicular to the pulling direction was 465, respectively.
The film had a rating of 0ki/stop 2165-/kan 2, and had poor tear resistance.

[Brief explanation of drawings]

FIG. 1 is a vertical cross-sectional view showing an embodiment of the T-die connected to an extruder, FIG. 2 is a cross-sectional view of the T-die shown in FIG. 1, and FIG. 3 is a T-die in the film manufacturing apparatus of the present invention. FIG. 7 is a cross-sectional view showing another embodiment of the tie. (1) (11)...T-die, (41+141...slit, (5)...rotating means, (61(16aH16b)・Z-dress belt Fig. 1 Fig. 2

Claims (1)

[Claims] 1. A polymer film formed by a T-die method, wherein the polymer of the film is oriented in the extrusion direction, and the polymer of at least one of the front and back layers of the film is oriented in the extrusion direction. , a film characterized in that it is oriented in a direction different from the extrusion direction. 2. The film according to claim 1, wherein the polymer is a liquid crystalline polymer. 3. The film according to claim 1, wherein the polymer in at least one of the front and back layers of the film is oriented in a direction perpendicular to the extrusion direction. 4. A method of manufacturing a film by melt-extruding a polymer film through a slit of a T-die, wherein in the slit of the T-die, at least one layer of the front and back layers of the molten polymer is injected in the extrusion direction. A method for producing a film, comprising melt extrusion while applying shear stress in orthogonal directions. 5. A film comprising an extruder equipped with an extrusion mechanism for melting and extruding a polymer having film-forming ability, and a T-die communicating with the extrusion mechanism of the extruder and having a slit through which the molten polymer is extruded. A manufacturing device,
A film manufacturing apparatus characterized in that a rotating means is provided on at least one side of the slit to contact the molten polymer and apply shear stress in a direction perpendicular to the extrusion direction of the molten polymer. 6. The film manufacturing apparatus according to claim 5, wherein the rotating means is an endless belt.