JPS6169860A - Resin composition and connector for optical communication molded therefrom - Google Patents

Abstract

PURPOSE:To provide a resin compsn. which gives connectors for optical communication with good productivity, which has excellent dimensional stability, by blending carbon black and a phosphite compd. with an arom. polyester. CONSTITUTION:0.01-1pt.wt. carbon black (pref. channel carbon black whose surface acidity is a pH of 4-6), 0.01-5pts.wt. phosphite compd. (e.g. tridecyl phosphite), 0-10pts.wt. titanium oxide and 0-10pts.wt. metal salt of an org. acid (e.g. zinc stearate) are blended with 100pts.wt. arom. polyester having an intrinsic viscosity of 0.7dl/g at 32 deg.C in chloroform, composed of an arom. dicarboxylic acid and a dihydric phenol compd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an aromatic polyester resin composition and an optical component molded using the same.

[Conventional technology]

In recent years, optical communication technology has been attracting attention amid the rapid development of the communications field. Optical communication systems using quartz glass fibers are capable of transmitting large amounts of information at high speeds, and are expected to greatly change society in the future. However, in optical fiber technology, connecting fibers to each other is an important issue, and various angles are being studied to achieve this goal. Optical connectors occupy an important position as such components. These are currently metal.

It is made of ceramics, etc., but the productivity is too low.

[Problem that the invention seeks to solve]

Therefore, it is desired to use plastics instead of metals and ceramics. The present invention can meet these demands. Highly productive.

It also provides a material with good dimensional stability.

[Means for solving problems]

That is, the present invention provides an aromatic polyester comprising an aromatic dicarboxylic acid and a dihydric phenolic compound, carbon black, and a phosphite compound.

The present invention relates to a resin composition containing titanium oxide and an organic carboxylic acid metal salt. More specifically, the following general formula (1)
and 100 parts by weight of an aromatic polyester polymer or copolymer containing (1) as a constituent component;
10 alkylene groups, or cycloalkylene groups or cycloalkyritene groups having 5 to 15 carbon atoms, -o-, -s-
, -5o2- and -Co- (iIfi)
Group, J, It, 2; monovalent group selected from alkyl, allyl, aralkyl, alkoxyl, alkoxyl and allyl alkoxyl groups and derivatives thereof, halokene atoms and mixtures thereof having 1 to 20 carbon atoms, p, q; p+ (1
= integer from 1 to 8, provided that 1≦p, q≦4, m, n; 0 or 1, provided that when m = 1, n\0, k, eiO or 1 provided that Lk
When =1(7), the molar ratio in the polymer is (1)/((1)+(II)) =
0.01 to 1 part by weight of carbon black, 0.01 to 5 parts by weight of a phosphite compound, 0 to 10 parts by weight of titanium oxide, and 0 to 1 part by weight of an organic carboxylic acid metal salt.
The present invention relates to a resin composition containing 0 parts by weight, and an optical component formed by molding the same, which has excellent dimensional stability, moisture resistance, and surface properties, particularly a connector for optical fiber communication.

Aromatic polyester polymers have been known for a long time. The first manufacturing method is an interfacial polymerization method, that is, a method in which aromatic dicarboxylic acid cybaride dissolved in an organic solvent that is incompatible with water is mixed with hisphenols dissolved in an alkaline aqueous solution (Japanese Patent Publication No. 1959),
The second method is solution polymerization, which is a method in which aromatic dicarboxylic acid halides and hisphenols are reacted together in an organic solvent (
The third method is the transesterification method of heating phenyl esters of aromatic dicarboxylic acids and bisphenols.
Several methods are known, such as the method using a phase transfer catalyst (28119) or a method using a phase transfer catalyst.

The aromatic polyester polymer thus obtained has excellent properties in terms of heat resistance, mechanical properties, acidity, and electrical properties, and can be used as a polymer alone or as a resin composition to form molded objects, films, fibers, etc. It has a wide range of uses.

The polymer used in the present invention can be produced by the various methods described above.

The aromatic polyester used in the present invention is as described above (
The repeating units represented by formulas 1) and <If) are constituent components, and preferably the molar ratio in the polymer is (1)/l.
10th grade (1)) = 1~0. It's an OIO thing. From the point of view of higher heat distortion temperature, the molar ratio of Tele (where A represents hisphenol residue in formulas (I) and (It)) in the polymer is (ID/(GID+■)=1). to 0.4, more preferably 1 to 0.9. Preferably, formula (1) is represented by the following formula (V').

(X1m,n; same as above, R3-1t6; carbon number 1
-4 monovalent groups selected from alkyl groups, alkoxynyl groups, and phenyl groups) Specifically, the acid component is derived from terephthalic acid and isophthalic acid. Some of these aromatic nuclei may have substituents.

The bisphenol component is derived from the following general formulas (IX) and (X).

(In the formula, X, 几+, R2, p, C1, m, n, k.

(4 is the same as above) More preferably, formula (IX) is particularly represented by the following formula Ql).

(wherein, phenyl)ethane, 2.2-his(4-hydroxyphenyl)propane, his(4-hydroquinphenyl)sulfono, his(4-hydroxyphenyl)ketone, 4.
Examples include 4-hydroxyn phenyl ether and 4,4-dihydroquine diphenyl sulfide. -1r: 2
'A phenol (X) is an example of 2,2-his(3
, 5-dimethyl-4-hydroxyphenyl)propane,
2.2-bis(3,5-di-5ec-butyl-4-hydroxyphenyl)propane, 2,2-his(3,5-di-tert-butyl-4-hydroxyphenyl)propane, his(3,5-dimethyl) -4-hydroxyphenyl)methane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)ethane, t,t-His<3.5-dimethyl-4-hydroxyphenyl)cyclohexane, His(3, 5-dimethyl-4-hydroxyphenyl) sulfone, his(3,5-dimethyl-4-hydroquinophenyl)ketone, bis(3,5-dimethyl-4-hydroxyphenyl)ether, his(3,5-dimethyl- 4-hydroquinphenyl) sulfide, 2,2-his(3,5
-dimethyl-4-hydroquinphenyl)hexafluoropropane, 2,2-his(3,5-dino-1-xy-4-
Hydroquine phenylpropane, bis(3,5-diphthoquine-4=hydroxyphenyl)methane, 2,2-his(
3-Methoxy-4,-hydroquine-5-methylphenyl)propane, bis(3-methoxy-4-hydroquine-5
-methylphenyl)methane, bis(3,5=diphenyl-4-hydroxyphenyl)methane, 2,2-bis(3
, 5-diphenoxy-4-(hydroxyphenyl)furopane, bis(3-phenoxy-4-hydroxy-5-methyl)methane, 4,4'-dihydroxy-3,3,5,
5-tetraethylbiphenyl, 4,4-dihydroxy-
Examples include 3,3,5,5-tetraethylbiphenyl.

In addition, condensed polycyclic bisphenols such as dihydroxynaphthalene and dihydroquinanthracene, bisphenolic pigments such as alizarin, phenolphthalein, fluorescein, naphthophthaleino, thymolphthalein, aurino, phenolsulfocrein, and dibromophenolsulfophthalein, 2 ,2'-dihydroxy-1
, 1-dinaphthylmethane, 4.4-dihydroxydinaphthyl-1,1,2,2-dihydroxydinaphthyl-1,
1,1,1'-His(4-hydroxynaphthyl) -2
, 2,2-trichloroethane, dinaphthyl compounds such as 2,2-dihydroxydinaphthyl-phenyl-methane,
It can also be used as part of hisphenols.

Usually, in addition to a portion of these dicarboxylic acid components and bisphenol components, -functional compounds are used for controlling the molecular weight. For example, phenol.

Monophenols such as methoxyphenol, t-butylphenol, octylphenol, nonylphenol,
Monothiophenols, acid chlorides, and amines are used.

The preferred molecular weight of the polymer is ηsp/C=0.50-0
．． 80 (32°C, 0.32 dt/g in chloroform)
It is.

The aromatic polyester represented by such a structure is (X
The component represented by formula I) provides superior properties in terms of water resistance and alkali resistance compared to conventional commercially available products.

Carbon black in the present invention is used in an amount of 0.01 to 1 part by weight per 100 parts by weight of the resin. The purpose of this is to block light from the outside and protect optical signals passing through the internal optical fiber. Preferably it is 0.05 to 0.5 part by weight. There are two types of carbon black, such as channel type and furnace type.
4 to 6 is preferred.

Furthermore, if light-shielding properties are desired on the surface layer, it is desirable to use titanium oxide in combination, and it is desirable to use titanium oxide in an amount of 0 to 100 parts by weight per 100 parts by weight of the resin.
It is used in an amount of 10 parts by weight, preferably 0.01 to 1 part by weight. The finer the titanium oxide, the easier it is to disperse into the polymer, so it is preferable.To further improve the dispersibility, it is preferable to use 0 to 10 parts by weight of an organic carboxylic acid metal salt. More preferably, it is 0.01 to 1 part by weight.

The carboxylic acid metal salt used in the present invention has the following general formula (
(R8CO2)mM (I'll) is a metal salt of an aliphatic or aromatic carboxylic acid having 7 to 30 carbon atoms and a metal belonging to Groups 2 to 4 of the short periodic table. be. Preferred carbonic acids include aliphatic ones having 11 to 23 carbon atoms, specifically lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid,
linoleic acid.

Examples include oleino acid and erucic acid. Also, preferred metals include magnesium and calcium.

Examples include barium, zinc, lead, tin, and cadmium.

Furthermore, in the present invention, a phosphite compound (U) is used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the resin in order to improve the long-term thermal stability during molding of such a resin composition.

The phosphite compound used in the present invention is represented by the following general formula (■).

(R70+rP (Vl) (R7i a group selected from alkyl, cycloalkyl, allyl, allylalkyl, and alkylaryl groups having 8 to 30 carbon atoms) (Vl) Specific examples of the formula include tridenlphosphi!- , triisothene sulfosphite, tris (tritesyl phosphite), phenyl (dithene sulfosphite), phenylon (tritesyl) phosphite, diphenyl octyl phosphite, diphenyl tesyl phosphite, nphenyl tridecyl phosphite, tris( nonylphenyl) phosphite, di(dinonylphenyl)-nonylphenyl phosphite, tris(di-t-butylphenyl) phosphite.

or tetraphenyldipropyleneglyfur diphosphite, 4,4'-butylidene-bis(3-methyl-6
-t-Butylphenyl-didodecyl phosphite, tetra(tridecyl)-4,4'-isopropylidene diphenyl diphosphite, and compounds represented by the following formulas are also compounds that can be used in the present invention.

(C12-C15 alkyl group) Conventionally known methods can be used to produce the resin composition of the present invention. For example, aromatic polyester granules or powder and the above additives are mixed in a U-type blender, Henschel mixer, Super 2 mixer, kneader, etc.
After melting and blending, pelletize.

[Action and effect]

When the resin composition according to the present invention is used as a material for an optical connector, it has various advantages as shown in the Examples. First, since it is a thermoplastic resin, productivity is high.

Second, it has excellent light blocking properties. Thirdly, it has sufficient strength and high heat distortion temperature (
Over 180°C.

18.6 kg/ci load), it has good surface smoothness and good dimensional stability. Fourth, it has excellent stability against humidity and moisture, so it can withstand use under high temperature and high humidity conditions. Fifth, it has even higher flame retardancy.

Therefore, the resin composition of the present invention is useful as a material for optical communication connectors and the like. Various types of heat molding can be used to form the optical communication connector, but injection molding is particularly advantageous, and ordinary injection molding methods can be used.

〔Example〕

Examples are shown below, but the invention is not limited only to these.

Reference Example 1 Production of aromatic polyester Bisphenol A 221.1813,1,5.5-
Tetramethylbisphenol F 124.57y.

Paramethoxyphenol 9.97f, sodium hydrosal 7ft 2.64f, 4N-NaOH
960 liters of scraps and 1660 g of water! 3 in a nitrogen atmosphere
The mixture was mixed in a flask and cooled to 2°C to prepare an alkaline aqueous solution of bisphenol. Meanwhile, in another 34 flasks 274.05f of terephthalic acid chloride.

Isophthalic acid chloride 80.459 to methylene chloride 2
The solution was dissolved in a nitrogen atmosphere to 500 g/ml and cooled to 2°C.

81 In a separable flask, 10001 I11 water 0.4 benzyltributylammonium chloride as catalyst
79 was placed under a nitrogen atmosphere and cooled in the same manner.

While vigorously stirring the mixture, the above two liquids were each added continuously using a pump for 800 seconds. After 5 hours from the end of the addition, 4.229 g of benzoyl chloride was added to the system in which 10 (1+/) of methylene chloride was dissolved. After 20 minutes, when stirring was stopped, a methylene chloride solution containing the polymer, salt, and hydric soda was added. It was separated into an aqueous solution after about 10 minutes. After decanting the aqueous layer, the same amount of water was added and neutralized with a small amount of hydrochloric acid while stirring. After repeated desalination by water washing, the same amount was added to a methylene chloride solution. of acetone was gradually added to precipitate the polymer to obtain a powder.The molecular weight of the polymer was approximately p10 = 0.70 (0.32 dl/f in chloroform at 32°C).

Examples 1 to 4 Table 1 shows the poly, mer, carbon black, titanium oxide, organic carboxylic acid metal salt, and phosphite compound of Reference Example 1.
They were blended in a Henschel mixer in the following proportions. 380
After extrusion into pellets at °C, injection molding was performed to obtain test pieces.

Mechanical and Thermal Properties of Test Pieces For the samples of Examples 1-4, the light transmission coefficient of the 0.8fl thick plate is 400-700 u
It was 0% in the wavelength range of m.

Next, Table 3 shows the results of testing the wet heat durability of the sample of Example 1.2.

Table 3: Change in tensile properties in wet heat test As shown above, it can be seen that the product has excellent wet heat durability.

Claims (13)

[Claims] (1) 0.01 to 1 part by weight of carbon black, 0.01 to 5 parts by weight of phosphite compound, and 0 to 10 parts by weight of titanium oxide to 100 parts by weight of aromatic polyester consisting of aromatic dicarboxylic acid and dihydric phenolic compound. A resin composition containing 0 to 10 parts by weight of an organic carboxylic acid metal salt. (2) Aromatic polyester has the following general formula (I) and (
II) The composition according to claim 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, X: Alkylene group with 1 to 10 carbon atoms or cycloalkylene group with 5 to 15 carbon atoms or a cycloalkylidene group, a divalent group selected from -O-, -S-, -CO-, -SO_2-, R_1, R_2; alkyl having 1 to 20 carbon atoms, allyl, aralkyl, alkoxyl, allyloxyl and allyl alkoxyl A monovalent group selected from the group p
, q; p+q=integer from 1 to 8, provided that 1≦p, q≦4, m
, n; 0 or 1, but when m=1, n≠0, K, l; 0 or 1, but when k=1, l≠0, and the molar ratio of (I) and (II) is (I)/{ (
I ) + (II)} = 1 to 0.01) (3) Terephthalic acid component in aromatic polyester (III
) and the isophthalic acid component (IV) in a molar ratio of (III)/
{(III) + (IV)} = 1 to 0.1 ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(IV) (However, A is (I), The composition according to claim 2, which represents a bisphenol residue in formula (II). (4) The composition according to claim 3, wherein the molar ratio of (III) and (IV) in the aromatic polyester is (III)/{(III)+(IV)}=1 to 0.4. thing. (5) The composition according to claim 3, wherein the molar ratio of (III) and (IV) in the aromatic polyester is (III)/{(III)+(IV)}=1 to 0.9. thing. (6) The composition according to claim 2, wherein formula (I) is represented by the following formula (V). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (X, m, n; same as above, R_3 to R_6; carbon number 1
~4 monovalent groups selected from alkyl groups, alkoxyl groups, and phenyl groups) (7) The aromatic polyester has an intrinsic viscosity of 0.50 to 0.
70 dl/g (32°C, in chloroform). (8) The composition according to claim 1, wherein the phosphite compound has the following general formula (VI). (R_7O)-_3P(VI) (R_7; group selected from alkyl, cycloalkyl, allyl, allylalkyl, and alkylaryl groups having 8 to 30 carbon atoms) (9) The composition according to claim 8, wherein R_7 in the phosphite compound (VI) is an allyl group or an alkylaryl group having 8 to 30 carbon atoms. (10) Claim 1 in which the organic carboxylic acid used in the organic carboxylic acid metal salt is represented by the following formula (VII).
Compositions as described in Section. R_8CO_2H (VII) (R_8; aliphatic or aromatic group having 7 to 30 carbon atoms) (11) The composition according to claim 10, wherein the organic carboxylic acid is a saturated or unsaturated fatty acid having 11 to 23 carbon atoms. (12) The composition according to claim 1, wherein the metal used in the organic carboxylic acid metal salt belongs to Groups 2 to 4 of the short periodic table. (13) 0.01 to 1 part by weight of carbon black, 0.01 to 5 parts by weight of phosphite compound, and 0 to 10 parts by weight of titanium oxide to 100 parts by weight of aromatic polyester consisting of aromatic dicarboxylic acid and dihydric phenolic compound. 1. An optical communication connector formed by thermoforming a resin composition containing 0 to 10 parts by weight of an organic carboxylic acid metal salt.