JPH03149774A - Connector - Google Patents

Abstract

PURPOSE:To obtain excellent tenacity, strength, size precision and heat resistance by molding liquid crystal polyester with a specific structure and a composite material mainly made of liquid crystal polyester with a specific structure. CONSTITUTION:Liquid crystal polyester is molded, where structure units are constituted of formulas (I)-(IV), structure units (I)+(II) are 75-95 mole % of structure units (I)+(II)+(III), the structure unit (III) is 25-5 mole % of structure units (I)+(II)+(III), and the mole fraction of structure units (I)/(II) is 75/24-95/5. R1 in the formula II indicates one or more groups selected from formulas V and VI, and R2 in the formula IV indicates one or more groups selected from formulas VII and VIII. An electric/electronic circuit connecting connector which has excellent tenacity, strength and size precision and very high heat resistance and can be used for surface mounting is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a connector for connecting electric/electronic equipment circuits that has excellent heat resistance and mechanical properties.

<Prior Art> Various plastic connectors have been used to connect electrical and electronic equipment circuits.

As the density of electrical and electronic equipment continues to increase, connectors are also becoming smaller and thinner, and 1-Last Snack as a material for connectors is required to have excellent molding fluidity and dimensional accuracy. Furthermore, the method of soldering electrical and electronic components such as connectors to printed wiring boards is rapidly transitioning from the conventional pin-up method to surface mount technology (hereinafter abbreviated as SMT), and more and more connectors, etc. High heat resistance is required for electrical and electronic components.

In order to meet these demands, for example,
Publication No. 404 discloses a connector made of wholly aromatic polyester.

Problems to be Solved by the Invention However, even the connector made of wholly aromatic polyester disclosed in JP-A No. 64-72404,
It was found that the heat resistance was not sufficient for SMT compatibility, and that cracks occurred when press-fitting the pins into the connector. Furthermore, it has been found that there is a problem that the fluidity during molding is not always sufficient.

Therefore, the present invention not only has excellent formability and dimensional accuracy, but also has S
It is an object of the present invention to provide a connector for connecting electrical and electronic equipment circuits that has both heat resistance that can be used for MT applications and excellent toughness that does not cause cracks or cracks due to stress during bottle press-fitting.

Means for Solving the Problems〉 As a result of intensive studies by the present inventors to achieve the above problems,
The inventors have discovered that a connector formed by molding a composition mainly composed of a liquid crystalline polyester of a specific type and a liquid crystalline polyester of a specific type meets the objective of achieving the above object, and has thus arrived at the present invention.

That is, the present invention consists of (1) the following elliptical units ω, ■, @, and O #I3
The ti unit [■10] is 75 to 95 mol% of [■1010], the structural unit 0 is 25 to 5 mol% of [■ + ■ 10], and the mol of the ti unit ■/■ is A connector formed by molding liquid crystal polyester with a ratio of 75/25 to 9515 and -40-1ti-0-to
...-...(D-[0-C11
2Cl-12-0...
-・Hot-(-Co-R2-Co)
...--D-! - represents one or more groups selected from R2, and X in the formula represents a hydrogen atom or a chlorine atom,
)(2) The present invention provides the connector according to item (1), which further contains 0.2 to 30 parts by weight of an organic flame retardant to 100 parts by weight of the liquid crystal polyester described in item (1).

The above structural unit (■) is a structural unit of polyester produced from p-droxybenzoic acid, and the acetate unit (■) is 4.4'
-Dioxybiphenyl, hydroquinone, 2.6-
dichloroxinaphthalene, t-butylhydroquinone,
A structural unit produced from one or more aromatic diols selected from 3.3", 5.5"-tetramethyl-4,4-dihydroxybiphenyl and phenylhyde monoquinone, #lyri unit 0 is derived from ethylene glycol. The structural unit ■ is terphthalic acid, 4.4'-
Diphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-
Dicarboxylic acid, 1,2-bis(2-chlorophenoxy)
Produced from one or more aromatic dicarboxylic acids selected from ethane-4,4-dicarboxylic acid and 4,4'-diphenyl ether dicarboxylic acid! RT! Each unit is indicated.

Among these, as R1 (OXO8 is the above-mentioned Kozueki unit ■~O, #l unit [■10] is [■1010]
It is 75 to 95 mol%, preferably 82 to 92 mol%, and more preferably 85 to 90 mol%. In addition, the structural unit 0 is 25 to 5 mol% of ([)1010],
Preferably 18 to 8 mol%, more preferably 15 to 1
It is 0 mol%. S construction unit [■＋■] is [■1010]
If it is larger than 95 mol%, the melt fluidity will decrease and it will solidify during polymerization, and if it is smaller than 75 mol%, the heat resistance will be poor, which is not preferable. Also, the structural unit ■/■ molar ratio is 75/2
5 to 9515, preferably 78/22 to 93/7
It is. If it is less than 75/25 or greater than 9515, the heat resistance and fluidity will be poor and the purpose of the present invention cannot be achieved. is equimolar to

The method for producing the liquid crystal polyester used in the present invention is not particularly limited, and it can be produced according to known polyester polycondensation methods.

Furthermore, the melt viscosity of the liquid crystal polyester used in the present invention is 1
0-15. OOO boys are preferred, especially 20 to 5.
000 voids is more preferred.

Note that this melt viscosity is a value measured using a Koka type flow tester under conditions of (liquid crystal start temperature + 40° C.) and a slip rate of 1,000 (1/sec).

On the other hand, the logarithmic viscosity of this liquid crystal polyester is 0°1 g/a
The fi degree can be measured in pentafluorophenol at 60°C, preferably 0.5 to 5.0 a/g, and IO to 3.
Particularly preferred is 0a/g.

In addition, when polycondensing the liquid crystal polyester used in the present invention, in addition to the components constituting the above-mentioned permeable units 1 to 0, isophthalic acid, 3.3'-diphenyldicarboxylic acid, 2.2'
- aromatic dicarboxylic acids such as diphenyldicarboxylic acid,
Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, alicyclic dicarboxylic acids such as hexadroterephthalic acid, chlorohydroquinone, methylhydroquinone, 4゜4''-dihydroxydiphenyl sulfide, 4.4 Aromatic diols such as '-di-hydroxybenzophenone, 4,4'-di-hydroxydiphenyl ether, 1,4-butanediol, 1,6-
Hexanediol, neopentyl glycol, 1,4-
Aliphatic and cycloaliphatic diols such as cyclohexanediol and 1,4-cyclohexanedimethanol; and aromatic and hydroxycarboxylic acids such as m-h droxybenzoic acid and 2,6-t droxynaphthoic acid, or aromatic imide compounds. Further copolymerization can be carried out in a small proportion so as not to impair the purpose of the present invention.

The liquid crystal polyester used in the present invention can be imparted with flame retardancy by adding an organic flame retardant, and if flame retardancy is required for the use or purpose of the connector of the present invention, It is preferable to add a 11fi flame agent and use it as a flame retardant liquid crystalline polyester composition.

The anionic refueling agent that can be used in the present invention is an organic bromine compound and/or an organic phosphorus compound, and an organic bromine compound has a bromine atom in the molecule, and the organic bromine compound has a bromine content of 20% by weight or more. Preferably.

Specifically, low molecular weight organic bromine compounds such as decabromodiphenyl ether and ethylene bis(tetrabromophthalimide), brominated polycarbonates (for example, polycarbonate oligomers produced using brominated bisphenol A as a raw material or copolymers thereof with bisphenol A) ), brominated epoxy compounds (e.g. jepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin, and monoepoxy compounds obtained by the reaction of brominated phenols with ebichlorodolino), poly(brominated benzyl acrylate) , brominated polyphenylene ether, brominated bisphenol A, condensates of cyanuric chloride and brominated phenol, brominated polystyrene, crosslinked brominated polystyrene, crosslinked brominated poly(a-methylstyrene) and other halogenated polymers or oligomers or mixtures. among others, ethylene bis-(tetrabromophthalimide), brominated epoxy oligomers or polymers, brominated polystyrene,
Crosslinked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are preferred, and ethylene bis-(tetrabromophthalimide), brominated polystyrene and brominated polycarbonate are particularly preferably used.

The amount of these IIB refueling agents added is 10% of the liquid crystal polyester.
0 parts by weight, (preferably 12 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, but the flame retardance is closely related to the copolymerization amount of the IIM pre-0 of the liquid crystal polyester. Therefore, the amount of the organic bromine compound added is preferably 60 to 280 parts by weight, and 100 to 200 parts by weight, based on 100 parts by weight of structural unit 0 in the liquid crystal polyester. is particularly preferred.

On the other hand, the organic phosphorus compounds used in the present invention have a phosphorus atom in the molecule, and include compounds such as phosphine, phosphine oxide, and phosphorane, which are synthesized from phosphoric acid, phosphorous acid, and phosphonic acid, as well as compounds with the following structure. and polymers containing these compounds as at least one component.

Polymers may be mentioned.

-+P-0-R201-, +R1-0-R20-)-,
l I R1OItl <ζMogo-1me ear> -40-P
1-R2-Co-0=P1-0Rt-40-Ar-02-CR1CO-)-The most preferred organic phosphorus compounds among these are the following polymers.

+P -0-R20-)-, -+R1-0-R-20+
, I Note that some of these organic phosphorus compounds may be metal salts, and the amount of this organic phosphorus compound added is 11312,
01 to 30 parts by weight, preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the liquid crystal polyester consisting of
It is preferably 2 to 150 parts by weight, and 10 to 150 parts by weight.
-100 parts by weight are particularly preferred.

Further, in the present invention, the organic phosphorus compound may be an organic phosphorus compound containing bromine, such as a polymer consisting of the following structural unit.

0 Qr CH3Far In the liquid crystal polyester of the present invention, structural unit 0 is the structural unit [■
The flame retardant content is 5 to 25 mol% of
D790 standard), it can be made into V-O with a thickness of 1/32".If the structural unit (■) is less than 5 mol%, the melting point of the liquid crystal polyester will be high, so the flame retardant will decompose the liquid crystal polyester during melting and reduce polymerization. Even if a filler is added, the mechanical properties may deteriorate or the molded product may drip during combustion, which is undesirable.

On the other hand, if the 1114 unit (■) is more than 25 mol%, not only will heat resistance such as deflection temperature under load be greatly reduced, but it will also be necessary to add a large amount of organic bromine compound or phosphorus compound to impart flame retardancy. In addition, it is necessary to further add a combustion aid such as an antimony compound, which is undesirable because heat resistance and mechanical properties are greatly reduced.

A composition in which a filler is further added to the liquid crystal polyester and the long-flammable liquid crystal polyester composition used in the present invention can be more preferably used in the present invention. When adding a filler, the amount added is 200 parts by weight per 100 parts by weight of liquid crystal polyester. Preferably below the ljt part, 15 to 10
Particularly preferred is 0 parts by weight.

Fillers that can be used in the present invention include glass fibers, carbon fibers, aromatic polyamide fibers, potassium titanate fibers, gypsum fibers, brass fibers, stainless steel fibers,
Fibrous and powdered materials such as steel fibers, ceramic fibers, boron whisker fibers, mica, talc, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, wollastenite, titanium oxide, etc.
Examples include granular or plate-shaped inorganic fillers.

Among the fillers mentioned above, glass fibers are preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing resins, and can be selected from, for example, long fiber type, short fiber type chopped strand, milled fiber, etc. Further, the glass fibers may be coated or bundled with a thermoplastic resin such as ethylene/vinyl acetate copolymer, a thermosetting resin such as an epoxy resin, and a coupling agent such as a silane type or titanate type, It may also be treated with other surface treatment agents.

Furthermore, the composition of the present invention may contain antioxidants and heat stabilizers (for example, hindered phenol, hydroquinone, phosphites, and substituted products thereof), ultraviolet rays, etc., to the extent that the object of the present invention is not impaired. Absorbents (e.g. resorcinol, salitate, benzotriazoles,
benzophenone, etc.), lubricants and mold release agents (such as montanic acid and its salts, its esters, its halfesters, stearyl alcohol, stearamide and polyethylene wax), dyes II (such as nidrodium, etc.)
and customary additives such as colorants, plasticizers, antistatic agents, including pigments (e.g. cadmium sulphide, phthalocyanines, carbon black, etc.) and other thermoplastics can be added to impart the desired properties. .

The resin composition of the present invention is preferably melt-kneaded, and known methods can be used for melt-kneading. For example, the composition can be prepared by melt-kneading at a temperature of 200 to 350° C. using a Banbury mixer, a rubber roll machine, a kneader, a single-screw or two-wheel extruder, or the like.

The connector of the present invention can be easily obtained by injection molding the above-mentioned liquid crystal polyester or flammable liquid crystal polyester composition (filler may be added if necessary). - <Examples> The present invention will be explained in detail below using examples.

Reference Example 1 881 parts by weight of p-droxybenzoate, 1581 parts by weight of 4.4'-dihydroxybiphenyl, 907 parts by weight of acetic anhydride, 1141 parts by weight of terephthal, and an intrinsic viscosity of about 0.
．． 245 parts by weight of 6a/H polyethylene terephthalate was charged into a reaction vessel equipped with a stirring blade and a distillation tube, and acetic acid depolycondensation was carried out under the following conditions.

First, under a nitrogen gas atmosphere at 100 to 250°C for 5 hours,
After reacting at 50-300℃ for 1.5 hours, 300℃
, the pressure was reduced to 0.5■■9 in 1 hour, and the reaction was further carried out for 2.25 hours to complete the polycondensation, and a nearly theoretical amount of acetic acid was distilled out, resulting in a resin (a) having the following theoretical structural formula. > obtained.

K/J! / m / n = 75 / 10
/ 15 / 25 In addition, this polyester was placed on the sample stage of a polarizing microscope and the temperature was raised to confirm the optical anisotropy. As a result, the liquid crystal onset temperature was 264 ° C, indicating good optical anisotropy. Ta. Logarithmic viscosity of this polyester (0.1 g
The melt viscosity at 304° C. and a sliding speed of 1,000 (1/sec) was 910 voids.

Example] 100 parts by weight of the resin (a) obtained in Reference Example 1 and 8.5 parts by weight of brominated polystyrene (II Pyrocheck" 68P manufactured by Nissan Ferro ■) glass fiber [45 parts by weight were heated at 300°C
The mixture was melt-mixed and pelletized using a 30IIIφ twin-screw extruder set at .

The obtained composition was provided to an injection molding machine, 10x3x3m,
An 8 x 2 row 16 pin connector was molded.

The resulting connector was completely filled to the thin wall, and no whiskers or blisters were observed. In addition, when we conducted a solder heat resistance test (immersion test) on this connector, we found that
No blistering or deformation was observed even after immersion at 80℃ for 10 seconds.
It was found that it has excellent heat resistance. Furthermore, when we conducted a terminal (bottle) press-fit test, no cracks were observed.
It was found to have excellent strength and toughness.

<Effects of the Invention> According to the present invention, a connector for connecting electric/electronic circuits can be obtained which has excellent toughness, strength, and dimensional accuracy, and has extremely high heat resistance that can also be used for surface mounting.

Claims (1)

[Claims] (1) The following structural units (I), (II), (III) and (
IV), and the structural unit [(I) + (II)] is [(I)
+ (II) + (III)], the structural unit (
III) is 25 to 5 mol% of [(I)+(II)+(III)], and the molar ratio of structural units (I)/(II) is 75/
A connector made of liquid crystal polyester with a ratio of 25 to 95/5. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) ■O-R_1-O■・・・・・・(II) ■O-CH_2CH_2-O■・・・・・・(III)■
CO-R_2-CO■・・・・・・(IV) However, R_1 in the formula has ▲a mathematical formula, a chemical formula, a table, etc.▼, ▲a mathematical formula,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R_2 is ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ Indicates one or more groups selected from. Moreover, X in the formula represents a hydrogen atom or a chlorine atom. ) (2) 0.2 to 30 parts by weight of an organic flame retardant per 100 parts by weight of liquid crystal polyester
2. The connector according to claim 1, wherein the connector contains a weight part.