JP2022115387A - liquid crystal polymer composition - Google Patents

Abstract

To provide a liquid crystal polymer composition having improved adhesion.SOLUTION: A liquid crystal polymer composition contains 100 pts.mass of a liquid crystal polymer having a crystal melting temperature of 210-300°C and 1-100 pts.mass of an imine-modified polyolefin.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a liquid crystal polymer composition having significantly improved adhesion, containing a liquid crystal polymer and a specific modified polyolefin.

Thermotropic liquid crystal polymer (hereinafter also referred to as liquid crystal polymer or LCP) has excellent mechanical properties such as heat resistance and rigidity, chemical resistance, dimensional accuracy, and dielectric properties. Its use is expanding in various applications such as films. Furthermore, since it has excellent gas barrier properties, it is expected to be used as a packaging material.

However, when the liquid crystal polymer is processed into a film, although it exhibits high strength in the processing direction (MD direction), there is a problem that the strength in the direction transverse to the processing direction (TD direction) is significantly reduced.

On the other hand, conventionally, polyolefins such as polypropylene and polyethylene, which have been widely used as packaging materials, have the problem of being inferior in gas barrier properties, although they are excellent in processability into films.

Therefore, in order to improve the gas barrier properties of polyolefin films, it has been investigated to laminate liquid crystal polymer films to form a composite film. However, liquid crystal polymers have insufficient adhesion to other resins, particularly polyolefins, and require special treatments to form composite films.

For example, a composite film has been proposed in which a thermoplastic resin is laminated on one surface of a liquid crystal polymer layer without an adhesive layer (adhesive) interposed therebetween by subjecting the liquid crystal polymer layer to a surface treatment such as corona discharge (Patent Document 1). .

JP-A-4-135750

However, the composite film described in Patent Document 1 requires a surface treatment by corona discharge or the like, which complicates the process, and the adhesive strength is not sufficient.
Therefore, it has been desired to develop a liquid crystal polymer with improved adhesion to other resins.

It is an object of the present invention to provide a liquid crystal polymer composition with improved adhesion. Another object of the present invention is to provide a molded article composed of the liquid crystal polymer composition, particularly a blow molded article using the liquid crystal polymer composition as an adhesive layer between the liquid crystal polymer and the polyolefin.

In view of the above problems, the inventors of the present invention conducted intensive studies and found that a liquid crystal polymer composition with significantly improved adhesiveness can be obtained by blending an imine-modified polyolefin with a liquid crystal polymer, and completed the present invention. came to.

［式中、
Ａｒ_１およびＡｒ_２は、それぞれ１種または２種以上の２価の芳香族基を表し、ｐ、ｑ、ｒおよびｓは、それぞれ、全芳香族液晶ポリエステル中での各繰返し単位の組成比（モル％）であり、以下の条件を満たす：
０．５≦ｐ／ｑ≦２．５
２≦ｒ≦１５、および
２≦ｓ≦１５］
で表される繰返し単位を含む全芳香族液晶ポリエステルである、〔１〕または〔２〕に記載の液晶ポリマー組成物。
〔４〕式（ＩＩＩ）～式（ＩＶ）で表される繰返し単位は、Ａｒ_１およびＡｒ_２が、それぞれ互いに独立して、式（１）～（４）

で表される芳香族基から選択される、それぞれ１種以上の繰返し単位である、〔３〕に記載の液晶ポリマー組成物。
〔５〕イミン変性ポリオレフィンはイミン変性ポリエチレンである、〔１〕～〔４〕のいずれかに記載の液晶ポリマー組成物。
〔６〕〔１〕～〔５〕のいずれかに記載の液晶ポリマー組成物から構成される成形品。
〔７〕液晶ポリマー層（ａ）とポリオレフィン層（ｂ）が接着層（ｃ）を介して積層された構造を有する成形品であって、該接着層（ｃ）は〔１〕～〔５〕のいずれかに記載の液晶ポリマー組成物からなる、成形品。
〔８〕ポリオレフィン層（ｂ）は、ポリエチレン層またはポリプロピレン層である、〔７〕に記載の成形品。
〔９〕多層ブロー成形品である、〔７〕または〔８〕に記載の成形品。 That is, the present invention includes the following preferred embodiments.
[1] A liquid crystal polymer composition containing 100 parts by mass of a liquid crystal polymer having a crystal melting temperature of 210 to 300° C. or less and 1 to 100 parts by mass of an imine-modified polyolefin.
[2] The liquid crystal polymer composition according to [1], wherein the crystal melting temperature of the liquid crystal polymer is 215 to 250°C.
[3] The liquid crystal polymer has formulas (I) to (IV)

[In the formula,
Ar ₁ and Ar ₂ each represent one or more divalent aromatic groups, and p, q, r and s respectively represent the composition ratio of each repeating unit in the wholly aromatic liquid crystalline polyester ( %) and satisfies the following conditions:
0.5≦p/q≦2.5
2≦r≦15, and 2≦s≦15]
The liquid crystal polymer composition according to [1] or [2], which is a wholly aromatic liquid crystal polyester containing a repeating unit represented by:
[4] In the repeating units represented by formulas (III) to (IV), Ar ₁ and Ar ₂ are each independently represented by formulas (1) to (4)

The liquid crystal polymer composition according to [3], each of which is one or more repeating units selected from aromatic groups represented by:
[5] The liquid crystal polymer composition according to any one of [1] to [4], wherein the imine-modified polyolefin is imine-modified polyethylene.
[6] A molded article composed of the liquid crystal polymer composition according to any one of [1] to [5].
[7] A molded article having a structure in which a liquid crystal polymer layer (a) and a polyolefin layer (b) are laminated via an adhesive layer (c), wherein the adhesive layer (c) is one of [1] to [5]. A molded article made of the liquid crystal polymer composition according to any one of .
[8] The molded article according to [7], wherein the polyolefin layer (b) is a polyethylene layer or a polypropylene layer.
[9] The molded article according to [7] or [8], which is a multilayer blow-molded article.

The liquid crystal polymer composition of the present invention can be used not only as a general molding material, but also as an adhesive layer for blow-molded products and laminated films due to its excellent adhesiveness. In addition, the liquid crystal polymer composition of the present invention is particularly suitable for use as an adhesive material between liquid crystal polymers and polyolefins.

The liquid crystalline polymer used in the liquid crystalline polymer composition of the present invention is a wholly aromatic liquid crystalline polyester or wholly aromatic liquid crystalline polyester amide that forms an anisotropic melt phase, referred to by those skilled in the art as a thermotropic liquid crystalline polymer.

The properties of the anisotropic melt phase of the liquid crystal polymer can be confirmed by a normal deflection inspection method using crossed polarizers, that is, by observing a sample placed on a hot stage under a nitrogen atmosphere.

The repeating units constituting the liquid crystal polymer used in the present invention include aromatic oxycarbonyl repeating units, aromatic dicarbonyl repeating units, aromatic dioxy repeating units, aromatic aminooxy repeating units, aromatic diamino repeating units, aromatic Aminocarbonyl repeat units and combinations thereof and the like.

Specific examples of monomers that give aromatic oxycarbonyl repeating units include, for example, aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2 -naphthoic acid, 5-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl- 3-benzoic acid and the like, alkyl, alkoxy or halogen-substituted products thereof, and ester-forming derivatives such as acylates, ester derivatives and acid halides thereof. Among these, 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferred because the mechanical properties, heat resistance, crystal melting temperature and moldability of the resulting liquid crystal polymer can be easily adjusted to appropriate levels.

Specific examples of monomers that give aromatic dicarbonyl repeating units include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7 -naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, etc., alkyl, alkoxy or halogen-substituted products thereof, ester derivatives thereof, ester-forming derivatives such as acid halides, etc. mentioned. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable because the mechanical properties, heat resistance, crystal melting temperature and moldability of the resulting liquid crystal polymer can be easily adjusted to appropriate levels.

Specific examples of monomers that give aromatic dioxy repeating units include aromatic diols such as hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether and the like, and alkyl, alkoxy or halogen substituted versions thereof; and ester-forming derivatives such as acylated products thereof. Among these, hydroquinone and 4,4'-dihydroxybiphenyl are preferable because the reactivity during polymerization and the mechanical properties, heat resistance, crystal melting temperature, and moldability of the resulting liquid crystal polymer can be easily adjusted to appropriate levels.

Monomers that provide aromatic aminooxy repeat units, aromatic diamino repeat units and aromatic aminocarbonyl repeat units include aromatic hydroxylamines, aromatic diamines and aromatic aminocarboxylic acids.

The liquid crystal polymer used in the present invention may contain aromatic oxydicarbonyl repeating units, aliphatic dihydroxy repeating units, aliphatic dicarbonyl repeating units and thioester bonds within a range that does not impair the object of the present invention. . Monomers that provide thioester bonds include mercaptoaromatic carboxylic acids, and aromatic dithiols and hydroxyaromatic thiols. The amounts of these monomers used are limited to aromatic oxycarbonyl repeating units, aromatic dicarbonyl repeating units, aromatic dioxy repeating units, aromatic aminooxy repeating units, aromatic diamino repeating units and aromatic aminocarbonyl repeating units. It is preferably 10 mol % or less with respect to the total including the total amount of monomers to be provided.

Copolymers that combine these repeating units may or may not form an anisotropic melt phase, depending on the composition and composition ratio of the monomers and the sequence distribution of each repeating unit in the copolymer. Although present, the liquid crystalline polymers used in the present invention are limited to copolymers that form anisotropic melt phases.

The liquid crystal polymer used in the present invention may be a blend of two or more liquid crystal polymers.

The crystal melting temperature of the liquid crystal polymer used in the present invention as measured by a differential scanning calorimeter is 210 to 300°C, preferably 212 to 255°C, more preferably 215 to 250°C.

When the crystal melting temperature of the liquid crystal polymer is 210 to 300° C., the imine-modified polyolefin is easily dispersed in the composition, and the moldability into films, sheets, bottles, etc. is improved, and the liquid crystal polymer and other materials are improved. It becomes easy to obtain adhesiveness with the resin.

In the present specification and claims, the term "crystal melting temperature" refers to the crystal melting temperature measured at a heating rate of 20°C/min with a differential scanning calorimeter (hereinafter abbreviated as DSC). It is obtained from the peak temperature. More specifically, after observing the endothermic peak temperature (Tm1) observed when measuring the liquid crystal polymer sample under the temperature rising condition of 20 ° C./min from room temperature, 10 at a temperature 20 to 50 ° C higher than Tm1 After holding the sample for 20 minutes and then cooling the sample to room temperature under the condition of temperature decrease of 20°C/minute, the endothermic peak was measured again under the condition of temperature increase of 20°C/minute. It is the crystalline melting temperature of the polymer. As a measuring instrument, for example, Exstar6000 manufactured by Seiko Instruments Inc. can be used.

As the liquid crystal polymer used in the present invention, a wholly aromatic liquid crystalline polyester is preferably used, and a wholly aromatic liquid crystalline polyester containing repeating units represented by formulas (I) to (IV) is more preferably used.

[In the formula,
Ar ₁ and Ar ₂ each represent one or more divalent aromatic groups, and p, q, r and s respectively represent the composition ratio of each repeating unit in the wholly aromatic liquid crystalline polyester ( mol%), which satisfies the following conditions:
0.5≦p/q≦2.5
2≦r≦15 and 2≦s≦15. ]

The molar ratio (p/q) of the composition ratio p (mol%) according to the formula (I) and the composition ratio q (mol%) according to the formula (II) is more preferably 0.6 to 1.8, and 0 0.8 to 1.6 is more preferred.

The total composition ratio of p and q in the above-mentioned wholly aromatic liquid crystal polyester preferably used is preferably 70 to 96 mol %, more preferably 76 to 90 mol %.

Regarding the wholly aromatic liquid crystal polyester that is preferably used, the composition ratio p according to formula (I) and the composition ratio q according to formula (II) are preferably 32 to 54 mol%, respectively, and 36 to 52 mol%. is more preferred.

In the wholly aromatic liquid crystal polyester preferably used in the present invention, the repeating units represented by formula (I) and formula (II) are at least the above molar ratio (p / q), and optionally the above p and By including the total composition ratio of q and/or the composition ratio (mol %) of each of p and q, a wholly aromatic liquid crystalline polyester exhibiting a crystal melting temperature of 250° C. or less can be suitably obtained.

Further, for the wholly aromatic liquid crystal polyester suitably used in the present invention, the composition ratio r according to formula (III) and the composition ratio s according to formula (IV) are preferably 2 to 15 mol%, respectively, and 5 to 15 mol%. 12 mol % is more preferred. Preferably, r and s are in equimolar amounts.

In the above repeating unit, for example, Ar ₁ (or Ar ₂ ) represents two or more divalent aromatic groups means that the repeating unit represented by formula (III) (or (IV)) is wholly aromatic It means that two or more types are contained in the liquid crystalline polyester according to the type of divalent aromatic group. In this case, the composition ratio r according to formula (III) (or the composition ratio s according to formula (IV)) represents the total composition ratio of two or more repeating units.

Specific examples of monomers that provide repeating units represented by formula (I) include 4-hydroxybenzoic acid and ester-forming derivatives such as acylates, ester derivatives and acid halides thereof.

Specific examples of monomers that give repeating units represented by formula (II) include 6-hydroxy-2-naphthoic acid and its acylated products, ester derivatives, and ester-forming derivatives such as acid halides. be done.

Specific examples of monomers that give repeating units represented by formula (III) include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 1,6-naphthalenedicarboxylic acid. , 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4′-dicarboxybiphenyl, etc., and alkyl, alkoxy or halogen-substituted products thereof, ester derivatives thereof, esters such as acid halides, etc. Formative derivatives are mentioned.

Specific examples of monomers that give repeating units represented by formula (IV) include aromatic diols such as hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, etc., and alkyl and alkoxy thereof Alternatively, halogen-substituted products and ester-forming derivatives such as acylated products thereof may be mentioned.

Further, among the wholly aromatic liquid crystal polyesters preferably used in the present invention, Ar ₁ and Ar ₂ related to the repeating units represented by the formulas (III) and (IV) are each independently represented by the formula ( A wholly aromatic liquid crystalline polyester containing one or more selected from the group consisting of aromatic groups represented by 1) to (4) is more preferably used. That is, in the repeating units represented by formulas (III) to (IV), Ar ₁ and Ar ₂ are each independently selected from aromatic groups represented by the following formulas (1) to (4). are preferably one or more repeating units, respectively.

Among them, the repeating units represented by formula (III) are aromatic groups represented by formulas (1) and (4), that is, the monomers giving these repeating units are terephthalic acid and The use of 2,6-naphthalenedicarboxylic acid and ester-forming derivatives thereof makes it easy to adjust the mechanical properties, heat resistance, crystal melting temperature and moldability of the obtained wholly aromatic liquid crystalline polyester to appropriate levels. Especially preferred.

Further, the repeating units represented by formula (IV) include aromatic groups represented by formulas (1) and (3). The use of '-dihydroxybiphenyl and ester-forming derivatives thereof adjusts the reactivity during polymerization and the mechanical properties, heat resistance, crystal melting temperature and moldability of the obtained wholly aromatic liquid crystalline polyester to appropriate levels. It is particularly preferred because it is easy to use.

In the above repeating unit, for example, Ar ₁ (or Ar ₂ ) contains two or more aromatic groups means that the repeating unit represented by formula (III) (or (IV)) is in the wholly aromatic liquid crystal polyester It means that two or more types are contained in the group according to the type of the divalent aromatic group. That is, in the repeating units represented by formulas (III) to (IV), Ar ₁ and Ar ₂ are each independently selected from aromatic groups represented by the above formulas (1) to (4). are preferably one or more repeating units, respectively. In this case, the composition ratio r according to formula (III) (or the composition ratio s according to formula (IV)) represents the total composition ratio of two or more repeating units.

In the wholly aromatic liquid crystalline polyester suitably used in the present invention, the total composition ratio [p + q + r + s] of the repeating units is preferably 100 mol%, but other repeating units within a range that does not impair the object of the present invention may further contain.

Monomers that give other repeating units constituting the wholly aromatic liquid crystalline polyester preferably used in the present invention include other aromatic hydroxycarboxylic acids, aromatic hydroxyamines, aromatic diamines and aromatic aminocarboxylic acids. , aromatic hydroxydicarboxylic acids, aromatic mercaptocarboxylic acids, aromatic dithiols, aromatic mercaptophenols and combinations thereof.

Specific examples of other aromatic hydroxycarboxylic acids include 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 5-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 4'-hydroxyphenyl -4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid and their alkyl, alkoxy or halogen substituted products, and their acylated products, ester derivatives and acid halides and ester-forming derivatives such as

The total compositional ratio of repeating units provided by these other monomer components is preferably 10 mol % or less in the entire repeating units.

A method for producing the liquid crystal polymer used in the present invention will be described below.

The method for producing the liquid crystal polymer used in the present invention is not particularly limited, and known polycondensation methods such as a melt acidolysis method and a slurry polymerization method for forming an ester bond or an amide bond consisting of a combination of the above monomers can be used. can be used.

The melt acidolysis method, which is the preferred method for use in the method of making the liquid crystalline polymers used in the present invention, involves first heating the monomers to form a melt of reactants followed by The reaction is continued to obtain molten polymer. A vacuum may be applied to facilitate the removal of volatiles (eg, acetic acid, water, etc.) that are by-produced in the final stages of condensation.

Slurry polymerization is a process in which the reaction is carried out in the presence of a heat exchange fluid and the solid product is obtained in suspension in the heat exchange medium.

In both the melt acidolysis method and the slurry polymerization method, the polymerizable monomer component used in the production of the liquid crystal polymer is, at room temperature, a modified form obtained by acylating hydroxyl groups and/or amino groups, that is, a low-grade It can also be subjected to the reaction as an acylated product. The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. Particularly preferred is a method of using an acetylated product of the above monomer for the reaction.

The acylated product of the monomer may be previously synthesized by acylation separately, or may be produced in the reaction system by adding an acylating agent such as acetic anhydride to the monomer during production of the liquid crystal polymer. can.

In either case of the melt acidolysis method or the slurry polymerization method, a catalyst may be used as necessary during the reaction.

Specific examples of catalysts include organotin compounds (dialkyltin oxides such as dibutyltin oxide, diaryltin oxides, etc.), titanium dioxide, antimony trioxide, organotitanium compounds (alkoxytitanium silicates, titanium alkoxides, etc.), and carboxylic acid compounds. Alkali and alkaline earth metal salts (potassium acetate, sodium acetate, etc.), Lewis acids ( _BF3 , etc.), gaseous acid catalysts such as hydrogen halides (HCl, etc.), and the like.

The proportion of the catalyst used is generally 1-1000 ppm, preferably 2-100 ppm, relative to the total amount of monomers.

The liquid crystal polymer thus obtained by the polycondensation reaction is extracted from the polymerization reactor in a molten state, and then processed into pellets, flakes, or powder.

The imine-modified polyolefin used in the present invention can be obtained, for example, by grafting a polyimine compound having a plurality of imino groups to a polyolefin in the presence of a radical generator. Examples of commercially available products include ADMER (registered trademark) IP AT3346 and AT2937 manufactured by Mitsui Chemicals, Inc. Two or more imine-modified polyolefins may be used in combination.

In the imine-modified polyolefin used in the present invention, examples of the polyolefin to be modified include polyethylene, polypropylene, ethylene-propylene copolymer, polymethylpentene, etc. Among them, polyethylene and polypropylene are preferred, and polyethylene is particularly preferred.

In the present invention, when imine-modified polyethylene is used as the imine-modified polyolefin, the raw material polyethylene is not particularly limited, and examples thereof include low-density polyethylene, linear low-density polyethylene, and high-density polyethylene. These may be used alone or in combination of two or more.

Among these, linear low-density polyethylene (LLDPE) is preferable from the viewpoint of processability of the resulting liquid crystal polymer composition.

In the present invention, when imine-modified polypropylene is used as the imine-modified polyolefin, the raw material polypropylene is not particularly limited, and examples thereof include homopolypropylene, block polypropylene, and random polypropylene. These may be used alone or in combination of two or more.

Among these, homopolypropylene is preferable from the viewpoint of workability of the obtained liquid crystal polymer composition.

In the liquid crystal polymer composition of the present invention, the proportion of the imine-modified polyolefin is 1 to 100 parts by mass with respect to 100 parts by mass of the liquid crystal polymer. 85 parts by mass is more preferable, 20 to 80 parts by mass is more preferable, and 40 to 70 parts by mass is particularly preferable.

The liquid crystal polymer composition of the present invention may optionally contain inorganic and/or organic fillers.

Specific examples of inorganic and/or organic fillers that the liquid crystal polymer composition of the present invention may contain include, for example, glass fiber, silica alumina fiber, alumina fiber, carbon fiber, potassium titanate fiber, and aluminum borate. fibers, aramid fibers, polyarylate fibers, polybenzimidazole fibers, talc, mica, graphite, wollastonite, dolomite, clay, glass flakes, glass beads, glass balloons, calcium carbonate, barium sulfate, titanium oxide and the like. These may be used alone or in combination of two or more.

Among these, talc is preferable because it has an excellent balance between physical properties and cost.

Also, the inorganic and/or organic fillers may be surface-treated. Examples of surface treatment methods include a method of adsorbing a surface treatment agent to the surface of the filler, a method of adding a surface treatment agent during kneading, and the like.

Examples of surface treatment agents include reactive coupling agents such as silane-based coupling agents, titanate-based coupling agents, and borane-based coupling agents; lubricants such as higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, and fluorocarbon-based Examples include surfactants.

When blending an inorganic and/or organic filler, the content thereof is preferably 1 to 150 parts by mass, preferably 10 to 100 parts by mass, with respect to 100 parts by mass of the total amount of the liquid crystal polymer and the imine-modified polyolefin. It is more preferable to have

If the content of the inorganic and/or organic filler is less than 1 part by mass, it is difficult to obtain the effect of improving the mechanical strength and heat resistance of the liquid crystal polymer composition by the inorganic and/or organic filler, and the content exceeds 150 parts by mass. and liquidity tends to decline. In the present invention, the liquid crystal polymer composition preferably does not contain inorganic and/or organic fillers.

In addition to the liquid crystal polymer and the imine-modified polyolefin, the liquid crystal polymer composition of the present invention may further contain other additives and resin components as long as the objects of the present invention are not impaired.

Specific examples of other additives include lubricants such as higher fatty acids, higher fatty acid esters, higher fatty acid amides, and higher fatty acid metal salts (herein, higher fatty acids refer to those having 10 to 25 carbon atoms). , release agents such as polysiloxane and fluorine resins, colorants such as dyes, pigments, and carbon black, flame retardants, antistatic agents, surfactants, nucleating agents such as talc, organic phosphates, and sorbitols. Antiblocking agents, antioxidants such as phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, weathering agents, heat stabilizers, neutralizers, and the like. These additives can be used alone or in combination of two or more.

When other additives are contained, the total amount thereof is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the total amount of the liquid crystal polymer and the imine-modified polyolefin. is.

If the total amount of the other additives is less than 0.01 part by mass, it is difficult to realize the function of the additive, and if it exceeds 5 parts by mass, the thermal stability of the liquid crystal polymer composition during molding tends to deteriorate. be.

Further, among the other additives mentioned above, when additives such as lubricants, mold release agents and anti-blocking agents are used, they may be added when the liquid crystal polymer composition is prepared, or may be added when the liquid crystal is molded. It may be attached to the surface of pellets of the polymer composition.

Specific examples of other resin components include, for example, thermoplastic resins such as polyamide, polyester, polyacetal, polyphenylene ether and modified products thereof, polysulfone, polyethersulfone, polyetherimide, and polyamideimide, and thermosetting resins. Some phenolic resins, epoxy resins, polyimide resins, and the like can be mentioned. These resin components may be used alone or in combination of two or more.

When other resin components are contained, the content thereof is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, per 100 parts by mass of the total amount of the liquid crystal polymer and the imine-modified polyolefin. In the present invention, the liquid crystal polymer composition preferably does not contain other additives and other resin components.

The liquid crystal polymer composition of the present invention is prepared by blending the above liquid crystal polymer, imine-modified polyolefin, and optionally the above inorganic filler and/or organic filler, other additives and other resin components in a predetermined composition. , a Banbury mixer, a kneader, a single-screw or twin-screw extruder, or the like, to obtain the liquid crystal polymer composition of the present invention. The liquid crystal polymer composition of the present invention can also be obtained by dry-blending the liquid crystal polymer and the imine-modified polyolefin and melt-kneading them in a molding machine.

The liquid crystal polymer composition of the present invention is processed into films, sheets, bottles, containers, packaging materials and the like by known molding methods such as injection molding, extrusion molding and blow molding.

Among these, injection molding, extrusion molding, or blow molding is preferable from the viewpoint of ease of molding, mass productivity, cost, and the like.

When injection molding is adopted, the injection molding machine used for injection molding is not particularly limited. Any injection method such as a screw pre-plasticizer type, an in-line screw type, etc.) or a plunger method (single plunger type, plunger pre-plasticizer type, etc.) may be used.

As for the direction of the cylinder, it may be of any type, such as horizontal or vertical, and may be driven by any type of drive mechanism, such as a hydraulic type, an electric type, or a combination of both types.

Optimal injection conditions can be appropriately selected according to the size of the injection molding machine, the shape of the mold, and the number of molded pieces. The gate position and the number of gates can be selected according to the type of injection molded product.

The injection molding method includes, in addition to the usual injection molding method described above, injection molding methods such as insert molding, injection compression molding, two-color molding, sandwich molding, and gas-assisted molding.

When extrusion molding or blow molding is adopted, it can be processed into films, sheets, containers, pipes, fibers, etc. It may be a single or single layer molded body, and from the viewpoint of functional improvement and cost reduction, other resin compositions It may be a composite or multi-layer molded article having portions or layers made of materials. It is also possible to uniaxially or biaxially stretch films, sheets, fibers and the like. In addition, the obtained molded article may be subjected to secondary processing such as bending, vacuum forming, blow molding, and press molding to obtain the intended molded article, if necessary.

The liquid crystal polymer composition of the present invention can be used not only as a general molding material, but also as an adhesive layer for blow-molded products and laminated films due to its excellent adhesiveness. For example, a molded article having a structure in which a liquid crystal polymer layer (a) and a polyolefin layer (b) are laminated via an adhesive layer (c), wherein the adhesive layer (c) is the liquid crystal polymer composition of the present invention. Molded articles are preferred. The polyolefin layer (b) is preferably a polyethylene layer or a polypropylene layer, particularly preferably a polyethylene layer. Although such a molded product can be obtained by the above molding method, it is preferably a multilayer blow-molded product obtained by blow molding.

Furthermore, the molded article composed of the liquid crystal polymer composition of the present invention is processed into a desired molded article by blow molding suitable for molding hollow products such as bottles. Specific blow molding methods include direct blow molding, injection blow molding, free blow molding and the like. In particular, since the adhesiveness to the liquid crystal polymer layer and the polyolefin layer is improved, it is suitable for multi-layer blow molding by direct blow molding or injection blow molding.

The temperature conditions for molding using the liquid crystal polymer composition of the present invention are preferably in the range of the crystal melting temperature (210 to 300°C) of the liquid crystal polymer used to 350°C.

The molded article composed of the resin composition of the present invention is not particularly limited, but examples thereof include mechanical parts, electrical/electronic parts, construction/civil engineering materials, household/office supplies, furniture parts, and daily necessities. , particularly molded articles as containers are useful.

Examples of electric and electronic parts include housings for copiers, personal computers, printers, electronic musical instruments, home game machines, and portable game machines, and internal parts (connectors, switches, IC and LED housings, sockets, relays, resistors, capacitors, capacitors, coil bobbins, etc.).

In addition, since the liquid crystal polymer composition of the present invention has excellent adhesiveness to both liquid crystal polymers and resins such as polyolefins, it is also useful as an adhesive material, and can be used, for example, as an adhesive layer in laminated films. .

Examples of resins that can adhere to the liquid crystal polymer composition of the present invention include polyolefins such as polyethylene and polypropylene, polyesters, and polyamides. Among these, polyolefins are preferred, and polyethylene is more preferred.

The adhesiveness of the liquid crystal polymer composition of the present invention to the liquid crystal polymer can be evaluated by adhesive strength (tensile shear strength) according to JIS-K-7162. A composite in which the adhesive strength between the liquid crystal polymer composition of the present invention and the liquid crystal polymer is usually 220N or more, preferably 250 to 750N, more preferably 280 to 600N, is suitable.

The adhesiveness of the liquid crystal polymer composition of the present invention to polyolefin can be evaluated by adhesive strength (90 degree peel strength) according to JIS-C-6471 when the polyolefin is polyethylene. A composite in which the adhesive strength of the liquid crystal polymer composition of the present invention to a polyolefin (eg, LLDPE) is usually 5N or more, preferably 8 to 60N, more preferably 10 to 50N, is suitable.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these.

Crystal melting temperature and adhesiveness in the examples were measured by the methods described below.

<Measurement of crystal melting temperature>
The measurement was performed using a differential scanning calorimeter (DSC) Exstar 6000 manufactured by Seiko Instruments Inc. A sample of the liquid crystal polymer is measured under the condition of increasing the temperature from room temperature by 20° C./min, and after observing the endothermic peak temperature (Tm1), the temperature is maintained at a temperature 20 to 50° C. higher than Tm1 for 10 minutes. Then, after cooling the sample to room temperature under the temperature decreasing condition of 20°C/min, the endothermic peak was measured again under the temperature increasing condition of 20°C/min. and

<Adhesion test with liquid crystal polymer>
Using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), at a molding temperature of 250 ° C. and a mold temperature of 40 ° C., a liquid crystal polymer (the following wholly aromatic liquid crystal polyester resin) and an adhesive layer (examples and Each bar flow test piece (length 150 mm×width 13 mm×thickness 0.8 mm) of the liquid crystal polymer composition obtained in Comparative Example) was molded. The obtained bar flow test pieces were overlapped by 70 mm and placed in a heater at 250° C. for 30 seconds to bond the bar flow test pieces together. Adhesive strength (tensile shear strength) was measured according to JIS-K-7162 using INSTRON5567 (universal testing machine manufactured by Instron Japan Company Limited).

<Adhesion test with linear low-density polyethylene>
Using an injection molding machine (UH1000-110 manufactured by Nissei Plastic Industry Co., Ltd.), at a molding temperature of 250 ° C. and a mold temperature of 40 ° C., a linear low-density polyethylene bar flow test piece (length 150 mm × width 13 mm × thickness 0.8 mm) was molded. Further, a color plate test piece (90 mm×55 mm×0.8 mm thickness) of the adhesive layer was molded under the same conditions. The resulting bar flow and color plate were overlapped by 90 mm and placed in a heater at 250° C. for 30 seconds to bond them. Adhesive strength (90 degree peel strength) was measured according to JIS-C-6471 using INSTRON5567 (a universal testing machine manufactured by Instron Japan Company Limited).

The following abbreviations in Examples and Comparative Examples represent the following compounds.
LCP: liquid crystal polymer LLDPE: linear low density polyethylene POB: 4-hydroxybenzoic acid BON6: 6-hydroxy-2-naphthoic acid HQ: hydroquinone TPA: terephthalic acid

[Synthesis of LCP]
POB, BON6, HQ and TPA were charged in a composition ratio shown in Table 1 in a reaction vessel equipped with a stirring device equipped with a torque meter and a distillation tube so that the total amount was 6.5 mol, and further the amount of hydroxyl groups in all the monomers. Acetic anhydride was charged in an amount of 1.03 mol per (mol), and deacetic acid polymerization was carried out under the following conditions.

In a nitrogen gas atmosphere, the temperature was raised from room temperature to 145° C. in 1 hour and maintained at the same temperature for 30 minutes. Next, the temperature was raised to 330° C. over 7 hours while distilling off the acetic acid produced as a by-product, and then the pressure was reduced to 10 mmHg over 80 minutes. When a predetermined torque was exhibited, the polymerization reaction was terminated, the contents of the reaction vessel were taken out, and pellets of a wholly aromatic liquid crystalline polyester resin were obtained with a pulverizer. The amount of acetic acid distilled off during polymerization was almost the same as the theoretical value.

The crystalline melting temperature of the obtained LCP measured by DSC was 218°C.

Materials used in Examples and Comparative Examples in addition to the LCP synthesized in the above Synthesis Examples are shown below.
LLDPE: "Urtozex (registered trademark) 4570" manufactured by Prime Polymer Co., Ltd.
Imine-modified polyethylene: "ADMER (registered trademark) IP AT3346" manufactured by Mitsui Chemicals, Inc.
Imine-modified polypropylene: "Admer (registered trademark) IP AT2937" manufactured by Mitsui Chemicals, Inc.
Ethylene-glycidyl methacrylate copolymer: Sumitomo Chemical Co., Ltd., "Bond First (registered trademark) E"

Examples 1-3 and Comparative Examples 1-2
The synthesized LCP and the above materials are blended so that the content is shown in Table 2, and melt-kneaded at 250 ° C. using a twin-screw extruder (TEX-30 manufactured by Nippon Steel Co., Ltd.) to obtain a liquid crystal. Pellets of the polymer composition were obtained. A bar flow test piece was prepared by the method described above, and an adhesion test was conducted. Table 2 shows the results.

As shown in Table 2, all of the liquid crystal polymer compositions of Examples 1 to 3 had improved adhesive strength and excellent adhesion to LCP and LLDPE.

On the other hand, the liquid crystal polymer compositions of Comparative Examples 1 and 2 had poor adhesiveness and were unfavorable as adhesive materials.

Claims (9)

A liquid crystal polymer composition comprising 100 parts by mass of a liquid crystal polymer having a crystal melting temperature of 210 to 300° C. and 1 to 100 parts by mass of an imine-modified polyolefin. The liquid crystal polymer composition according to claim 1, wherein the liquid crystal polymer has a crystalline melting temperature of 215-250°C. The liquid crystal polymer has formulas (I)-(IV)

[In the formula,
Ar ₁ and Ar ₂ each represent one or more divalent aromatic groups, and p, q, r and s respectively represent the composition ratio of each repeating unit in the wholly aromatic liquid crystalline polyester ( %) and satisfies the following conditions:
0.5≦p/q≦2.5
2≦r≦15, and 2≦s≦15]
3. The liquid crystal polymer composition according to claim 1, which is a wholly aromatic liquid crystal polyester containing a repeating unit represented by: In the repeating units represented by formulas (III) to (IV), Ar ₁ and Ar ₂ are each independently represented by formulas (1) to (4)

4. The liquid crystal polymer composition according to claim 3, wherein each is one or more repeating units selected from aromatic groups represented by: 5. The liquid crystal polymer composition according to any one of claims 1 to 4, wherein the imine-modified polyolefin is imine-modified polyethylene or imine-modified polypropylene. A molded article composed of the liquid crystal polymer composition according to any one of claims 1 to 5. A molded product having a structure in which a liquid crystal polymer layer (a) and a polyolefin layer (b) are laminated via an adhesive layer (c), wherein the adhesive layer (c) is according to any one of claims 1 to 5. A molded article made of a liquid crystal polymer composition of 8. The molded article according to claim 7, wherein the polyolefin layer (b) is a polyethylene layer or a polypropylene layer. The molded article according to claim 7 or 8, which is a multilayer blow-molded article.