JP3453981B2 - A liquid crystal resin composition for a fine pitch connector molded product and a fine pitch connector molded product comprising the same. - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent dimensional accuracy, few burrs, easy press-fitting of contact terminals, excellent weld strength, and multi-core for high density.
The present invention relates to an improved fine pitch connector molded product made of a liquid crystalline resin, which has surface mountable heat resistance.

[0002]

2. Description of the Related Art A connector is required as a connecting functional part for electronic equipment, from consumer equipment such as a VTR and a mobile phone to industrial equipment such as a computer and a communication device, and high reliability such as an aircraft and a nuclear reactor. It is used in various fields such as equipment. Various resin materials are used for these purposes, such as polypropylene resin, polybutylene terephthalate resin, nylon resin, and polyphenylene sulfide resin, depending on the purpose.

[0003] In recent years, along with the high performance of electronic equipment, connectors are required to have high heat resistance (improvement of productivity by mounting technology), high density (multicore), and miniaturization as demands of the times. For high heat resistance, super engineering plastic with high heat resistance is used as a resin material for connectors instead of conventional general-purpose engineering plastics, and high productivity is obtained by surface mounting technology. In addition, in order to achieve high density (multi-core), the pitch interval between terminals is narrowed, that is, so-called fine pitch, that is, the resin portion that holds the contact terminals is thin and has sufficient strength. It is necessary to have high strength and high rigidity.

Polyphenylene sulfide resin connectors, 4,6 nylon connectors and the like are disclosed in Plastic Molding Technology, Volume 10, No. 4, pp. 45-59 as a method for achieving these high performances of connectors. Although the polyphenylene sulfide resin connector has excellent heat resistance, it has a limitation in thinning (fluidity), easily causes burrs, and is brittle.
Although the 4,6 nylon connector has excellent toughness, it suffers from problems such as decreased rigidity and large dimensional fluctuation due to water absorption, and its performance is not suitable for use as a fine pitch connector with a pitch interval between terminals of 0.8 mm or less. It was insufficient.

As a fine pitch connector having a pitch interval of 0.8 mm or less, a 0.8 mm pitch LCP connector is a polyphenylene sulfide resin connector in Plastic Molding Technology, Volume 10, No. 4, pp. 45-59. It is disclosed that the fluidity at the time of molding is good and the occurrence of burrs is small as compared with the above. However, since the weld strength is low, cracks are likely to occur,
It has been pointed out that there is a large amount of warp deformation, the occurrence of burrs is smaller than that of the polyphenylene sulfide resin connector, but it is not sufficient, and that the thin wall portion is easily deformed at the time of mold release. There is a problem that a fine pitch connector having a pitch interval of 0.8 mm or less is not necessarily obtained.

[0006]

SUMMARY OF THE INVENTION Therefore, the present invention solves the above-mentioned problems, reduces burr generation, facilitates press-fitting of contact terminals, has excellent weld strength, and has a large number of cores for high density. The present invention relates to an improved fine pitch connector molded product made of a liquid crystalline resin, which is capable of surface mounting and has heat resistance.

[0007]

The present inventors have arrived at the present invention as a result of extensive studies to solve the above problems.

That is, the present invention provides (A) an anisotropic molten phase
-Forming liquid crystalline polyester and liquid crystalline polyester
100 weight of one or more liquid crystalline resins selected from luamide
0 parts by weight to 400 parts by weight of the filler (B)
And the melt viscosity is within the following condition range.
Fine pitch connector with a pitch interval of 0.8 mm or less
-Liquid crystalline resin composition for molded products, (melting viscosity measurement condition) Temperature: melting point (Tm) of liquid crystalline resin + 10 ° C Nozzle size: nozzle diameter 1.0 mmφ, nozzle length
10 mm (melt viscosity) The melt viscosity at a shear rate of 1200 (1 / sec) is 200 Pa.
s or less and the melt viscosity at a shear rate of 12 (1 / sec) is 3
0 to 2500 Pa · s (A) 100 parts by weight of one or more liquid crystalline resins selected from liquid crystalline polyesters and liquid crystalline polyester amides that form an anisotropic molten phase, and (B) filler 0 to 40
A liquid crystal resin composition containing 0 parts by weight, and a composition having a melt viscosity of the composition within the following condition range is molded by injection molding. Fine pitch connector molded product of 0.8 mm or less, (melting viscosity measurement condition) Temperature: Melting point of liquid crystalline resin (Tm) + 10 ° C Nozzle size: Nozzle diameter 1.0 mmφ, nozzle length 10 mm (melt viscosity) Shear rate Melt viscosity of 1200 (1 / sec) is 200 Pa
s or less and the melt viscosity at a shear rate of 12 (1 / sec) is 3
00-2500 Pa · s Further, a fine pitch connector molded product having a pitch interval between terminals of 0.8 mm or less, characterized by molding a composition having the above melt viscosity within the following condition range by injection molding, (melt viscosity Measurement conditions) Temperature: melting point (Tm) of liquid crystalline resin + 10 ° C Nozzle size: nozzle diameter 1.0 mmφ, nozzle length 10 mm (melt viscosity) Melt viscosity at shear rate 1200 (1 / sec) is 90 Pa · s
Below, and the melt viscosity of shear rate 12 (1 / second) is 35
0~1300Pa · s The pitch interval between the terminals is the fine pitch connector moldings is 0.6mm or less.

The liquid crystalline resin (A) is selected from wholly aromatic polyesters, wholly aromatic liquid crystalline polyesteramides, liquid crystalline polyesters having ethylenedioxy units, and liquid crystalline polyesteramides having ethylenedioxy units. The fine pitch connector molded article which is one or more kinds of liquid crystalline resin, and (A) the liquid crystalline resin has the following [(I), (II) and (IV)], [(I), (I
II) and (IV)] or [(I), (II),
(III) and (IV)] the fine pitch connector molded product, which is a liquid crystalline polyester comprising the structural unit,

[Chemical 5] (However, R1 in the formula is

[Chemical 6] R1 represents one or more groups selected from

[Chemical 7] Represents one or more groups selected from Further, in the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(II) + (I
II)] and structural unit (IV) are substantially equimolar. In addition, the liquid crystalline resin composition further comprises (A) 100 parts by weight of the liquid crystalline resin, polyethylene, polypropylene, a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms, and propylene and carbon. A copolymer obtained by copolymerizing an α-olefin having a number of 4 or more, and ethylene and a carbon number of 3
A copolymer obtained by copolymerizing the above α-olefin and a non-conjugated diene, and α- having 4 or more carbon atoms and propylene.
One or more olefin-based polymers selected from copolymers obtained by copolymerizing olefins and non-conjugated dienes 0.01
The fine pitch connector molded product and the liquid crystalline resin composition prepared by blending 10 to 10 parts by weight of the liquid crystalline resin composition with 100 parts by weight of the (A) liquid crystalline resin further contain an organic bromide of 0.1.
The fine-pitch connector molded product is prepared by blending 5 to 60 parts by weight, and the organic bromide has a weight average molecular weight of 1 or more of the following structural units produced from brominated styrene monomer as a main constituent. × 10 ^{3 to} 12
The fine pitch connector molded product, which is 0 × 10 ⁴ polybrominated styrene,

[Chemical 8] In addition, the fine pitch connector molded product is obtained by further mixing 0.01 to 10 parts by weight of carbon black with 100 parts by weight of the liquid crystalline resin (A) in the liquid crystalline resin composition.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid crystalline resin (A) in the present invention is at least one selected from liquid crystalline polyester and liquid crystalline polyesteramide.

The liquid crystal polyester referred to in the present invention is a polyester which forms an anisotropic melt phase composed of structural units selected from aromatic oxycarbonyl units, aromatic dioxy units, aromatic dicarbonyl units, ethylenedioxy units and the like. And so on. Further, the liquid crystalline polyesteramide is a liquid crystalline polyesteramide that forms an anisotropic molten phase composed of the structural unit and an aromatic iminocarbonyl unit, an aromatic diimino unit, a structural unit selected from aromatic diiminooxy units and the like. is there.

The liquid crystalline resin used in the present invention is a wholly aromatic liquid crystalline polyester having a naphthalene ring, a wholly aromatic liquid crystalline polyesteramide having a naphthalene ring, a liquid crystalline polyester having an ethylenedioxy unit, Examples thereof include liquid crystalline polyesteramides having an ethylenedioxy unit.

Preferred examples of the liquid crystalline polyester include the above [(I), (II) and (IV)],
A liquid crystalline polyester comprising a structural unit of [(I), (III) and (IV)] or [(I), (II), (III) and (IV)] can be mentioned.

The structural unit (I) is a structural unit formed from p-hydroxybenzoic acid, and the structural unit (II) is 4,4'-dihydroxybiphenyl, 3,3 ', 5,5.
′ -Tetramethyl-4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4'-
Structural units formed from an aromatic dihydroxy compound selected from dihydroxydiphenyl ether, structural units (III) are structural units formed from ethylene glycol, structural units (IV) are terephthalic acid, isophthalic acid,
4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,
Each of the structural units formed from an aromatic dicarboxylic acid selected from 4′-diphenyl ether dicarboxylic acid is shown.

Of these, R1 is

[Chemical 9] And R2 is

[Chemical 10] Are particularly preferred.

The liquid crystalline polyester which can be preferably used in the present invention includes the above structural units [(I), (II) and (I).
V)], [(I), (III) and (IV)] or a copolymer composed of [(I), (II), (III) and (IV)] and having the structural unit (I), (II),
The copolymerization amount of (III) and (IV) is arbitrary. However, from the viewpoint of fluidity, the following copolymerization amount is preferable.

That is, when the structural unit (III) is contained, the structural unit [(I) + (II)] is [(I) + (from the viewpoint of heat resistance, flame retardancy, fluidity and mechanical properties). I
I) + (III)] is preferably 60 to 95 mol%,
5 to 93 mol% is more preferable. In addition, the structural unit (II
I) is preferably 40 to 5 mol% of [(I) + (II) + (III)], and more preferably 25 to 7 mol%. The molar ratio of structural unit (I) / (II) is preferably 75/25 to 95/5 from the viewpoint of the balance between heat resistance and fluidity.
And more preferably 78/22 to 93/7.
Further, the structural unit (IV) is a structural unit [(II) + (II
I)] is substantially equimolar.

On the other hand, when the structural unit (II) is not included, the structural unit (I) is [(I) +
(II)] is preferably 40 to 90 mol%, and 60 to 88.
It is particularly preferable that the amount is mol%, and the structural unit (IV) is substantially equimolar to the structural unit (II). As the liquid crystal polyesteramide, the above structural units (I) to (I
In addition to V), polyesteramides that form an anisotropic melt phase containing p-aminophenoxy units generated from p-aminophenol are preferred.

When polycondensing the above-mentioned liquid crystalline polyester and liquid crystalline polyesteramide which can be preferably used in the present invention, 3,3'-diphenyldicarboxylic acid is contained in addition to the components constituting the structural units (I) to (IV). Acid, 2 '
An aromatic dicarboxylic acid such as diphenyldicarboxylic acid,
Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, methylhydroquinone, 4,4'-dihydroxydiphenylsulfone, 4,4 ' -Dihydroxydiphenyl sulfide, aromatic diol such as 4,4'-dihydroxybenzophenone, 1,4-butanediol, 1,6-
Hexanediol, neopentyl glycol, 1,4-
Aliphatic and alicyclic diols such as cyclohexanediol and 1,4-cyclohexanedimethanol and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and p-aminophenol and p-aminobenzoic acid An acid or the like can be further copolymerized in a small proportion.

The method for producing the liquid crystalline resin (A) in the present invention is not particularly limited and can be produced according to the known polycondensation method of polyester.

For example, in the production of the above-mentioned preferably used liquid crystalline polyester, the above structural unit (III)
(1) and (2) not containing the structural unit (II
When I) is included, the production method of (3) is preferable.

(1) p-acetoxybenzoic acid and 4,
A method for producing a diacylated aromatic dihydroxy compound such as 4′-diacetoxybiphenyl or 4,4′-diacetoxybenzene and an aromatic dicarboxylic acid such as terephthalic acid by a deacetic acid polycondensation reaction. (2) p-Hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, aromatic dihydroxy compounds such as hydroquinone, aromatic dicarboxylic acids such as terephthalic acid are reacted with acetic anhydride to acylate the phenolic hydroxyl group, A method for producing by deacetic acid polycondensation reaction. (3) Produced by the method (1) or (2) in the presence of a polyester polymer such as polyethylene terephthalate, an oligomer, or a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate. how to.

Although these polycondensation reactions proceed without a catalyst, it is sometimes preferable to add a metal compound such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, or magnesium metal. .

Some of the liquid crystalline resins (A) in the present invention are capable of measuring the logarithmic viscosity in pentafluorophenol, and in that case, they are measured at a concentration of 0.1 g / dl at 60 ° C. The value is preferably 0.5 dl / g or more,
In particular, when the structural unit (III) is included, 1.0 to 3.
0 dl / g is preferable, and 2.0-10.0 dl / g is preferable when the structural unit (III) is not included.

In the present invention, since it is not essential to mix other additives and fillers, the fine pitch connector molded product may be composed of the liquid crystalline resin alone. In that case, the liquid crystalline resin alone is used. However, it may be expressed as a liquid crystalline resin composition.

As the filler (B) usable in the present invention, glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless fiber, steel fiber, ceramic fiber,
Boron whisker fiber, aluminum borate fiber, asbestos fiber, mica, talc, silica, calcium carbonate, glass powder, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastenite, titanium oxide, calcium polyphosphate, graphite Examples thereof include fibrous, powdery, granular or plate-like fillers.

Among the above fillers, glass fiber is preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcement, and for example, long fiber type or short fiber type chopped strand, milled fiber or the like can be selected and used.

When the above-mentioned filler is added, the addition amount is usually 0 to 400 parts by weight, preferably 50 to 250 parts by weight, more preferably 70 to 200 parts by weight, based on 100 parts by weight of the liquid crystalline resin. is there.

The surface of the above-mentioned filler used in the present invention is treated with a known coupling agent (eg, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agent before use. You can also

The glass fibers may be coated or bundled with a thermoplastic resin such as ethylene / vinyl acetate copolymer or the like, or a thermosetting resin such as an epoxy resin or the like.

In the present invention, an olefin polymer may be further added. Examples of the olefin polymer used in the present invention include polyethylene, polypropylene, a copolymer obtained by copolymerizing ethylene with an α-olefin having 3 or more carbon atoms, and a copolymer obtained by copolymerizing propylene with an α-olefin having 4 or more carbon atoms. Copolymer, copolymer of ethylene, α-olefin having 3 or more carbon atoms and non-conjugated diene, copolymer of propylene and α-olefin having 4 or more carbon atoms and non-conjugated diene It is one or more selected from coalescence.

Examples of the α-olefin having 3 or more carbon atoms include propylene, butene-1, pentene-1, 3-methylpentene-1, octacene-1, and the like, with propylene and butene-1 being more preferable. Alternatively, two or more kinds can be used in combination. Further, the α-olefin having 4 or more carbon atoms is one other than propylene among the α-olefins having 3 or more carbon atoms.

The non-conjugated diene is preferably 5-ethylidene-2-norbornene, dicyclopentadiene, 1,
4-hexadiene or the like can be used.

When the non-conjugated diene is not contained, the copolymerization ratio of ethylene and α-olefin having 3 or more carbon atoms is usually 4
0/60 to 99/1 (molar ratio), preferably 70/30
To 95/5 (molar ratio), and the copolymerization ratio of propylene and α-olefin having 4 or more carbon atoms is usually 40/60 to 9
9/1 (molar ratio), preferably 70/30 to 95/5
(Molar ratio).

When the non-conjugated diene is contained, the copolymerization amount of the α-olefin having 3 or more carbon atoms or the α-olefin having 4 or more carbon atoms is usually 3 to 80 mol%, preferably 15 to 60 mol%. And the copolymerization amount of non-conjugated diene is
Usually, it is 0.1 to 15 mol%, preferably 0.5 to 10 mol%.

Specific examples of these copolymers include ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / pentene-1 copolymer, ethylene / propylene / butene-1 copolymer, ethylene. /propylene/
5-ethylidene-2-norbornene copolymer, ethylene / propylene / 1,4-hexadiene copolymer, ethylene / propylene / dicyclopentadiene copolymer, etc., among which ethylene / propylene copolymer and ethylene / butene -1 copolymer is more preferable because of its excellent heat resistance.

Two or more of the above olefin polymers may be used in combination.

The olefin polymer has a weight average molecular weight of 10,000 to 600,000, preferably 30,000 to
500,000, more preferably 100,000 to 450
It is desirable to be in the range of 000.

The amount of the above olefin polymer added is 0.0
10 to 10 parts by weight, preferably 0.05 to 5 parts by weight, 0.0
1-2 parts by weight are particularly preferred.

In the present invention, a flame retardant such as an organic bromide may be added.

The organic bromide used in the present invention includes known organic bromides usually used as flame retardants, and those having a bromine content of 20% by weight or more are particularly preferable.

Specifically, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether,
Hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, ethylene-bis (tetrabromophthalimide), low molecular weight organic bromine compounds such as tetrabromobisphenol A, brominated polycarbonate (for example, a polycarbonate oligomer produced from brominated bisphenol A as a raw material) Or its bisphenol A
Copolymer), brominated epoxy compound (for example, diepoxy compound produced by reaction of brominated bisphenol A with epichlorohydrin, monoepoxy compound obtained by reaction of brominated phenol with epichlorohydrin), poly (brominated Benzyl acrylate),
Halogenated polymers and oligomers such as brominated polyphenylene ether, brominated bisphenol A, condensate of cyanuric chloride and brominated phenol, brominated polystyrene, crosslinked brominated polystyrene, crosslinked hydrogenated poly α-methylstyrene, or the like. Examples thereof include a mixture of ethylene bis (tetrabromophthalimide), brominated epoxy oligomer or polymer, brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate, and brominated polystyrene is most preferably used. .

The above-mentioned preferable organic bromide will be described in more detail. As the brominated epoxy polymer, those represented by the following general formula (i) are preferable.

[0044]

[Chemical 11]

The polymerization degree n in the general formula (i) is preferably 15 or more, more preferably 50 to 80.

The brominated polystyrene used in the present invention includes brominated polystyrene and crosslinked brominated polystyrene produced by brominating polystyrene obtained by radical polymerization or anionic polymerization, or radical polymerization or anion polymerization of brominated styrene monomer. , Preferably produced by radical polymerization (i
Examples thereof include polybrominated styrene having a brominated styrene unit represented by the formula i) and / or (iii), and particularly, represented by the following general formula (ii) and / or (iii) prepared from a brominated styrene monomer. The structural unit shown is the main constituent and the weight average molecular weight is 1 × 1.
Polybrominated styrene of 0 ^{3 to} 120 × 10 ⁴ is preferable.

[0047]

[Chemical 12]

The term “brominated styrene monomer” as used herein is preferably one in which 2 to 3 bromine atoms are introduced into the aromatic ring by a substitution reaction per styrene monomer, such as dibrominated styrene and / or tribrominated. In addition to styrene, monobrominated styrene and the like may be contained.

The above polybrominated styrene preferably contains dibrominated styrene and / or tribrominated styrene units in an amount of 60% by weight or more, more preferably 70% by weight or more. In addition to dibrominated polystyrene and / or tribrominated styrene, 40 monobrominated styrene
It may be polybrominated styrene copolymerized in an amount of not more than 30% by weight, preferably not more than 30% by weight. The weight average molecular weight of this polybrominated styrene is more preferably 1 × 10 ⁴ to 15 × 10 ⁴ . The weight average molecular weight is a value measured using a gel permeation chromatograph and is a relative value based on polystyrene molecular weight. As the crosslinked brominated polystyrene, polystyrene obtained by brominated porous polystyrene crosslinked with divinylbenzene is preferable.

As the brominated polycarbonate, those represented by the following general formula (iv) are preferable.

[0051]

[Chemical 13] (R3 and R4 represent a substituted or unsubstituted aryl group, and a pt-butylphenyl group is most preferable.)

The degree of polymerization n in the above general formula (iv) is preferably 4 or more, more preferably 8 or more, especially 8 to 2
5 can be used more preferably. The blending amount of these organic bromides is 0.5 to 6 per 100 parts by weight of the liquid crystalline resin.
0 parts by weight, especially 1 to 30 parts by weight are preferred.

In the liquid crystalline resin molded product of the present invention, the organic bromide has an average diameter of 25 μm in the resin composition before molding.
It is preferably dispersed below, and more preferably 2.0 μm or less.

The carbon black used in the present invention is not particularly limited, but from the viewpoint of mechanical properties of the resulting composition, PH of 3 to 10 is preferable, and PH of 5 to 9 is particularly preferable. .

The liquid crystalline resin molded article of the present invention includes an antioxidant and a heat stabilizer (eg, hindered phenol, hydroquinone, phosphites and their substitution products), an ultraviolet absorbing agent (eg, resorcinol, salicylate, benzo). Triazoles, benzophenones, etc., lubricants and mold release agents (such as montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax), dyes (eg nigrosine) and pigments (eg cadmium sulfide, phthalocyanine etc.) Ordinary additives such as a colorant, a plasticizer, a flame retardant aid, an antistatic agent, and the like, and other thermoplastic resins (fluorine resin, etc.) may be contained.

The pitch interval between terminals of the present invention is 0.8 mm.
The following fine pitch connector molded product is a connector molded product having a pitch interval between terminals of 0.8 mm or less, particularly 0.6 mm or less, further 0.5 mm or less, and further 0.4 mm or less.

In the present invention, the thickness of the resin portion between the terminals is 0.4 mm or less, particularly 0.3 mm or less, and 0.2
It can be a connector molded product having a size of not more than mm.

The method for producing the fine pitch connector molded article of the present invention is not particularly limited, but a desired molded article can be obtained by producing a liquid crystalline resin composition by melt kneading and then performing melt molding.

The method for producing the liquid crystalline resin composition is not particularly limited, but the liquid crystalline resin composition can be produced by melt-kneading and then melt-molded to obtain a desired molded article.

Specifically, for example, a Banbury mixer,
The composition can be obtained by melt-kneading at a temperature of 200 to 400 ° C. using a rubber roll machine, a kneader, a single-screw or twin-screw extruder, and the like. Among them, a twin-screw extruder is used, and the raw materials (A) liquid crystalline resin, (B) filler, (C) olefin polymer and other additives are blended together, and then the extruder is blended. It is recommended to apply the method of feeding, the method of melt-kneading the raw materials sequentially and continuously to the extruder, or the like.

In the present invention, it is important that the melt viscosity of the liquid crystalline resin composition is within the following condition range. That is, measurement temperature: melting point (Tm) of liquid crystalline resin + 10 ° C. Nozzle size: nozzle diameter 1.0 mmφ, nozzle length 10 mm, melt viscosity was 200 Pa · s or less at a shear rate of 1200 (1 / sec), And the shear rate 12 (1 /
Second) 300 to 2500 Pa · s, preferably 90 Pa · s or less at a shear rate of 1200 (1 / second),
And, at a shear rate of 12 (1 / sec), 350 to 130
0 Pa · s, particularly preferable offset speed 1200 (1 /
Second) 70 Pa · s or less and a shear rate of 12
It is preferably 450 to 900 Pa · s at (1 / sec).

2 at a shear rate of 1200 (1 / sec)
If it exceeds 00 Pa · s, the fluidity at the time of molding will decrease, and not only the shaping of the molded product will not be possible, but also the molding pressure will need to be increased for shaping, and burrs are likely to occur in the molded product. . Also, when the shear rate is 12 (1 / sec), it is 2
If it exceeds 500 Pa · s, the resin is not sufficiently filled especially in the thin-walled tip portion in the mold, and it becomes difficult to stably form a fine pitch connector having a pitch interval of 0.8 mm or less. On the other hand, when the shear rate is 12 (1 / sec), 3
If it is less than 00 Pa · s, burrs will be noticeable.

The fine pitch connector molded product of the present invention is preferably formed by injection molding of the above-mentioned liquid crystalline resin composition. Although not particularly limited, a preferable injection molding method includes, for example, an in-line type injection molding machine in which the melting point of the liquid crystalline resin is set to −30 ° C. to + 50 ° C. Providing the composition,
It is recommended that a method such as obtaining a fine pitch connector molded product by injection molding into a mold of a molded product in which the mold temperature is set to a temperature condition of about 70 ° C to 150 ° C.

[0064]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Reference Example 1 p-Hydroxybenzoic acid 994 parts by weight, 4,4'-dihydroxybiphenyl 126 parts by weight, terephthalic acid 112
By weight, 216 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 960 parts by weight of acetic anhydride are charged in a reaction vessel equipped with a stirring blade and a distilling tube to carry out polycondensation to complete polycondensation. (A) was obtained. The melting point (Tm) of this resin was 314 ° C.

Reference Example 2 994 parts by weight of p-hydroxybenzoic acid, 222 parts by weight of 4,4'-dihydroxybiphenyl, 147 parts by weight of 2,6-diacetoxynaphthalene, 1078 parts by weight of acetic anhydride and 299 parts by weight of terephthalic acid were stirred. The resin (B) was obtained by charging into a reaction vessel equipped with blades and a distilling tube, polycondensation was carried out, and polycondensation was intermittently carried out. The melting point (Tm) of this resin is 33
It was 6 ° C.

Reference Example 3 1296 parts by weight of p-acetoxybenzoic acid and 346 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g were charged in a reaction vessel equipped with a stirring blade and a distilling tube to carry out polycondensation. Resin (C) was obtained. Melting point of this resin (T
m) was 283 ° C.

Reference Example 4 654 parts by weight of p-hydroxybenzoic acid, 266 parts by weight of 4,4'-dihydroxybiphenyl, 6-hydroxy-2
-61 parts by weight of naphthoic acid, 237 parts by weight of terephthalic acid and 890 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distillation tube to carry out polycondensation to complete polycondensation to obtain a resin (D). It was The melting point (Tm) of this resin was 347 ° C.

Reference Example 5 921 parts by weight of p-acetoxybenzoic acid and 435 parts by weight of 6-acetoxy-2-naphthoic acid were charged into a reaction vessel equipped with a stirring blade and a distillation tube, and polycondensation was carried out by changing the polymerization time. , Resin (E) was obtained. The melting point (Tm) of this resin is 28
It was 3 ° C.

Here, the melting point (Tm) means Tm1 after the endothermic peak temperature Tm1 observed when the polymer is measured by a differential calorimetry at a temperature rising condition from room temperature to 20 ° C./min.
After raising the temperature to + 20 ° C. and holding at the same temperature for 5 minutes, once cooling to room temperature under a temperature lowering condition of 20 ° C./minute,
The endothermic peak temperature observed when measured again under the temperature rising condition of 20 ° C./min.

Examples 1 to 7 and Comparative Examples 1 to 5 Using a 35 mmφ twin-screw extruder having a raw material supply port and an intermediate addition port, the liquid crystalline resins obtained in Reference Examples 1 to 4 were used at different cylinder temperatures. The mixture was supplied to the raw material supply port of a 35 mmφ twin-screw extruder set to the melting point of the liquid crystalline resin, and then the filler shown in Table 1 was supplied from the intermediate addition port at a ratio shown in Table 1, and melt-kneaded. Then, a pellet of the liquid crystalline resin composition was obtained. Next, the melt viscosity of the obtained pellets was measured under the following conditions, and the results are shown in Table 1.

(Conditions for Measuring Melt Viscosity) Temperature: Melting point (Tm) of liquid crystalline resin + 10 ° C. Nozzle size: Nozzle diameter 1.0 mmφ, Nozzle length 10 mm Shear rate 1200 (1 / sec) and shear rate 12 (1 /
Further, the obtained pellets were subjected to Sumitomo Nestal injection molding machine Promat (manufactured by Sumitomo Heavy Industries, Ltd.), and the outer dimensions had a width of 0. 0 when the cylinder temperature was the melting point + 10 ° C and the mold temperature was 130 ° C. 3mm x 22mm x 5mm in height, pitch interval between terminals is 0.5mm, and resin part thickness between terminals is 0.3mm.
A fine pitch connector molded product was injection-molded using a single-piece mold (gate shape: pinpoint gate).
FIG. 1 is a conceptual cross-sectional view of a four-cavity mold of the fine pitch connector molded product. Each molded product is formed by the resin filled in the molded product cavity 4 from the runner 2 through each gate 3. .

The four cavities (E, F, G, H) are filled with resin, and the minimum pressure (minimum moldable pressure) at which a molded product can be injection-molded and the wall thickness of each molded product is 0.3 mm. The resin filling state of the portion (resin portion between terminals) was observed. Moreover, the size of the burr generated in the portion M of the molded product of the cavity H was measured. FIG. 2 is a perspective view of a molded product molded in the cavity H, in which the position of the portion M is shown. Further, the molded product of the cavity H was immersed in a solder bath set to each temperature for 20 seconds, and the maximum temperature at which abnormalities such as foaming and deformation did not occur in the molded product was determined as the solder heat resistant temperature.

The results are shown in Table 1.

[0075]

[Table 1]

Examples 8 to 15 Examples 8 to 15 were carried out except that a liquid crystalline resin composition prepared by adding the olefin polymer and carbon black to 100 parts by weight of the liquid crystalline resin in the proportion shown in Table 2 was used. The procedure was as in Example 1.

The results are shown in Table 2.

[0078]

[Table 2]

Reference Example 6 Table 3 shows the structures of the organic bromine compounds used in the following examples.

[0080]

[Table 3]

Examples 16 to 21 Liquid crystalline resin compositions prepared by blending the organic bromide shown in Table 3 (Reference Example 6) in Example 13 in a ratio shown in Table 4 with respect to 100 parts by weight of the liquid crystalline resin were prepared. Pellets of the composition were produced in the same manner as in Example 1 except that the pellets were used. Sumitomo Nestal injection molding machine Promat 40/25
(Sumitomo Heavy Industries, Ltd.), 0.5 mm under the conditions of the cylinder temperature is melting point + 10 ° C and the mold temperature is 90 ° C.
Example 1 except that a flame test piece of (thickness) × 12.7 mm × 127 mm was molded, and a vertical flame test was performed according to UL94 standard by using the test piece to evaluate flame retardancy.
It carried out similarly to.

The results are shown in Table 4.

[0083]

[Table 4]

[0084]

The pitch interval between terminals of the present invention is 0.8 m.
Fine pitch connector molded products of m or less have excellent heat resistance, mechanical properties, dimensional accuracy, and weld strength, so electrical / electronic related equipment, precision machinery related equipment, office equipment, automobile / vehicle related parts, etc. It is useful as a fine pitch connector used for various other purposes.

[Brief description of drawings]

FIG. 1 is a conceptual sectional view of a four-cavity mold of a fine pitch connector molded product molded in an example.

FIG. 2 is a perspective view of a molded product molded in a cavity H.

[Explanation of symbols]

1. Mold 2. runner 3. Gate 4. Molded product cavity

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 67/00-67/03 C08L 77/12

Claims (8)

(57) [Claims] 1. A liquid crystalline poly which forms an anisotropic molten phase (A).
Selected from ester and liquid crystalline polyesteramide
(B) is added to 100 parts by weight of one or more liquid crystalline resins.
It is composed of 0 to 400 parts by weight of filler and has a melt viscosity.
Is the following condition range, the pitch interval between terminals is 0.8m
Liquid crystalline resin for fine pitch connector molded products of m or less
Composition. (Conditions for measuring melt viscosity) Temperature: melting point (Tm) of liquid crystalline resin + 10 ° C Nozzle size: Nozzle diameter 1.0 mmφ, nozzle length
10 mm (Melt viscosity) The melt viscosity at a shear rate of 1200 (1 / sec) is 200 Pa.
s or less, and Melt viscosity at shear rate 12 (1 / sec) is 300 to 2500
Pa · s 2. The filler (B) 0 to 400 is added to 100 parts by weight of one or more liquid crystalline resins selected from liquid crystalline polyesters and liquid crystalline polyester amides which form (A) an anisotropic molten phase. A liquid crystal resin composition containing 1 part by weight of the composition, wherein a composition having a melt viscosity of the composition within the following condition range is molded by injection molding. Fine pitch connector molded product of 0.8 mm or less. (Melt viscosity measurement conditions) Temperature: Melting point (Tm) of liquid crystalline resin + 10 ° C Nozzle size: Nozzle diameter 1.0 mmφ, Nozzle length 10 mm (Melt viscosity) Melt viscosity at shear rate 1200 (1 / sec) is 200 Pa・
s or less, and the melt viscosity at a shear rate of 12 (1 / second) is 300 to 2500.
Pa · s 3. A fine pitch connector according to claim 2, wherein the composition has a melt viscosity of the liquid crystalline composition within the following range of conditions and is molded by injection molding. The pitch interval between terminals is 0.8 mm or less. Molding. (Melt viscosity measurement conditions) Temperature: Melting point (Tm) of liquid crystalline resin + 10 ° C Nozzle size: Nozzle diameter 1.0 mmφ, Nozzle length 10 mm (Melt viscosity) Melt viscosity at shear rate 1200 (1 / sec) is 90 Pa・ S
Below, and the melt viscosity at a shear rate of 12 (1 / second) is 350 to 1300.
Pa · s 4. The liquid crystalline resin (A) is selected from a wholly aromatic polyester, a wholly aromatic liquid crystalline polyesteramide, a liquid crystalline polyester having an ethylenedioxy unit, and a liquid crystalline polyesteramide having an ethylenedioxy unit. The fine pitch connector molded product according to any one of claims 2 to 3 , which is one or more kinds of liquid crystalline resins. 5. The liquid crystal resin (A) comprises the following [(I) and (I
I) and (IV)], [(I), (III) and (IV)] or [(I), (II), (III) and (IV)] structural units. Item 5. A fine pitch connector molded product according to any one of items 2 to 4. [Chemical 1] (However, R1 in the formula is R1 represents one or more groups selected from Represents one or more groups selected from Further, in the formula, X represents a hydrogen atom or a chlorine atom, and the structural unit [(II) + (I
II)] and structural unit (IV) are substantially equimolar. ) 6. The liquid crystalline resin composition is (A) liquid crystalline resin 10.
0 parts by weight of polyethylene, polypropylene, a copolymer obtained by copolymerizing ethylene and an α-olefin having 3 or more carbon atoms, and propylene and α- having 4 or more carbon atoms.
Copolymers obtained by copolymerizing olefins, copolymers obtained by copolymerizing ethylene and α-olefins having 3 or more carbon atoms and non-conjugated dienes, and propylene and α-olefins having 4 or more carbon atoms and non-conjugated A composition comprising 0.01 to 10 parts by weight of at least one olefin polymer selected from copolymers obtained by copolymerizing diene.
The fine pitch connector molded product according to any one of 2 to 5. 7. A liquid crystalline resin composition is (A) a liquid crystalline resin 10.
Relative to 0 parts by weight, Ri further greens blended with organic bromide 0.5 to 60 parts by weight, the organic bromide is a brominated styrene
Main constituent of one or more of the following structural units manufactured from monomers
Weight average molecular weight as a component is 1 × 10 ^{3 to} 120 × 10 ⁴
7. The polybrominated styrene according to any one of claims 2 to 6.
Fine pitch connector molded product listed. [Chemical 4] 8. A liquid crystal resin composition is (A) liquid crystal resin 10.
With respect to 0 part by weight, carbon black of 0.01 to
The fine pitch connector molded product according to any one of claims 2 to 8, which is obtained by mixing 10 parts by weight.