JP7355523B2 - liquid crystal polymer composition - Google Patents

Description

The present invention relates to a liquid crystal polymer composition capable of forming articles such as molded articles with improved metal adhesion while maintaining weld strength.

Liquid crystal polymers have excellent mechanical properties such as heat resistance and rigidity, chemical resistance, and dimensional accuracy, so their use is expanding not only to molded products but also to various applications such as fibers and films. Particularly in the information and communication fields such as personal computers and mobile phones, components are rapidly becoming more highly integrated, smaller, thinner, and lower in height, and extremely thin parts with a thickness of 0.5 mm or less are progressing. In many cases, liquid crystal polymers are formed, and by taking advantage of the excellent moldability of liquid crystal polymers, which is characterized by good fluidity and no burrs, which are not found in other polymers, the amount of liquid crystal polymers used has increased significantly. There is.

However, liquid crystal polymers have the property that their molecules tend to align even with a small amount of shearing force, and the anisotropy of mechanical strength is large in the flow direction (MD) and the direction perpendicular to it (TD) during molding. When a product has a welded part, there is a problem that the strength of the welded part is weak.

In order to solve such problems, for example, Patent Document 1 discloses that the anisotropy and weld strength of a liquid crystal polymer are improved by incorporating a cyclic olefin resin (also referred to as a cycloolefin polymer or a cycloolefin copolymer). It describes how to do this.

Japanese Patent Application Publication No. 10-316841

However, when such a cyclic olefin resin is contained, the metal adhesion of the molded article decreases, so that the physical properties of the molded article may be insufficient when used for applications such as electrical and electronic parts.
An object of the present invention is to provide a liquid crystal polymer composition that can be used to form articles such as molded articles with improved metal adhesion while maintaining weld strength.

In view of the above-mentioned problems, the present inventors have made extensive studies and found that by blending a carbodiimide group-containing compound into a liquid crystal polymer and a cyclic olefin resin, the weld strength of articles such as molded products can be maintained while maintaining metal adhesion. The present inventors have discovered that this can be improved, and have completed the present invention.

で表される繰返し単位を含む液晶ポリエステル樹脂である、〔１〕に記載の液晶ポリマー組成物。
〔３〕液晶ポリマーは、式（Ｉ）～式（ＩＶ）

［式中、Ａｒ_１およびＡｒ_２はそれぞれ２価の芳香族基を表す］
で表される繰返し単位から構成される全芳香族液晶ポリエステル樹脂である、〔１〕または〔２〕に記載の液晶ポリマー組成物。
〔４〕Ａｒ_１およびＡｒ_２は、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１種以上である、〔３〕に記載の液晶ポリマー組成物。
〔５〕Ａｒ_１は式（１）で表される芳香族基であり、Ａｒ_２は式（１）および／または（３）で表される芳香族基である、〔３〕または〔４〕に記載の液晶ポリマー組成物。
〔６〕さらに針状フィラーを含む、〔１〕～〔５〕のいずれかに記載の液晶ポリマー組成物。
〔７〕針状フィラーは針状酸化チタンである、〔６〕に記載の液晶ポリマー組成物。
〔８〕針状フィラーの含有量は液晶ポリマー１００質量部に対して１～１００質量部である、〔６〕または〔７〕に記載の液晶ポリマー組成物。
〔９〕〔１〕～〔８〕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。
〔１０〕成形品は、コネクタ、スイッチ、リレー、コンデンサ、コイル、トランス、カメラモジュール、およびアンテナからなる群から選択される１種を構成する部品である、〔９〕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, 0.1 to 10 parts by mass of a cyclic olefin resin, and 0.1 to 5 parts by mass of a carbodiimide group-containing compound.
[2] Liquid crystal polymer has formula (I) and formula (II)

The liquid crystal polymer composition according to [1], which is a liquid crystal polyester resin containing a repeating unit represented by:
[3] Liquid crystal polymer has formulas (I) to (IV)

[In the formula, Ar ₁ and Ar ₂ each represent a divalent aromatic group]
The liquid crystal polymer composition according to [1] or [2], which is a wholly aromatic liquid crystal polyester resin composed of repeating units represented by:
[4] Ar ₁ and Ar ₂ are each independently expressed by formulas (1) to (4)

The liquid crystal polymer composition according to [3], which is one or more types selected from aromatic groups represented by:
[5] Ar ₁ is an aromatic group represented by formula (1), and Ar ₂ is an aromatic group represented by formula (1) and/or (3), [3] or [4] The liquid crystal polymer composition described in .
[6] The liquid crystal polymer composition according to any one of [1] to [5], further comprising an acicular filler.
[7] The liquid crystal polymer composition according to [6], wherein the acicular filler is acicular titanium oxide.
[8] The liquid crystal polymer composition according to [6] or [7], wherein the content of the acicular filler is 1 to 100 parts by mass based on 100 parts by mass of the liquid crystal polymer.
[9] A molded article comprising the liquid crystal polymer composition according to any one of [1] to [8].
[10] The molded product according to [9], wherein the molded product is a component constituting one type selected from the group consisting of a connector, a switch, a relay, a capacitor, a coil, a transformer, a camera module, and an antenna.

Since the liquid crystal polymer composition of the present invention has excellent weld strength and metal adhesion, it can be suitably used in various applications such as electric/electronic parts and automobile parts that are integrated by injection insert molding.

The liquid crystal polymer (hereinafter also referred to as LCP) used in the liquid crystal polymer composition of the present invention is a polyester or polyester amide that forms an anisotropic melt phase, and is known in the art as a thermotropic liquid crystal polyester or a thermotropic liquid crystal polyester amide. It is not particularly limited as long as it is called.

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 by using a Leitz polarizing microscope and observing a sample placed on a Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere. The liquid crystal polymer in the present invention is one that exhibits optical anisotropy, ie, one that transmits light when examined between crossed polarizers. If the sample is optically anisotropic, polarized light will pass through it even if it is at rest.

The liquid crystal polymer used in the present invention preferably has a crystal melting temperature of 320 to 360°C, more preferably 335 to 345°C, and more preferably 337 to 343°C, as measured by differential scanning calorimetry. More preferred.

In this specification and claims, "crystal melting temperature" refers to the crystal melting temperature measured by a differential scanning calorimeter (hereinafter abbreviated as DSC) at a heating rate of 20°C/min. This is calculated from the peak temperature. More specifically, after observing the endothermic peak temperature (Tm1) observed when measuring a liquid crystal polymer sample under heating conditions of 20°C/min from room temperature, the sample was heated at a temperature 20 to 50°C higher than Tm1 for 10 min. After holding the sample for 20 minutes, the sample was cooled to room temperature under the temperature decreasing condition of 20℃/min, and the endothermic peak was observed when the sample was measured again under the temperature increasing condition of 20℃/min. Let it be the crystalline melting temperature of the polymer. As the measuring device, for example, Exstar 6000 manufactured by Seiko Instruments Co., Ltd. can be used.

Examples of the polymerizable monomers constituting the structural units of the liquid crystal polymer in the present invention include aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic aminocarboxylic acids, aromatic hydroxyamines, aromatic diamines, Included are aliphatic diols and aliphatic dicarboxylic acids. Only one type of such polymerizable monomers may be used, or two or more types of polymerizable monomers may be used in combination. Preferably, a polymerizable monomer having at least one hydroxy group and one carboxyl group is used.

The polymerizable monomer constituting the structural unit of the liquid crystal polymer may be an oligomer formed by bonding one or more of the above compounds, that is, an oligomer formed from one or more of the above compounds.

Specific examples of aromatic hydroxycarboxylic acids include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 2-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, and 7-hydroxybenzoic acid. -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 Examples thereof include alkyl, alkoxy, or halogen substituted products, and ester-forming derivatives thereof such as acylated products, ester derivatives, and acid halides. Among these, one or more compounds selected from the group consisting of 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid from the viewpoint of easy adjustment of the heat resistance, mechanical strength, and melting point of the obtained liquid crystal polymer. is preferred.

Specific examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4'-dicarboxybiphenyl, 3 , 4'-dicarboxybiphenyl and 4,4"-dicarboxyterphenyl, alkyl, alkoxy or halogen substituted products thereof, and ester-forming derivatives thereof such as ester derivatives and acid halides. Among these, From the viewpoint of effectively increasing the heat resistance of the obtained liquid crystal polymer, one or more compounds selected from the group consisting of terephthalic acid, isophthalic acid, and 2,6-naphthalene dicarboxylic acid are preferred; - Naphthalene dicarboxylic acid is more preferred.

Specific examples of aromatic diols include hydroquinone, resorcinol, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, Examples include ester-forming derivatives such as 4,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether and 2,2'-dihydroxybinaphthyl, alkyl, alkoxy or halogen substituted products thereof, and acylated products thereof. Among these, from the viewpoint of excellent reactivity during polymerization, one or more compounds selected from the group consisting of hydroquinone, resorcinol, 4,4'-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene are preferred; , 4'-dihydroxybiphenyl, and 2,6-dihydroxynaphthalene are more preferred.

Specific examples of aromatic aminocarboxylic acids include 4-aminobenzoic acid, 3-aminobenzoic acid, 6-amino-2-naphthoic acid, alkyl, alkoxy or halogen substituted products thereof, and acylated products and ester derivatives thereof. and ester-forming derivatives such as acid halides.

Specific examples of aromatic hydroxyamines include 4-aminophenol, N-methyl-4-aminophenol, 3-aminophenol, 3-methyl-4-aminophenol, 4-amino-1-naphthol, 4-amino- 4'-hydroxybiphenyl, 4-amino-4'-hydroxybiphenyl ether, 4-amino-4'-hydroxybiphenylmethane, 4-amino-4'-hydroxybiphenyl sulfide and 2,2'-diaminobinaphthyl, alkyl thereof , alkoxy or halogen substituted products, and ester-forming derivatives such as acylated products thereof. Among these, 4-aminophenol is preferred from the viewpoint of easily balancing the heat resistance and mechanical strength of the resulting liquid crystal polymer.

Specific examples of aromatic diamines include 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, alkyl, alkoxy or halogen substituted products thereof, and their Examples include amide-forming derivatives such as acylated products.

Specific examples of aliphatic diols include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and acylated products thereof. In addition, polymers containing aliphatic diols such as polyethylene terephthalate and polybutylene terephthalate are reacted with the above-mentioned aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, and their acylated products, ester derivatives, acid halides, etc. You may let them.

Specific examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, fumaric acid, and maleic acid. and hexahydroterephthalic acid. Among these, oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid and dodecanedioic acid are preferred from the viewpoint of excellent reactivity during polymerization.

The polymerizable monomer forming the structural unit of the liquid crystal polymer in the present invention may include dihydroxyterephthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, etc. as other copolymerization components to the extent that the object of the present invention is not impaired. , trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid or alkyl, alkoxy or halogen substituted products thereof, and ester-forming derivatives thereof such as acylated products, ester derivatives and acid halides. It's okay to stay. The amount of these polymerizable monomers used is preferably 10 mol % or less based on all the structural units constituting the liquid crystal polymer.

In the present invention, the liquid crystal polymer may contain a thioester bond as long as the object of the present invention is not impaired. Examples of polymerizable monomers that provide such bonds include mercapto aromatic carboxylic acids, aromatic dithiols, and hydroxyaromatic thiols. The content of these polymerizable monomers is preferably 10 mol % or less based on all the structural units constituting the liquid crystal polymer.

Polymers that combine these repeating units can be classified into those that form an anisotropic melt phase and those that do not, depending on the monomer composition, composition ratio, and sequence distribution of each repeating unit in the polymer. However, the liquid crystal polymer used in the present invention is limited to those that form an anisotropic melt phase.

As the liquid crystal polymer used in the present invention, liquid crystal polyester resins containing repeating units represented by formula (I) and formula (II) are preferably used because they have excellent fluidity and mechanical properties.

［式中、Ａｒ_１およびＡｒ_２はそれぞれ２価の芳香族基を表す。］ Further, as the liquid crystal polymer used in the present invention, wholly aromatic liquid crystal polyester resins composed of repeating units represented by formulas (I) to (IV) are preferably used because of their excellent fluidity and mechanical properties. used.

[In the formula, Ar ₁ and Ar ₂ each represent a divalent aromatic group. ]

Here, formula (III) and formula (IV) may each contain multiple types of Ar ₁ and Ar ₂ . Furthermore, the term "aromatic group" refers to an aromatic group that is a 6-membered monocyclic ring or a condensed ring having 2 rings.

In terms of excellent fluidity and mechanical properties, Ar ₁ and Ar ₂ are each independently one or more types selected from the aromatic groups represented by the following formulas (1) to (4). is more preferable. It is particularly preferable that Ar ₁ is an aromatic group represented by formula (1), and Ar ₂ is an aromatic group represented by formula (1) and/or formula (3).

Specific examples of combinations of polymerizable monomers forming the structural units of the liquid crystal polymer used in the present invention include the following.
1) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid,
2) 4-hydroxybenzoic acid/terephthalic acid/4,4'-dihydroxybiphenyl,
3) 4-hydroxybenzoic acid/terephthalic acid/isophthalic acid/4,4'-dihydroxybiphenyl,
4) 4-hydroxybenzoic acid/terephthalic acid/isophthalic acid/4,4'-dihydroxybiphenyl/hydroquinone,
5) 4-hydroxybenzoic acid/terephthalic acid/hydroquinone,
6) 6-hydroxy-2-naphthoic acid/terephthalic acid/hydroquinone,
7) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/4,4'-dihydroxybiphenyl,
8) 6-hydroxy-2-naphthoic acid/terephthalic acid/4,4'-dihydroxybiphenyl,
9) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/hydroquinone,
10) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/hydroquinone/4,4'-dihydroxybiphenyl,
11) 4-hydroxybenzoic acid/2,6-naphthalene dicarboxylic acid/4,4'-dihydroxybiphenyl,
12) 4-hydroxybenzoic acid/terephthalic acid/2,6-naphthalene dicarboxylic acid/hydroquinone,
13) 4-hydroxybenzoic acid/2,6-naphthalene dicarboxylic acid/hydroquinone,
14) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/2,6-naphthalene dicarboxylic acid/hydroquinone,
15) 4-hydroxybenzoic acid/terephthalic acid/2,6-naphthalene dicarboxylic acid/hydroquinone/4,4'-dihydroxybiphenyl,
16) 4-hydroxybenzoic acid/terephthalic acid/4-aminophenol,
17) 6-hydroxy-2-naphthoic acid/terephthalic acid/4-aminophenol,
18) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/4-aminophenol,
19) 4-hydroxybenzoic acid/terephthalic acid/4,4'-dihydroxybiphenyl/4-aminophenol,
20) 4-hydroxybenzoic acid/terephthalic acid/ethylene glycol,
21) 4-hydroxybenzoic acid/terephthalic acid/4,4'-dihydroxybiphenyl/ethylene glycol,
22) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/ethylene glycol,
23) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/4,4'-dihydroxybiphenyl/ethylene glycol,
24) 4-hydroxybenzoic acid/terephthalic acid/2,6-naphthalene dicarboxylic acid/4,4'-dihydroxybiphenyl.

Among these, liquid crystal polymers consisting of structural units derived from the polymerizable monomers in 10) are preferred.

The above liquid crystal polymers may be used alone or as a mixture of two or more liquid crystal polymers.

One particularly preferred embodiment of the liquid crystal polymer used in the present invention is a wholly aromatic liquid crystal polyester resin composed of repeating units represented by the following formulas (A) to (E).

[式中、ｐ、ｑ、ｒ、ｓおよびｔは、各繰返し単位の液晶ポリエステル樹脂中での組成比（モル％）を示し、以下の条件を満たす：
２５≦ｐ≦４５；
２≦ｑ≦１０；
１０≦ｒ≦２０；
１０≦ｓ≦２０；
２０≦ｔ≦４０；
ｒ＞ｓ；
ｐ＋ｑ＋ｒ＋ｓ＋ｔ＝１００。]

[Wherein, p, q, r, s, and t represent the composition ratio (mol%) of each repeating unit in the liquid crystal polyester resin, and satisfy the following conditions:
25≦p≦45;
2≦q≦10;
10≦r≦20;
10≦s≦20;
20≦t≦40;
r>s;
p+q+r+s+t=100. ]

Hereinafter, a method for producing a liquid crystal polymer used in the present invention will be explained.

There are no particular limitations on the method for producing the liquid crystal polymer used in the present invention, and the liquid crystal polymer can be produced by subjecting a polymerizable monomer to a known polycondensation method for forming an ester bond or an amide bond, such as a melt acidolysis method or a slurry polymerization method. Polymers can be obtained.

Melt acidolysis is a preferred method for producing the liquid crystal polymer used in the liquid crystal polymer composition of the present invention. This method involves first heating the polymerizable monomer to form a molten solution of the reactants, and then continuing the polycondensation reaction to obtain a molten polymer. Note that a vacuum may be applied to facilitate the removal of volatile by-products (eg, acetic acid, water, etc.) in the final stage of condensation.

Slurry polymerization is a method in which polymerizable monomers are reacted in the presence of a heat exchange fluid, whereby a solid product is obtained suspended in the heat exchange medium.

In both the melt acidolysis method and the slurry polymerization method, the polymerizable monomer used to produce the liquid crystal polymer is a modified form (lower acyl) in which hydroxyl groups and/or amino groups are acylated at room temperature. group), that is, it can also be subjected to the reaction as a lower acylated product.

The lower acyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms. In a preferred embodiment of the present invention, the acetylated product of the polymerizable monomer is subjected to the reaction.

The lower acylated polymerizable monomer may be acylated separately and synthesized in advance, or it may be added to the polymerizable monomer in the reaction system by adding an acylating agent such as acetic anhydride during the production of the liquid crystal polymer. It can also be generated.

In either the melt acidolysis method or the slurry polymerization method, the polycondensation reaction is usually carried out at a temperature of 150 to 400°C, preferably 250 to 370°C, under normal pressure and/or reduced pressure. A catalyst may be used as appropriate.

Specific examples of catalysts include organotin compounds such as dialkyltin oxide (e.g. dibutyltin oxide) and diaryltin oxide; titanium dioxide; antimony trioxide; organotitanium compounds such as alkoxytitanium silicates and titanium alkoxides; alkalis and alkalis of carboxylic acids. Gaseous acid catalysts such as earth metal salts (eg, potassium acetate); Lewis acids (eg, boron trifluoride), hydrogen halides (eg, hydrogen chloride), and the like can be mentioned.

When a catalyst is used, the amount of the catalyst is preferably 1 to 1000 ppm, more preferably 2 to 100 ppm, based on the total amount of polymerizable monomers.

The liquid crystal polymer obtained by such a polycondensation reaction is usually extracted from a polymerization reaction tank in a molten state, processed into pellets, flakes, or powder, and then melt-kneaded with other components. be done.

Liquid crystalline polyester in pellet, flake, or powder form becomes substantially solid when placed under reduced pressure, vacuum, or an atmosphere of an inert gas such as nitrogen or helium in order to increase the molecular weight and improve heat resistance. Heat treatment may be performed in a phase state.

The liquid crystal polymer composition of the present invention contains a cyclic olefin resin in addition to the above liquid crystal polymer.

The cyclic olefin resin used in the liquid crystal polymer composition of the present invention includes a polymer of cyclic olefin such as norbornene or a polycyclic norbornene monomer, or a copolymer thereof. The cyclic olefin resin may include a ring-opened structure, or may be obtained by hydrogenating a cyclic olefin-based resin containing an open ring structure. Further, the cyclic olefin resin may contain a structural unit derived from a chain olefin and a vinylated aromatic compound, as long as the transparency is not significantly impaired and the hygroscopicity is not significantly increased. Further, the cyclic olefin resin may have a polar group introduced into its molecule.

Examples of chain olefins include ethylene and propylene. Furthermore, examples of the vinylated aromatic compound include styrene, α-methylstyrene, and alkyl-substituted styrene.

When the cyclic olefin resin is a copolymer of a cyclic olefin and a chain olefin and/or a vinylated aromatic compound, the content of structural units derived from the cyclic olefin is equal to the total structural units of the copolymer. On the other hand, it is usually 50 mol% or less, preferably 15 to 50 mol%, more preferably 20 to 45 mol%, and still more preferably 25 to 40 mol%.

When the cyclic olefin resin is a terpolymer of a cyclic olefin, a chain olefin, and a vinylated aromatic compound, the content of structural units derived from the chain olefin is equal to the total structure of the copolymer. The content of structural units derived from the vinylated aromatic compound is usually 5 to 80 mol% based on the total structural units of the copolymer. Such terpolymers have the advantage that the amount of expensive cyclic olefins used can be relatively small.

Cyclic olefin resins are commercially available. Commercially available cyclic olefin resins include Topas (registered trademark) (Ticona (Germany)), Arton (registered trademark) (JSR Corporation), ZEONOR (registered trademark) (Nippon Zeon Co., Ltd.), Examples include ZEONEX (registered trademark) (Nippon Zeon Co., Ltd.) and APEL (registered trademark) (Mitsui Chemicals Co., Ltd.).

The content of the cyclic olefin resin in the liquid crystal polymer composition of the present invention is from 0.1 to 10 parts by weight, preferably from 0.5 to 8 parts by weight, and more preferably from 0.5 to 8 parts by weight, based on 100 parts by weight of the liquid crystal polymer. is 1 to 7 parts by weight, more preferably 2 to 6 parts by weight. When the content of the cyclic olefin resin is within the above range, the deterioration of moldability due to a decrease in melt viscosity is suppressed, the weld strength is maintained, and the metal adhesion of the molded product is significantly improved. can.

The liquid crystal polymer composition of the present invention may further contain other resin components in addition to the above-mentioned cyclic olefin resin as long as the object of the present invention is not impaired. Other resin components include, for example, thermoplastic resins such as polyamide, polyester, polyacetal, polyphenylene ether and modified products thereof, polysulfone, polyethersulfone, polyetherimide, polyamideimide, phenol resin, epoxy resin, polyimide resin, etc. Examples include thermosetting resins.

Other resin components may be contained alone or in combination of two or more. The content of other resin components is not particularly limited, and may be determined as appropriate depending on the use and purpose of the liquid crystal polymer composition. Typically, the total content of other resins is preferably 0.1 to 100 parts by weight, more preferably 0.2 to 80 parts by weight based on 100 parts by weight of the liquid crystal polymer.

The liquid crystal polymer composition of the present invention contains a carbodiimide group-containing compound in addition to the above liquid crystal polymer and cyclic olefin resin.

The carbodiimide group-containing compound used in the liquid crystal polymer composition of the present invention is a compound having a carbodiimide group (-N=C=N-), and is not particularly limited as long as it is a compound having at least one carbodiimide group. It's not a thing.

Examples of carbodiimide group-containing compounds include polycarbodiimide compounds and monocarbodiimide compounds.

Specific examples of polycarbodiimide compounds include poly(4,4'-diphenylmethanecarbodiimide), poly(p-phenylenecarbodiimide), poly(m-phenylenecarbodiimide), poly(diisopropylphenylcarbodiimide), and poly(triisopropylphenyl). Aromatic polycarbodiimides such as carbodiimide); alicyclic polycarbodiimides such as poly(dicyclohexylmethanecarbodiimide).

Examples of monocarbodiimide compounds include diphenylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, di-2,6-diethylphenylcarbodiimide, di-2,6-diisopropylphenylcarbodiimide, and di-2,6-di-tert-butylphenyl. Carbodiimide, di-o-tolylcarbodiimide, di-p-tolylcarbodiimide, di-2,4,6-trimethylphenylcarbodiimide, di-2,4,6-triisopropylphenylcarbodiimide, di-2,4,6-tri Examples include aromatic monocarbodiimide compounds such as isobutylphenylcarbodiimide; alicyclic monocarbodiimide compounds such as di-cyclohexylcarbodiimide and di-cyclohexylmethanecarbodiimide; and aliphatic monocarbodiimide compounds such as di-isopropylcarbodiimide and di-octadecylcarbodiimide. .

The carbodiimide group-containing compounds may be used alone or in combination of two or more. Among these, preferred specific compounds are aliphatic polycarbodiimide compounds, and commercially available products thereof include, for example, Carbodilite (registered trademark) HMV-8CA and Carbodilite (registered trademark) LA manufactured by Nisshinbo Chemical Co., Ltd. -1 is mentioned.

The content of the carbodiimide group-containing compound in the liquid crystal polymer composition of the present invention is 0.1 to 5 parts by weight, preferably 0.3 to 4 parts by weight, and more preferably 0.3 to 4 parts by weight, based on 100 parts by weight of the liquid crystal polymer. is 0.5 to 3 parts by weight, more preferably 0.7 to 2.5 parts by weight. When the content of the carbodiimide group-containing compound is within the above range, deterioration of moldability due to a decrease in melt viscosity is suppressed, weld strength is maintained, and metal adhesion of the molded product can be significantly improved. can.

It is preferable that the liquid crystal polymer composition of the present invention further contains a needle filler. Examples of acicular fillers include calcium silicate such as wollastonite, moss hyde, xonotlite, calcium titanate, aluminum borate, acicular calcium carbonate, acicular titanium oxide, and tetrapot type zinc oxide, which have excellent mechanical strength. Acicular titanium oxide is preferred. Acicular fillers can be used alone or in combination of two or more.

The content of the acicular filler in the liquid crystal polymer composition of the present invention is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, even more preferably 4 parts by mass, based on 100 parts by mass of the liquid crystal polymer. 50 parts by weight, particularly preferably 5 to 20 parts by weight. By containing the acicular filler within the above range, particles generated when a molded article is subjected to ultrasonic cleaning can be reduced.

The liquid crystal polymer composition of the present invention may contain, in addition to the above-mentioned acicular filler, other fibrous, plate-like, or granular inorganic fillers or organic fillers, as long as the effects of the present invention are not impaired. good.

When the liquid crystal polymer composition of the present invention contains an inorganic filler or an organic filler other than the acicular filler, the content thereof is preferably 0.1 to 30 parts by mass, and more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the liquid crystal polyester. Preferably it is 0.5 to 20 parts by mass. If the content of these other fillers exceeds the above upper limit, moldability tends to decrease and thermal stability tends to deteriorate.

Other fibrous fillers include, for example, milled glass, silica alumina fibers, alumina fibers, carbon fibers, aramid fibers, polyarylate fibers, polybenzimidazole fibers, potassium titanate whiskers, aluminum borate whiskers, etc. These can be used alone or in combination of two or more.

Examples of other plate-shaped fillers include silicates such as talc, mica, kaolin, clay, vermiculite, feldspar powder, acid clay, waxite clay, sericite, sillimanite, bentonite, glass flakes, slate powder, and silane; Carbonates such as calcium carbonate, chalk, barium carbonate, magnesium carbonate, dolomite, barite powder, precipitated calcium sulfate, calcined gypsum, sulfates such as barium sulfate, hydroxides such as hydrated alumina, alumina, antimony oxide, magnesia , oxides such as plate-shaped titanium oxide, zinc white, silica, silica sand, quartz, white carbon, diatomaceous earth, sulfides such as molybdenum disulfide, plate-shaped wollastonite, etc. These may be used alone or in combination. The above can be used together.

Other granular fillers include, for example, calcium carbonate, glass beads, barium sulfate, and granular titanium oxide, and these can be used alone or in combination of two or more.

Furthermore, the liquid crystal polymer composition of the present invention may contain other additives other than those mentioned above, within a range that does not impair the effects of the present invention.

Other additives include, for example, higher fatty acids as lubricants, higher fatty acid esters, higher fatty acid amides, higher fatty acid metal salts (here, higher fatty acids refer to those having 10 to 25 carbon atoms, for example), fluorocarbon-based Surfactants, mold release improvers such as polysiloxane, fluorine resins, coloring agents such as dyes, pigments, carbon black, flame retardants, antistatic agents, surfactants, and phosphorus antioxidants. Examples include weathering agents, heat stabilizers, neutralizing agents, etc., phenolic antioxidants, sulfur-based antioxidants, etc. Additives that have an external lubricant effect, such as higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, and fluorocarbon surfactants, are added to the surface of pellets of the liquid crystal polymer composition in advance when molding the liquid crystal polymer composition. You may let them. These additives may be used alone or in combination of two or more.

The content of these other additives is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the liquid crystal polymer. If the content of these other additives exceeds the above upper limit, there is a tendency for moldability to decrease and thermal stability to deteriorate.

The liquid crystal polymer, cyclic olefin resin, and carbodiimide group-containing compound are blended with other inorganic fillers and/or organic fillers, other additives, and other resin components as desired in a predetermined composition, and then mixed with a Banbury mixer or kneader. The liquid crystal polymer composition of the present invention can be obtained by melt-kneading using a single-screw or twin-screw extruder.

The liquid crystal polymer composition of the present invention thus obtained can be molded or processed by a known molding method using an injection molding machine, an extruder, etc. to obtain a desired molded article.

Molded products made from the liquid crystal polymer composition of the present invention have improved metal adhesion while maintaining weld strength, so they can be used for connectors, switches, relays, capacitors, coils, transformers, camera modules, antennas, etc. Suitable for use in electronic components.

EXAMPLES Hereinafter, the present invention will be explained with reference to Examples, but the present invention is not limited to the following Examples. In addition, the measurement and evaluation of melt viscosity, deflection temperature under load, tensile strength, bending strength, number of particles, weld strength, and metal adhesion in Examples were performed by the methods described below.

<Melt viscosity>
Using a melt viscosity measuring device (Capillograph 1D manufactured by Toyo Seiki Co., Ltd.) using a 1.0 mmφ x 10 mm capillary, the temperature was measured at a shear rate of 1000 sec ^-1 at a temperature of the crystal melting temperature (Tm) of the sample + 20°C. The melt viscosity of each was measured.

<Load deflection temperature>
A rectangular test piece (length 127 mm x width 12.7 mm x thickness 3.2 mm) was molded using an injection molding machine (UH1000-110 manufactured by Nissei Jushi Kogyo Co., Ltd.), and was tested according to ASTM D648. In accordance with this, the temperature at which a predetermined amount of deflection (0.254 mm) was obtained was measured at a load of 1.82 MPa and a temperature increase rate of 2° C./min.

<Tensile strength>
An ASTM No. 4 dumbbell test piece was produced by injection molding using an injection molding machine (UH1000-110, manufactured by Nissei Jushi Kogyo Co., Ltd.) at a cylinder temperature of 20 to 40° C. above the crystal melting temperature and a mold temperature of 70° C. Measurement was performed using INSTRON5567 (universal testing machine manufactured by Instron Japan Company Limited) in accordance with ASTM D638.

<Bending strength>
The measurement was carried out in accordance with ASTM D790 using the same test piece used for measuring the deflection temperature under load.

<Number of particles generated>
The same test piece as that used for load deflection temperature measurement was placed in a cylindrical glass container with an outer diameter of 50 mm, an inner diameter of 45 mm, and a height of 100 mm containing 50 mL of pure water so that the gate part was not submerged in water. Thereafter, the cylindrical glass container was placed in an ultrasonic cleaning tank (US-102 manufactured by SND Co., Ltd.) having a length of 140 mm, a width of 240 mm, and a depth of 100 mm and containing 1000 mL of water. After performing ultrasonic cleaning for 10 minutes at an output of 38 kHz and 100 W, the number of particles with a particle diameter of 2 μm or more (particles that have fallen off from the test piece) contained in 1 mL of pure water is counted using a particle counter ( The measurement was performed three times using LiQuilaz-05 (manufactured by Spectris), and the average value was taken as the measurement result.

<Weld strength>
A cylindrical test piece with a welded part was produced by injection molding using an injection molding machine (NEX15-1E manufactured by Nissei Jushi Kogyo Co., Ltd.) with a mold clamping pressure of 15 tons at a cylinder temperature of +20 to 40°C with a melting point and a mold temperature of 70°C. (thickness 0.8 mm, outer diameter 10 mm, height 5 mm) was produced. A compression test was performed on each test piece using INSTRON 5567 (a universal testing machine manufactured by Instron Japan Company Limited), and the strength at which the weld part broke was measured.

<Metal adhesion>
A metal rivet (diameter 12 mm, height 8 mm) with 12 mg of adhesive (AE-421D manufactured by Ajinomoto Fine Techno Co., Inc.) applied to the same test piece as the test piece used for load deflection temperature measurement at a position 10 mm away from the gate on the opposite side. was attached and heated at 80° C. for 30 minutes to solidify the adhesive to prepare an adhesive evaluation test piece. For each test piece, a metal rivet was pulled horizontally to the test piece using INSTRON 5567 (a universal testing machine manufactured by Instron Japan Company Limited) to measure the adhesive strength.

In Examples and Comparative Examples, the following abbreviations represent the following compounds.
POB: parahydroxybenzoic acid BON6: 6-hydroxy-2-naphthoic acid HQ: hydroquinone BP: 4,4'-dihydroxybiphenyl TPA: terephthalic acid

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

The temperature was raised from room temperature to 150° C. in 1 hour under a nitrogen gas atmosphere, and maintained at the same temperature for 30 minutes. Next, the temperature was raised to 350°C over 7 hours while distilling off the by-produced acetic acid, and then the pressure was reduced to 5 mmHg over 80 minutes. The polymerization reaction was terminated when a predetermined torque was exhibited, the contents of the reaction vessel were taken out, and pellets of liquid crystal polyester resin were obtained using a crusher. The amount of acetic acid distilled during the polymerization was almost the same as the theoretical value.

The fillers used in the following Examples and Comparative Examples are shown below.
Cyclic olefin resin (COP): cycloolefin polymer “ZEONOR (registered trademark) 1420R” manufactured by Nippon Zeon Co., Ltd.
Carbodiimide group-containing compound (CI): Polycarbodiimide "Carbodilite (registered trademark) LA-1" manufactured by Nisshinbo Chemical Co., Ltd.
Acicular filler: Acicular titanium oxide “FTL-400” manufactured by Ishihara Sangyo Co., Ltd.

Examples 1 to 5, Comparative Examples 1 to 4
The LCP, cyclic olefin resin (COP), carbodiimide group-containing compound (CI), and acicular filler synthesized in Synthesis Example 1 were blended to have the contents listed in Table 2, and Melt-kneading was performed at 350° C. using TEX-30 (manufactured by Co., Ltd.) to obtain pellets of the liquid crystal polymer composition. Melt viscosity, deflection temperature under load, tensile strength, bending strength, number of particles generated, weld strength, and metal adhesion were measured and evaluated by the above methods. The results are shown in Table 2.

As shown in Table 2, all of the liquid crystal polymer compositions of Examples 1 to 5 had excellent metal adhesion while maintaining weld strength.

On the other hand, for the liquid crystal polymer compositions of Comparative Examples 1 to 4, the melt viscosity decreased, resulting in deterioration in moldability, etc. (deterioration in measurement stability, generation of blisters due to air entrainment, etc.), and weld strength decreased. A decrease in adhesiveness or a decrease in metal adhesion was confirmed, making it undesirable as a molding material.

In addition, the liquid crystal polymer compositions of Examples 4 and 5 containing a predetermined amount of acicular filler exhibited suppressed generation of particles.

Claims (9)

Containing 100 parts by mass of a liquid crystal polymer, 0.1 to 10 parts by mass of a cyclic olefin resin, and 0.1 to 5 parts by mass of a carbodiimide group-containing compound,
The liquid crystal polymer has formula (I) and formula (II)

A liquid crystal polymer composition, which is a liquid crystal polyester resin containing a repeating unit represented by: The liquid crystal polymer has formulas (I) to (IV)

[In the formula, Ar ₁ and Ar ₂ each represent a divalent aromatic group]
The liquid crystal polymer composition according to claim 1, which is a wholly aromatic liquid crystal polyester resin composed of repeating units represented by the following. Ar ₁ and Ar ₂ are each independently expressed by formulas (1) to (4)

The liquid crystal polymer composition according to claim 2, which is one or more types selected from aromatic groups represented by the following. The liquid crystal polymer composition according to claim 3 , wherein Ar ₁ is an aromatic group represented by formula (1), and Ar ₂ is an aromatic group represented by formula (1) and/or (3). . The liquid crystal polymer composition according to any one of claims 1 to 4, further comprising an acicular filler. 6. The liquid crystal polymer composition according to claim 5, wherein the acicular filler is acicular titanium oxide. The liquid crystal polymer composition according to claim 5 or 6, wherein the content of the acicular filler is 1 to 100 parts by mass based on 100 parts by mass of the liquid crystal polymer. A molded article comprising the liquid crystal polymer composition according to any one of claims 1 to 7. The molded product according to claim 8, wherein the molded product is a component constituting one type selected from the group consisting of a connector, a switch, a relay, a capacitor, a coil, a transformer, a camera module, and an antenna.