JP2003306598A - Liquid-crystalline resin composition and molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid-crystalline resin composition suitable for electrical/ electronic parts which gives unprecedentedly high flame retardancy, is excellent in thin-gage flow property and thin-gage rigidity, and is low in gas evolution and anisotropy. <P>SOLUTION: The resin composition incorporates, to 100 pts.wt. of a liquid- crystalline resin (A), 0.01-5 pts.wt. of a branched organopolysiloxane (B) represented by the average molecular formula: (R<SP>1</SP><SB>3</SB>SiO<SB>1/2</SB>)<SB>a</SB>(R<SP>2</SP>SiO<SB>3/2</SB>)<SB>b</SB>(SiO<SB>4/2</SB>)<SB>c</SB>(R<SP>3</SP>O<SB>1/2</SB>)<SB>d</SB>(HO<SB>1/2</SB>)<SB>e</SB>(wherein R<SP>1</SP>and R<SP>2</SP>are each a monovalent hydrocarbon group selected form the group consisting of 1-12C alkyl and 6-12C aryl groups; the content of the aryl group in the whole monovalent hydrocarbon group totalizing R<SP>1</SP>and R<SP>2</SP>is 15-100 mole%; R<SP>3</SP>is an alkyl group; a is 0 or a positive number; b is a positive number; and c, d and e are each 0 or a positive number). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a liquid crystalline resin composition which is excellent in thin-wall fluidity, thin-wall rigidity, low gas property and low anisotropy and which has been imparted with an unprecedentedly high degree of flame retardancy. is there.

[0002]

2. Description of the Related Art In recent years, the demand for higher performance of plastics has been increasing, and many polymers having various new properties have been developed and put on the market. Among them, optics featuring parallel arrangement of molecular chains Liquid crystalline resins such as anisotropic liquid crystalline polyester resins have been attracting attention because of their excellent moldability and mechanical properties, and demand is expanding mainly for electrical and electronic component applications.

Among them, heat resistance, thermal stability (low gas property), thin-wall fluidity, thin-wall rigidity, and flame-retardancy are required to meet the demand for miniaturization and high integration of electronic components compatible with surface mounting technology such as connectors and relays. Excellent liquid crystal resins are being used more and more. However, in recent years, as molded products have become thinner, have a larger area, and have become more complex, the thin-walled fluidity, thin-wall rigidity, low gas properties, low anisotropy, and higher flame retardancy in thin-walled products have become even higher. Has been requested.

For example, in surface mount type board-to-board connectors and connectors for flexible circuit boards, in recent years, the pitch has been narrowed, and some terminals are connected at 0.3 mm pitch intervals, and resin molded products used as insulators The thickness of the thinnest part is 0.1 mm. Therefore, the molding resin is required to have excellent thin-wall fluidity and high rigidity for holding terminals. Liquid crystal resin is also used for the case of the surface mount type relay, and further improvement in thin-wall fluidity and low gas property for sealing the relay contact are desired for miniaturization.

On the other hand, the liquid crystalline resin is generally superior in flame retardancy to polybutylene terephthalate resin and polyethylene terephthalate resin. However, it cannot be said that the high level of flame retardancy required in recent years, for example, the flame retardancy against electrostatic sparks, is sufficient. Further, it is desired to reduce the amount of additives in terms of cost and physical properties.

A method in which an organic bromine compound and an antimony compound are added together for the purpose of further improving the flame retardancy of the liquid crystalline resin (Japanese Patent Laid-Open No. 118567/1989).
And a method of adding red phosphorus (JP-A-6-299050) and a method of adding a silicone rubber and / or a silicone resin (JP-A-2000-239503) are disclosed.

[0007]

However, in the method of adding a halogen-based flame retardant such as an organic bromine compound described in JP-A-1-118567, the flame retardant itself burns and decomposes to generate a halogen gas. It extinguishes by suffocation and extinguishes the flame after a certain amount of time, but the flame retardancy is not sufficient, and if the addition amount is increased, the fluidity and rigidity will decrease and the gas generation amount will also increase. . In addition, in the method of adding a phosphorus-based flame retardant such as red phosphorus described in JP-A-6-299050, etc., a flammable gas is adsorbed and fixed, or formation of a carbonized film is promoted to make it flame-retardant. However, it took a long time for the flame to completely extinguish the flame, and it was difficult to obtain high flame retardancy.

Further, the method of adding silicone rubber and / or silicone resin disclosed in Japanese Patent Laid-Open No. 2000-239503 gives V-0 in the test according to UL94, but does not meet the requirement of flame retardancy. On the other hand, it was not sufficient, and it did not give the additional thin-wall fluidity, rigidity, low gas property and low anisotropy desired for precision molded products.

The present invention has been made in view of the background of the prior art, and is thin-walled fluidity, thin-walled rigidity, low gas-property and low-abnormality that meet the demands for miniaturization and high integration of electric and electronic parts. An object of the present invention is to provide a liquid crystalline resin composition having excellent toughness and excellent flame retardancy, which is a requirement for higher flame retardancy.

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that by adding a very small amount of an organopolysiloxane having a specific structure to a liquid crystalline resin,
It has been found that a higher degree of flame retardancy can be obtained, and a liquid crystalline resin composition having excellent thin-wall fluidity, thin-wall rigidity, low gas property and low anisotropy can be obtained, and reached the present invention.

That is, in the present invention, (1) 100 parts by weight of the liquid crystalline resin (A) is used, and the average molecular formula: (R ¹ ₃ S
_{iO 1/2) a (R} 2 SiO 3/2) b (Si
^{_{O 4/2) c (R 3 O}} 1/2) d (HO 1/2) e ( wherein, R ¹ and R ² are each an alkyl group having 1 to 12 carbon atoms, 6 to 12 carbon atoms It is a monovalent hydrocarbon group selected from the group consisting of aryl groups, and the content of aryl groups in the total monovalent hydrocarbon groups obtained by summing R ¹ and R ² is from ¹⁵ to ¹⁰⁰ .
Mol%. R ³ is an alkyl group. a is 0 or a positive number, b is a positive number, and c, d and e are 0 or a positive number. (2) The liquid crystalline resin composition obtained by blending 0.01 to 5 parts by weight of the branched organopolysiloxane (B) represented by the formula (2), wherein the liquid crystalline resin (A) is a liquid crystalline polyester resin and / or a liquid crystalline polyester. The liquid crystalline polyester resin composition according to (1), which is an amide resin composition, and (3) the liquid crystalline polyester resin comprising the following structural units (I), (II), (III) and (IV): A liquid crystalline resin composition according to (2), which comprises a selected structural unit,

[0012]

[Chemical 5] (However, R ⁴ in the formula is

[0013]

[Chemical 6] R ⁵ represents one or more groups selected from

[0014]

[Chemical 7] R ⁶ represents one or more groups selected from

[0015]

[Chemical 8] And one or more groups selected from However, in the formula, X represents a hydrogen atom or a chlorine atom. ) (4) Liquid crystalline resin (A) 10
It is characterized by further adding 0.01 to 10 parts by weight of a carbonate of a metal of Group 1A and / or a carbonate of a metal of Group 2A (D) to 0 part by weight (1). ~
The weight of the liquid crystalline resin composition according to any one of (3), (5) the organopolysiloxane (B) and a carbonate of a metal of Group 1A and / or a carbonate of a metal of Group 2A (C) in the periodic table of the elements. The composition ratio (B) / (C) is 2/1 to 1/3, and (6) the liquid crystalline resin (A) with respect to 100 parts by weight of the liquid crystalline resin (A). , Filling material (D) 2
The liquid crystalline resin composition according to any one of (1) to (5), which further comprises 5 to 300 parts by weight, and (7) to (1) to (6). The present invention provides a molded article for electric / electronic parts having a thinnest portion of 0.5 mm or less obtained by injection-molding the liquid crystalline resin composition.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The liquid crystalline resin (A) of the present invention is
It is a polymer that can form an anisotropic molten phase when melted, and includes liquid crystalline polyester resin, liquid crystalline polyesteramide resin, liquid crystalline polycarbonate resin, liquid crystalline polyester elastomer, etc. Among them, it has an ester bond in the molecular chain. A liquid crystalline polyester resin, a liquid crystalline polyesteramide resin and the like are particularly preferably used.

As the liquid crystalline polyester resin, for example,
Examples thereof include polyesters that form an anisotropic melt phase composed of structural units selected from aromatic oxycarbonyl units, aromatic dioxy units, aromatic dicarbonyl units, alkylenedioxy units, and the like. Further, as the liquid crystalline polyesteramide resin, in addition to the structural unit of the liquid crystalline polyester resin, an aromatic iminocarbonyl unit, an aromatic diimino unit, an anisotropic melt phase containing a structural unit selected from aromatic iminooxy units and the like. The polyester amide which forms is mentioned.

Examples of the aromatic oxycarbonyl unit include p-hydroxybenzoic acid and 6-hydroxy-2-
Examples of structural units and aromatic dioxy units generated from naphthoic acid include 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t -Structural units and aromatics formed from butyl hydroquinone, phenyl hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl ether, etc. Examples of the dicarbonyl unit include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-
Dicarboxylic acid, 1,2-bis (2-chlorophenoxy)
Structural units formed from ethane-4,4'-dicarboxylic acid and 4,4'-diphenyl ether dicarboxylic acid,
As the alkylenedioxy unit, for example, a structural unit produced from ethylene glycol, propylene glycol, 1,4-butanediol, cyclohexanedimethanol, and the like, and as the aromatic iminocarbonyl unit, for example, p-aminobenzoic acid, 6- Examples of the structural unit generated from amino-2-naphthoic acid or the like and the aromatic diimino unit include 1,4-phenylenediamine and 4,4′-
Examples of the structural unit formed from diaminobiphenyl, 2,6-diaminonaphthalene and the like and the aromatic iminooxy unit include structural units formed from 4-aminophenol and the like.

Specific examples of the liquid crystalline polyester resin include a structural unit formed from p-hydroxybenzoic acid and 6
-A liquid crystalline polyester resin comprising a structural unit produced from hydroxy-2-naphthoic acid, a structural unit produced from p-hydroxybenzoic acid, a structural unit produced from 6-hydroxy-2-naphthoic acid, an aromatic dihydroxy compound and / or Or a liquid crystalline polyester resin composed of a structural unit derived from an aliphatic dicarboxylic acid, a structural unit derived from p-hydroxybenzoic acid, a structural unit derived from 4,4′-dihydroxybiphenyl, and a structural unit derived from terephthalic acid. Liquid crystalline polyester resin, p-
A liquid crystalline polyester resin comprising a structural unit produced from hydroxybenzoic acid, a structural unit produced from ethylene glycol, a structural unit produced from terephthalic acid and isophthalic acid, a structural unit produced from p-hydroxybenzoic acid, produced from ethylene glycol Structural unit, 4,
A structural unit formed from 4'-dihydroxybiphenyl,
Liquid crystalline polyester resin composed of structural units produced from terephthalic acid and / or sebacic acid, structural unit produced from p-hydroxybenzoic acid, structural unit produced from ethylene glycol, liquid crystalline polyester resin produced from terephthalic acid, p- Structural unit produced from hydroxybenzoic acid, structural unit produced from ethylene glycol, structural unit produced from aromatic dihydroxy compound,
Examples thereof include liquid crystalline polyester resins produced from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid.

A preferable example of the liquid crystalline polyester resin is a liquid crystalline polyester resin containing an ethylenedioxy unit. Among them, the following structural units (I), (II), (II
A liquid crystalline polyester resin comprising a structural unit selected from I) and (IV) is preferable, more preferably a structural unit
A liquid crystalline polyester resin comprising (I), (II), (III) and (IV).

[0021]

[Chemical 9] (However, R ⁴ in the formula is

[0022]

[Chemical 10] R ⁵ represents one or more groups selected from

[0023]

[Chemical 11] R ⁶ represents one or more groups selected from

[0024]

[Chemical 12] And one or more groups selected from However, in the formula, X represents a hydrogen atom or a chlorine atom. ) The structural unit (I) is an aromatic oxycarbonyl unit, such as p-hydroxybenzoic acid and / or 2
Is a structural unit formed from -hydroxy-6-naphthoic acid, the structural unit (II) is an aromatic dioxy unit,
For example, 4,4'-dihydroxybiphenyl, 3,3 ',
5,5'-tetramethyl-4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone,
Phenylhydroquinone, methylhydroquinone, 2,
Structural units formed from one or more aromatic dihydroxy compounds selected from 6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, The structural unit (III) is an alkylenedioxy unit, for example, a structural unit produced from ethylene glycol, and the structural unit (IV) is an aromatic dicarbonyl unit, for example, 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 ' -One or more aromatic dicarbocarboxylic acid selected from dicarboxylic acid and 4,4'-diphenyl ether dicarboxylic acid The structural units generated from the acid are shown below. Of these, R ⁵

[0025]

[Chemical 13] And R ⁶ is

[0026]

[Chemical 14] Are particularly preferred.

The above structural units (I), (II), (III) and (IV)
The copolymerization amount of is arbitrary. However, the following copolymerization amounts are preferable in order to exert the characteristics of the present invention better.

That is, the above structural units (I), (II), (III)
In the case of a copolymer consisting of and (IV), the above structural unit
The total of (I) and (II) is structural units (I), (II) and (III)
30 to 95 mol% is preferable relative to the total of 40 to 9
2 mol% is more preferable. Further, the structural unit (III) is preferably 70 to 5 mol%, and more preferably 60 to 8 mol% with respect to the total of the structural units (I), (II) and (III). Also,
The molar ratio [(I) / (II)] of the structural units (I) and (II) is preferably 75/25 to 95/5, more preferably 78/2.
2 to 93/7. Further, the structural unit (IV) is the structural unit (I
It is preferably substantially equimolar to the total of I) and (III).

Those containing a p-iminophenoxy unit formed from p-aminophenol in addition to the above structural units (I) to (IV) can also be preferably used.

The liquid crystalline polyester resin which can be preferably used is, in addition to the components constituting the structural units (I) to (IV), 3,3'-diphenyldicarboxylic acid and 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 hexahydroterephthalic acid, chlorohydroquinone, 3,4 ′ -Dihydroxybiphenyl, 4,4'-
Aromatic diols such as dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone and 3,4'-dihydroxybiphenyl, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexane Aliphatic and alicyclic diols such as diols and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid can be further copolymerized to the extent that liquid crystallinity is not impaired.

The method for producing the above-mentioned liquid crystalline polyester resin used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method.

For example, in the production of the above liquid crystalline polyester resin, the following production method is preferably mentioned. (1) Diacylated products of aromatic dihydroxy compounds such as p-acetoxybenzoic acid and 4,4′-diacetoxybiphenyl and diacetoxybenzene, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester resin by a deacetic acid condensation polymerization reaction. (2) Aromatic dihydroxy compounds such as p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl and hydroquinone, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid are reacted with acetic anhydride. Then, after acylating the phenolic hydroxyl group, a liquid crystalline polyester resin is produced by deacetic acid polycondensation reaction. (3) Phenyl ester of p-hydroxybenzoic acid and aromatic dihydroxy compound such as 4,4′-dihydroxybiphenyl and hydroquinone, and diphenyl ester of aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester resin from a phenol by a polyphenol condensation reaction. (4) p-Hydroxybenzoic acid and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid are reacted with a predetermined amount of diphenyl carbonate to form diphenyl esters, respectively,
A method for producing a liquid crystalline polyester resin by adding an aromatic dihydroxy compound such as 4,4′-dihydroxybiphenyl or hydroquinone and performing a dephenol polycondensation reaction. (5) Liquid crystal by the method of (1) or (2) in the presence of polyester polymer such as polyethylene terephthalate, oligomer or bis (β-hydroxyethyl) ester of aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate. For producing a water-soluble polyester resin.

Although the polycondensation reaction of the liquid crystalline polyester resin proceeds without a catalyst, stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, metal compounds such as magnesium metal can also be used. .

The liquid crystalline resin (A) that can be preferably used in the present invention may be one in which the logarithmic viscosity can be measured in pentafluorophenol, in which case 0.1 g /
A value measured at 60 ° C. at a concentration of dl is preferably 0.3 or more. In the case of the liquid crystalline polyester resin containing the structural unit (III), 0.5 to 3.0 dl / g, and in the case of the liquid crystalline polyester resin not containing the structural unit (III), 1.0 to 15.0 d.
l / g is particularly preferred.

The melt viscosity of the liquid crystalline resin (A) in the present invention is preferably 5 to 200 Pa · s, and particularly 10 to 10
0 Pa · s is more preferable.

The melt viscosity is the melting point (Tm) +10.
It is a value measured by a Koka type flow tester under conditions of a shear rate of 1,000 (1 / sec) under conditions of ° C.

Here, the melting point (Tm) is the endothermic peak temperature (T) observed in the differential calorimetric measurement when the polymerized polymer is measured at a temperature rising condition from room temperature to 20 ° C./min.
After observing m1), the temperature was maintained at Tm1 + 20 ° C. for 5 minutes, and then once cooled to room temperature under a temperature lowering condition of 20 ° C./minute,
The endothermic peak temperature (Tm2) observed when measured again under the temperature rising condition of 20 ° C / min.

The organopolysiloxane (B) used in the present invention has an average molecular formula: (R ¹ ₃ SiO _1/2 ).
_a (R ² SiO _3/2 ) _b (SiO _4/2 ) _c (R ³ O
_1/2 ) _d (HO _1/2 ) _e (In the formula, R ¹ and R ² are each an alkyl group having 1 to 12 carbon atoms, and 6 carbon atoms.
To 12 are monovalent hydrocarbon groups selected from the group consisting of aryl groups, and the total content of aryl groups in the total monovalent hydrocarbon groups of R ¹ and R ² is ¹⁵ to ¹⁰⁰ mol%. R ³ is an alkyl group. a is 0 or a positive number, b is a positive number, and c, d and e are 0 or a positive number. ) Is a branched organopolysiloxane. In the above formula, as the alkyl group having 1 to 12 carbon atoms, a methyl group,
Examples are ethyl group, n-propyl group, isopropyl group, butyl group, and hexyl group, and among these, methyl group,
Ethyl and n-propyl groups are preferred. 6-carbon
The aryl group of 12 includes a phenyl group, a naphthyl group,
A tolyl group is exemplified, and among these, a phenyl group is preferable. Examples of the alkyl group of R ³ include a methyl group, an ethyl group, a propyl group and a butyl group, and examples of the group represented by the above formula R ³ O include a methoxy group, an ethoxy group, a propoxy group and a butoxy group. . The content of aryl groups in the total monovalent hydrocarbon groups obtained by summing R ¹ and R ² is 15 to 10
It is necessary to be 0 mol% and 30 to 100 mol%
Is preferable, and 50 to 100 mol% is more preferable. Particularly, the content of the aryl group of R ² is important, and R in the total monovalent hydrocarbon group obtained by adding R ¹ and R ² is
The content of the aryl group in ² is preferably 30 to 100 mol%, and more preferably 50 to 100 mol%.

The content of the group represented by the formula: R ³ O, that is, the alkoxy group, in the organopolysiloxane component is preferably 10% by weight or less based on the whole organopolysiloxane. Further, the content of the hydroxyl group in the component is preferably 10% by weight or less, more preferably 3% by weight or less, based on the whole organopolysiloxane.

The contents of the alkoxy group and the hydroxyl group are calculated as follows. Average molecular formula (R ¹ ₃ SiO
_1/2 ) _a (R ² SiO _3/2 ) _b (SiO _4/2 ) _{c
^{(R 3 O 1/2)}} d (HO 1/2) average unit formula from _e R ¹
_3a R ² _b Si _{(a + b + c)} O _{(
(A / 2) + (3b} / 2) + 2c) (R 3 O 1/2) d
(HO _1/2 ) e is obtained. Therefore, the molecular weight of the average unit formula is W, the molecular weight of the alkoxy group (R ³ O) _d is W1,
When the molecular weight of the hydroxyl group (HO) _e is W2, the content of the alkoxy group is represented by (W1 / W) × 100 (wt%), and the content of the hydroxyl group is represented by (W2 / W) × 100 (wt%). .

In the formula, the sum of a, b and c is 1, and in the formula, a is a positive number of 0 or more and less than 1, preferably 0.3 or less, more preferably 0.1 or less. Yes,
It is more preferably 0.05 or less, and particularly, when a is 0, the amount of gas is very small, which is preferable. Also,
In the formula, b is a positive number of 1 or less, preferably 0.7 to 1.
It is 0, and more preferably 0.9 to 1.0. In the formula, c is a positive number of 0 or more and less than 1, preferably 0.3 or less, more preferably 0.1 or less.

The weight average molecular weight of the organopolysiloxane (B) of the present invention is preferably 300 to 50,000, more preferably 1,000 to 20,000, and still more preferably 2,000 to 10,000.
Within this range, problems such as deterioration in moldability do not occur, which is preferable. The weight average molecular weight is usually determined by gel permeation chromatography (GPC).
Quantified by

The organopolysiloxane component used in the present invention has at least the formula: R ² SiO ² per molecule.
_A trifunctional siloxane unit (T unit) represented by _3/2 is indispensable, but in addition to the trifunctional siloxane unit (T unit), ^{1 represented} by the formula R ¹ ₃ SiO _1/2 Functional siloxane units (M units) and / or formula:
The inclusion of a tetrafunctional siloxane unit (Q unit) represented by SiO _4/2 is acceptable as long as the object of the present invention is not impaired.

The softening point of the organopolysiloxane component used in the present invention is preferably room temperature (25 ° C.) or higher, more preferably 50 ° C. or higher, still more preferably 50 ° C. or higher and 200 ° C. or lower. . In that case,
It is preferable because the dispersibility of the component in the liquid crystalline resin is good and the kneading can be easily performed by a usual method.

The blending amount of the organopolysiloxane (B) of the present invention is 0.01 with respect to 100 parts by weight of the liquid crystalline resin.
To 5 parts by weight, preferably 0.1 to 3 parts by weight, and more preferably 0.2 to 1.8 parts by weight.

The organopolysiloxane (B) having such a specific structure is added to the liquid crystalline resin (A) in a very small amount (0.01 to 5).
(Parts by weight) By blending, high flame retardancy, which is a feature of the present invention, is obtained, and mechanical properties, color tone, heat resistance, fluidity, hydrolysis resistance and thermal stability are excellent, and bleed-out is also excellent. A liquid crystalline resin composition is obtained.

Further, the liquid crystalline resin composition of the present invention further contains a carbonate of a metal of Group 1A and / or a carbonate of a metal of Group 2A (C) of the periodic table for further improving flame retardancy. It is preferably used in combination with the organopolysiloxane (B).

Examples of the metal of Group 1A and the metal of Group 2A of the Periodic Table of the Elements include sodium, potassium, calcium, magnesium, barium and the like, of which calcium is preferred.

Examples of the carbonate of the metal of Group 1A and / or the carbonate of the metal of Group 2A (C) in the periodic table include calcium carbonate, potassium carbonate, magnesium carbonate, barium carbonate, sodium carbonate and the like. Of these, calcium carbonate is preferred.

In the present invention, the compounding amount of the 1A group metal carbonate and / or 2A group metal carbonate (C) in the periodic table of the elements is 0. 01 to 10 parts by weight, preferably 0.1
To 5 parts by weight, more preferably 0.2 to 3 parts by weight.

When the liquid crystalline resin composition of the present invention further contains a carbonate of a metal of Group 1A and / or a carbonate of a metal of Group 2A (C) of the Periodic Table of Elements, a thin wall of 0.4 mm or less is obtained. In addition to achieving high flame retardancy in the molded product, the whiteness is further increased to improve the appearance, and the decrease in melt viscosity due to decomposition is suppressed. Also, when the resin for the next shot in the injection molding cycle is weighed and waiting for solidification in the mold and removal from the die on the previous shot, the weighed resin decomposes and the melt viscosity decreases The phenomenon of so-called flapping is suppressed, and the moldability is improved.

In order to bring out the effects of the present invention more remarkably, the organopolysiloxane (B) is mixed with a carbonate of a metal of Group 1A and / or a carbonate of a metal of Group 2A (C) of the periodic table of the elements. The ratio is 2 / weight ratio (B) / (C)
It is preferably in the range of 1 to 1/3, and more preferably 1/1 to 1/2.

As the carbonate of a metal of Group 1A and / or the carbonate of a metal of Group 2A (C) in the Periodic Table of Elements, commercially available products can be used, and the average particle diameter is not particularly limited. Is preferably 0.01 to 5 μm, more preferably 0.05 to 3 μm, and further preferably 0.1 to 2 μm. Also, regarding the specific surface area,
It is preferably 0.1 to 15 m ² / g, more preferably 0.5 to 12 m ² / g. The oil absorption is 10
The amount is preferably 50 ml / 100 g, more preferably 15 to 40 ml / 100 g, and further preferably 18 to 30 ml / 100 g.

The average particle diameter and the specific surface area (BET) can be measured, for example, by an air permeation method or a nitrogen gas adsorption method. The oil absorption amount (DOP) can be measured according to JISK5101.

In the present invention, in order to impart mechanical strength and other characteristics to the liquid crystalline resin composition, a filler (D) is further added.
Can be blended. The filler (D) is not particularly limited, but a fibrous, plate-like, powdery, granular or other filler can be used. Specifically, for example,
Glass fiber, PAN-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber and brass fiber,
Organic fibers such as aromatic polyamide fibers and liquid crystalline polyester fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers, alumina fibers, silica fibers, titanium oxide fibers, silicon carbide fibers, rock wool, potassium titanate whiskers, titanic acid Fibrous barium whiskers, aluminum borate whiskers, silicon nitride whiskers, etc., whisker-like fillers, mica, talc, kaolin, silica, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, titanium oxide, Examples thereof include powdery, granular or plate-like fillers such as zinc oxide, calcium polyphosphate and graphite. The surface of the above-mentioned filler used in the present invention may be treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or another surface treatment agent before use. .

Among these fillers (D), glass fiber is particularly preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and for example, long fiber type or short fiber type chopped strands and milled fibers can be selected and used. Also, two or more of these may be used in combination. As the glass fiber used in the present invention, weakly alkaline glass fiber is excellent in mechanical strength and can be preferably used. Further, the glass fiber is preferably treated with a coating or sizing agent such as an epoxy type, urethane type or acrylic type, and an epoxy type is particularly preferable. Further, it is preferably treated with a silane-based or titanate-based coupling agent or other surface treatment agent, and an epoxysilane- or aminosilane-based coupling agent is particularly preferable.

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

The amount of the filler (D) compounded is usually 25 to 300 parts by weight, preferably 30 to 250 parts by weight, more preferably 30 to 100 parts by weight, based on 100 parts by weight of the liquid crystalline resin (A). Is.

Further, the liquid crystalline resin composition of the present invention comprises
Antioxidants and heat stabilizers (eg hindered phenols, hydroquinones, phosphites and their substitutions), UV absorbers (eg resorcinol,
Salicylate), phosphite, hypophosphite, and other coloring preventing agents, lubricants and mold release agents (such as montanic acid and its metal salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax), dyes And a coloring agent containing a pigment, a carbon black as a conductive agent or a coloring agent, a crystal nucleating agent, a plasticizer, a flame retardant auxiliary agent, an ordinary additive such as an antistatic agent, and other polymers are blended to obtain a predetermined amount. Further characteristics can be imparted.

Further, depending on the necessity of further property improvement, olefin polymers such as polypropylene, polyethylene, polystyrene, etc., acid-modified olefin polymers such as maleic anhydride, ethylene / propylene copolymers, ethylene / 1- Butene copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene / propylene- 1 selected from elastomers such as g-maleic anhydride copolymers, olefin copolymers such as ABS, polyester polyether elastomers and polyester polyester elastomers
One kind or a mixture of two or more kinds can be blended to further impart predetermined characteristics.

The method of blending these additives and polymers is preferably melt kneading, and known methods can be used for melt kneading. For example, a liquid crystal resin composition can be obtained by melt-kneading at a temperature of 180 to 400 ° C. using a Banbury mixer, a rubber roll machine, a kneader, a single-screw or twin-screw extruder and the like. In that case,
1) Batch kneading method with liquid crystalline resin, filler, organopolysiloxane and other additives, 2) First, a liquid crystalline resin composition (master pellet) containing a high concentration of organopolysiloxane in the liquid crystalline resin is prepared. Then, a method of adding a liquid crystalline resin, a filler and other additives so as to obtain a specified concentration (master pellet method), 3) kneading the liquid crystalline resin and the organopolysiloxane once, and then filling the filler and other additives. Although any method such as a divided addition method of adding an additive may be used, the master pellet method is preferable among them.

If the dispersed particle size of the organopolysiloxane (B) in the liquid crystalline resin composition is 50 μm or more in a coarse dispersion form, mechanical properties are deteriorated, which is not preferable.
The smaller the blending amount of the organopolysiloxane (B) is, the smaller the dispersed particle diameter becomes, and the smaller the amount of the melt-kneading, such as the increase in the number of times of the melt-kneading, the smaller the dispersed particle diameter becomes.
Further, by using the master pellet method, the dispersed particle size is 3/4 to 1/1 as compared with the case of batch kneading.
It can be controlled to the size of 0. In the range of the extremely small amount of addition that exerts the effect of the present invention, the dispersed particle size of the organopolysiloxane in the liquid crystalline resin composition can be easily adjusted to a small range of 0.1 to 5 μm by using the master pellet method. The characteristics of the present invention can be more exerted. The dispersion morphology of the organopolysiloxane in the liquid crystalline resin composition can be measured, for example, by observing the cross section of the resin pellet with a scanning electron microscope (SEM).

The liquid crystalline resin composition of the present invention thus obtained has a high degree of flame retardancy and is excellent in thin-wall fluidity, thin-wall rigidity and low gas properties, and can be used in ordinary injection molding, extrusion molding, It can be processed into three-dimensional molded products, sheets, containers, pipes, films and fibers with excellent surface appearance (color tone), mechanical properties, heat resistance and flame retardancy by molding methods such as press molding. is there.

The liquid crystalline resin composition thus obtained is used, for example, in various gears, various cases, sensors, LEs.
D lamp, connector, socket, resistor, relay case, switch, coil bobbin, condenser, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphones, small size Motor, magnetic head base, power module, housing, semiconductor, liquid crystal display parts, FDD carriage, FDD
Chassis, HDD parts, motor brush holder,
Electric / electronic parts such as parabolic antennas and computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser disk (registered trademark) / compact disk, etc. Audio equipment parts, lighting parts, refrigerator parts, air conditioner parts, typewriter parts,
Various types of bearings such as household and office electrical products, office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, oilless bearings, stern bearings, underwater bearings, etc. , Mechanical parts such as motor parts, lighters and typewriters, optical devices such as microscopes, binoculars, cameras and watches, precision mechanical parts; alternator terminals, alternator connectors, IC regulators, light deer Various valves such as potentiometer base, exhaust gas valve,
Fuel related / Exhaust system / Intake system various pipes, Air intake nozzle snorkel, Intake manifold, Fuel pump, Engine cooling water joint, Carburetor main body, Carburetor spacer, Exhaust gas sensor, Cooling water sensor, Oil temperature sensor, Throttle position sensor, Crankshaft position sensor,
Air flow meter, brake butt wear sensor,
Thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust tributor,
Starter switches, starter relays, transmission wire harnesses, window washer nozzles, air conditioner panel switch substrates, fuel-related electromagnetic valve coils, fuse connectors, horn terminals, electrical component insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamps. It can be used for automobile / vehicle related parts such as housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, etc.

The liquid crystalline resin composition of the present invention can be practically obtained by injection molding from the viewpoint of its thin-wall fluidity and thin-walled rigidity, particularly a molded product having a thinnest portion of 0.5 mm or less. is there.

Since these molded products have extremely high flame retardancy (flame retardancy), electrical / electronic parts, particularly strict flame retardancy among the above applications, are required. It is most suitable for obtaining by injection molding an electric / electronic component having a thinnest portion of 0.5 mm or less.

[0067]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the gist of the present invention is not limited to the following examples. Liquid crystalline resin (A) (Reference Example 1) p-hydroxybenzoic acid 994 parts by weight,
126 parts by weight of 4,4'-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, 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 were added to a stirring blade and a distillation pipe. After charging in a polymerization vessel provided for 1 hour at 145 ° C., 4 hours at 145 ° C. to 250 ° C. and 1.5 hours at 250 to 330 ° C., 32
The pressure was reduced to 0.5 mmHg at 5 ° C. for 1.5 hours, and the reaction was continued for 10 minutes for polycondensation.

As a result, 8 aromatic oxycarbonyl units were obtained.
Melting point 314 ° C., melt viscosity 2 consisting of 0 molar equivalent, aromatic dioxy unit 7.5 molar equivalent, ethylenedioxy unit 12.5 molar equivalent, and aromatic dicarboxylic acid unit 20 molar equivalent.
A liquid crystalline polyester resin (A-1) of 0 Pa · s (shear rate 1000 / s, melting point + 10 ° C.) was obtained. Reference Example 2 907 parts by weight of p-hydroxybenzoic acid and 6
-Hydroxy-2-naphthoic acid (457 parts by weight) and acetic anhydride (873 parts by weight) were weighed in a polymerization vessel equipped with a stirring blade and a distillation tube, and polymerization was carried out under the same conditions as in Reference Example 1.

As a result, a melting point of 282 ° C. consisting of 73 molar equivalents of structural units derived from p-hydroxybenzoic acid and 27 molar equivalents of structural units derived from 6-hydroxy-2-naphthoic acid,
Melt viscosity 40 Pa · s (shear rate 1000 / s, melting point +1
A liquid crystalline polyester resin (A-2) having a temperature of 0 ° C. was obtained. Organopolysiloxane (B)

B-1: 400 g of toluene and 250 g of water were placed in a 2 L four-necked flask equipped with a stirrer, a cooling device, a dropping funnel, and a thermometer, and 147 g of phenyltrichlorosilane and n-propyl were cooled with an ice bath. A mixed solution of 55 g of trichlorosilane and 200 g of toluene was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 30 minutes and then refluxed for 3 hours. Then, it left still and the water layer was removed. Subsequently, water was added, and the mixture was stirred and allowed to stand to remove the aqueous layer. This water washing operation was repeated 3 times, 4% aqueous sodium hydrogen carbonate was added to the obtained toluene phase, the mixture was refluxed for 1 hour, cooled and washed 3 times with water to obtain a toluene solution of a branched organopolysiloxane. This toluene solution was filtered to remove insoluble matter, and toluene was removed by distillation under reduced pressure to obtain 115.2 g of the following solid branched organopolysiloxane (B-1). Average molecular formula: (nPrSiO _3/2 ) _0.30 (PhS
iO _3/2 ) _0.70 (HO _1/2 ) _0.44 (a = 0, b = 1.00, c = 0, d = 0, e = 0.4
4) (nPr = n-propyl group, Ph = phenyl group) Weight average molecular weight = 1600, softening point = 70 ° C. Total monovalent hydrocarbon group total of R ¹ and R ² Content of aryl group = 70 mol % Hydroxyl content = 6.0% by weight

B-2: A 300 mL four-necked flask equipped with a stirrer, a cooling device and a thermometer was charged with 35 g of the branched organopolysiloxane (B-1) obtained by the above method and 130 g of a dry toluene solution, Subsequently, 6 g of hexadimethyldisilazane was added, and the mixture was stirred at room temperature for 3 hours. Then, it stirred at 70 degreeC for 1 hour. The low-boiling substance was distilled under reduced pressure to obtain 35.7 g of the following colorless solid branched organopolysiloxane (B-2). Average molecular formula: (Me ₃ SiO _1/2 ) _0.05 (nPr
_{SiO 3/2) 0.29 - (PhSiO 3/2} )
_0.66 (HO _1/2 ) _0.10 (a = 0.05, b = 0.95, c = 0, d = 0, e =
0.10) (Me = methyl group, nPr = n-propyl group, Ph = phenyl group) Weight average molecular weight = 6760, softening point = 140 ° C. Aryl in all monovalent hydrocarbon groups obtained by summing R ¹ and R ^2. Group content = 60 mol% Hydroxyl content = 1.4% by weight

B-3: 400 g of toluene and 250 g of water were placed in a 2 L four-necked flask equipped with a stirrer, a cooling device, a dropping funnel, and a thermometer, and 21 g of phenyltrichlorosilane and n-propyl were cooled in an ice bath. A mixed solution of 164 g of trichlorosilane and 200 g of toluene was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 30 minutes and then refluxed for 3 hours. Then, it left still and the water layer was removed. Subsequently, water was added, and the mixture was stirred and allowed to stand to remove the aqueous layer. This water washing operation was repeated 3 times, 4% aqueous sodium hydrogen carbonate was added to the obtained toluene phase, the mixture was refluxed for 1 hour, cooled and washed 3 times with water to obtain a toluene solution of a branched organopolysiloxane. This toluene solution was filtered to remove insoluble materials, and toluene was removed by distillation under reduced pressure to obtain 94.5 g of the following solid branched organopolysiloxane (B-3). Average molecular formula: (nPrSiO _3/2 ) _0.90 (PhS
iO _3/2 ) _0.10 (HO _1/2 ) _0.44 (a = 0, b = 1.00, c = 0, d = 0, e = 0.4
4) (nPr = n-propyl group, Ph = phenyl group) Weight average molecular weight = 1900, softening point = 60 ° C. Content of aryl group in total monovalent hydrocarbon group of R ¹ and R ² = 10 mol % Hydroxyl content = 7.3% by weight

B-4: 40 mL of water in a 2 L four-necked flask equipped with a stirring device, a cooling device, a dropping funnel, and a thermometer.
0 g and 300 g of methyl isobutyl ketone were put in and vigorously stirred so as not to form two layers, and 149 g of methyltrichlorosilane dissolved in 100 g of methyl isobutyl ketone was added thereto so that the temperature of the reaction mixture did not exceed 50 ° C. It was dripped slowly. Then, the reaction mixture was heated and stirred at 50 ° C. for 2 hours. After completion of the reaction, the organic phase was washed until the washing water became neutral, and then the organic phase was dried using a desiccant. After removing the desiccant, the low boiling point substances were distilled off under reduced pressure, and vacuum drying was carried out for 8 hours to obtain 56.9 g of the following branched organopolysiloxane (B-4). Average molecular formula: (MeSiO _3/2 ) _1.00 (HO
_1/2 ) _0.19 (a = 0, b = 1.00, c = 0, d = 0, e = 0.1
9) (Me = methyl group) Weight average molecular weight = 7600, softening point = 50 ° C. Total monovalent hydrocarbon group of R ¹ and R ² Content of aryl group = 0 mol% Content of hydroxyl group = 4 .7% by weight

B-5: Stirring device, cooling device, reflux device,
A 200 mL flask equipped with a dropping funnel and a thermometer was charged with 79.0 g of phenyltrimethoxysilane, 14.1 g of octamethyltetracyclosiloxane, and 0.05 g of trifluoromethanesulfonic acid (manufactured by Kanto Kagaku), and heated with a mantle heater to 70 The mixture was heated and stirred at -80 ° C for 2 hours. Next, 6.8 g of water was added dropwise over about 1 hour. Since the methanol generated during the dropping was refluxed, heating and stirring was continued at the reflux temperature (65 to 70 ° C.) for 4 hours. After the reaction was completed, the reaction mixture was cooled, and ammonia gas was bubbled until the system became weakly alkaline. Next, 20 mmHg (2.7 kP
The mixture was heated and stirred at 80 ° C. under reduced pressure of aA) to remove by-produced methanol, unreacted raw materials and low-molecular-weight products. After cooling, the neutralized salt was removed with a glass filter to obtain a colorless and transparent liquid (B-5) shown below. The viscosity of the liquid at 25 ° C. was 153 centistokes. Average molecular formula: (Me ₂ SiO _2/2 ) _0.33 (PhS
iO _3/2 ) _0.67 (MeO _1/2 ) _0.73 (Me = methyl group, Ph = phenyl group) Weight average molecular weight = 1300, liquid R1 and R2, and monovalent hydrocarbon group of bifunctional siloxane unit The content of aryl groups in the total monovalent hydrocarbon groups totaled by 50 mol% = the content of methoxy groups = 17.7 wt% In the above, the weight average molecular weight and the average molecular formula were determined as follows. Weight average molecular weight measuring method: measuring instrument; HLC-8020 (manufactured by Tosoh Corporation) gel permeation chromatography (GPC) detector; refractive index detector sample; 1% by weight organopolysiloxane chloroform solution flow rate; 1 mL / min.

Calculation method of average molecular formula: Sample; Calculation method of heavy chloroform solution of organopolysiloxane; Average molecular formula was determined from ¹³ C-NMR and ²⁹ Si-NMR measurement charts. Examples 1-11, Comparative Examples 1-6

TE made by Japan Steel Works equipped with a side feeder
Liquid crystalline resin (A), organopolysiloxane (B) and calcium carbonate (C) obtained in Reference Example with an X30 type twin-screw extruder (Micropowder 3S manufactured by Bihoku Kouka Co., Ltd .:
Average particle size 1.0 μm, BET specific surface area 8.5 m ² / g,
2. DOP oil absorption 20 ml / 100 g) was charged from the hopper, and the filler (D) (glass chopped strand ECS-03T-790DE / P manufactured by Nippon Electric Glass Co., Ltd., fiber length 3.
2 mm, monofilament diameter 6.6 μm) was charged from the side,
Adjust the cylinder heater set temperature so that the resin temperature is the melting point + 10 ° C, and rotate the screw 100 rpm.
Were melt-kneaded under the conditions described above to obtain pellets. After hot air drying, the pellets were made into Sumitomo Nestal injection molding machine Promat 40/2.
5 (Sumitomo Heavy Industries, Ltd.), the mold temperature 90
℃, set the cylinder temperature to the melting point +10 ℃, the condition of 1 speed 1 pressure (injection speed 99%, injection pressure minimum filling pressure + 5k
The test pieces for measurement of (1) to (6) below were injection molded with gf / cm ² ). In Examples 2 to 4, master pellets based on a liquid crystalline polyester resin (A-1, A-2) having an organopolysiloxane (B-1, B-2) concentration of 20% by weight were prepared. Was blended so as to have the blending amount shown in the table.

Each evaluation was measured according to the following method. (1) Gas generation thermogravimetric measuring device Using TGA7 manufactured by Perkin Elmer Co., Ltd., one pellet (about 10 mg) of the liquid crystalline resin composition was melted in a nitrogen stream under the melting point of the liquid crystalline polyester resin + 10 ° C.
The weight loss after heating for 30 minutes was measured.

(2) Dispersion particle diameter of the component (B): width 12.7 mm × length 150 mm × thickness 0.5 mm The center of the cross section parallel to the length direction of the center in the width direction of the molded product. The part was observed with a scanning electron microscope (SEM), the major axis of the particles was measured, and the number average dispersed particle diameter was calculated for 50 particles.

(3) Difficult to ignite (average burning time) A molded product of length 150 x width 12.7 x thickness 0.4 mm is UL
A combustion test was performed according to the 94 standard, and the combustion time (seconds) from the time when the flame was released 10 seconds after the primary flame contact to the extinction was evaluated. Those that did not ignite were set to 0 seconds, and the results of 10 pieces were averaged to obtain the average burning time. The shorter the average burning time, the better the flame retardancy (flame retardancy).

(4) Thin-wall fluidity (bar flow length) A mold having a width of 12.7 mm, a length of 150 mm and a thickness of 0.3 mm was used in the above molding machine, and the injection speed was 99% and the injection pressure was 5
Molded at 00 kgf / cm ² , the resin flowing from the side gate at one end is a few mm in the length direction of the molded product.
It was evaluated whether to fill up to that point. The evaluated filling length (bar flow length) is the length up to the position where the flow molded product is completely filled in the width direction. The larger the length, the better the thin-wall fluidity.

(5) Thin-walled rigidity (0.5 mm thick bending strength) The bending strength of a molded product having a width of 12.7 mm, a length of 150 mm and a thickness of 0.5 mm was measured by the above-mentioned molding machine according to ASTM D790. The larger the measured value, the better the thin wall rigidity.

(6) Thin wall anisotropy (anisotropy of thin wall bending strength) A rectangular plate molded product having a side of 50 mm square × thickness 1 mm and a side of a film gate is injection speed 50%, injection pressure 800 kgf / cm. Molded with ² , the flow end direction from the gate is MD, the right angle direction is TD, and cut with a width of 12.7 mm parallel to each direction of MD and TD, and a length of 50 m.
Cutting pieces of m × width 12.7 mm × thickness 1 mm were obtained.

The bending strength of the cutting pieces in the MD and TD directions was measured according to ASTM D790, and the anisotropy of the thin-wall bending strength was calculated as (bending strength of cutting pieces in MD direction / bending strength of cutting pieces in TD direction). did. The smaller the calculated value, the better the low anisotropy.

[0084]

[Table 1]

From Table 1, by adding a small amount of the organopolysiloxane (B) having the specific structure of the present invention, the combustion time becomes almost 0, which makes it difficult to ignite. In particular, the organopolysiloxane (B) produced by the master pellet method is used. When compounded (Examples 2 to 4), it can be seen that even a very small amount makes the composition more difficult to ignite. Further, by using calcium carbonate (C) in combination with organopolysiloxane (B), the ignition resistance is improved. On the other hand, with the organopolysiloxane having a structure other than that of the present invention, the flame retardant effect cannot be obtained even if a large amount is blended. When the organopolysiloxane of the present invention is blended, fluidity and rigidity are further improved, and the effect of suppressing generated gas and anisotropy is obtained.

Comparative Example 7 Toray as an organopolysiloxane instead of B-1
DC4-7081 made by Dow Corning Silicone (a methylsiloxane type silicone rubber powder containing a methacryl group as a reactive functional group and containing 30% by weight of silica for powderization, in all monovalent hydrocarbon groups) Example 1 except that the aryl group content = 0 mol%) was used.
150 x length 12.7 x thickness 0.4mm
A molded product of No. 1 was obtained and a combustion test was conducted according to UL94 standard.
The average burning time is about 10 seconds, and UL94 is evaluated as V-
It was 2. On the other hand, the evaluation of UL94 in Example 1 was V-0.

Comparative Examples 8 and 9 Molded articles prepared in the same manner as in Example 6 and Comparative Example 1 except that a polycarbonate resin (Upilon S3000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) was used in place of the liquid crystalline resin (A). Then, the above (3) to (6) were evaluated. As the filler, the same glass fiber as in Example 6 was used, and in Comparative Example 8 only, 3 parts by weight of organopolysiloxane B-1 was blended. B for 100 parts by weight of polycarbonate resin
When -1 is not blended (Comparative Example 9), UL94 is evaluated as V.
However, even if 3 parts by weight of B-1 was added to 100 parts by weight of the polycarbonate resin (Comparative Example 8), the burning time was slightly shortened, but cotton ignited due to drip and V-
It was 2. Further, the rod flow length was 18 mm with or without blending B-1, and the thin-wall fluidity did not change. In addition, the bending strength of 0.5 mm was 180 MPa when B-1 was not blended (Comparative Example 9) and 171 MPa when B-1 was blended (Comparative Example 8), and the thin-wall rigidity was significantly reduced. Also, the thin-wall anisotropy was substantially changed to 1.58 when B-1 was added (Comparative Example 8) and 1.58 when B-1 was not added (Comparative Example 9). There was no.

Comparative Example 10 A molded article was obtained in the same manner as in Comparative Example 8 except that B-2 was used in place of the organopolysiloxane B-1, and the above (3) to (6) were evaluated. Even if 3 parts by weight of B-2 was added to 100 parts by weight of the polycarbonate resin (Comparative Example 10), UL94 evaluation was that the burning time was slightly shortened, but cotton was ignited by the drip and no organopolysiloxane was added (Comparative Example). It was V-2 as in 9). The rod flow length was 18 mm, and the thin-wall fluidity did not change with or without B-2. In addition, the bending strength of 0.5 mm is 173 MPa when B-2 is mixed,
By compounding, the thin-walled rigidity was significantly reduced. The thin-wall anisotropy was also 1.58 when B-2 was added, and there was no substantial change in the anisotropy even when blended.

As described above, the effect obtained by blending the organopolysiloxane (B) having the specific structure of the present invention in an extremely small amount is not a polycarbonate resin but a liquid crystal resin-specific effect.

[0090]

According to the present invention, by mixing the liquid crystalline resin (A) with the organopolysiloxane (B) having a specific structure, it is possible to obtain an unprecedentedly high degree of flame retardancy and to achieve thin-wall fluidity. , Thin-walled rigidity, low gas properties, and liquid crystal resin composition excellent in low anisotropy can be obtained, so that electric / electronic parts, home / office electric appliance parts, office computer related parts, telephone related parts, facsimile related parts, It is possible to provide materials suitable for copying machine-related parts.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshiki Makabe             1 East of 9 Oemachi, Minato-ku, Nagoya City, Aichi Prefecture             Les Nagoya Office (72) Inventor Haruhiko Furukawa             2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow             Corning Silicone Co., Ltd. R & D             In headquarters (72) Inventor Koji Morita             2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow             Corning Silicone Co., Ltd. R & D             In headquarters F term (reference) 4J002 CF003 CF041 CF101 CF161                       CL003 CL081 CP032 DA017                       DA067 DE187 DE226 DJ007                       DK007 DL007 FA047 FB097                       FD013 FD017 FD136

Claims (7)

[Claims] 1. To 100 parts by weight of the liquid crystalline resin (A)
And the average molecular formula: (R ¹ _ThreeSiO_1/2)_a(R²SiO
_3/2)_b(SiO_4/2)_c(R³O_1/2)_d(H
O_1/2)_e(In the formula, R¹And R²Are carbon atoms
Alkyl group having 1 to 12 carbon atoms and aryl having 6 to 12 carbon atoms
A monovalent hydrocarbon group selected from the group consisting of
¹And R²Containing aryl groups in all monovalent hydrocarbon groups
The amount is 15 to 100 mol%. R³Is an alkyl group
It a is 0 or a positive number, b is a positive number, and c, d
And e is 0 or a positive number. )
Blended with 0.01 to 5 parts by weight of Luganopolysiloxane (B)
A liquid crystalline resin composition obtained by 2. The liquid crystalline resin composition according to claim 1, wherein the liquid crystalline resin (A) is a liquid crystalline polyester resin and / or a liquid crystalline polyesteramide resin. 3. The liquid crystal polyester resin is a structural unit shown below.
The liquid crystalline resin composition according to claim 2, comprising a structural unit selected from (I), (II), (III) and (IV). [Chemical 1] (However, R ⁴ in the formula is It represents one or more groups selected from, R ⁵ is embedded image R ⁶ represents one or more groups selected from And one or more groups selected from However, in the formula, X represents a hydrogen atom or a chlorine atom. ) 4. A carbonate of a metal of Group 1A of the Periodic Table of Elements and / or 2 per 100 parts by weight of the liquid crystalline resin (A).
4. The liquid crystalline resin composition according to claim 1, further comprising 0.01 to 10 parts by weight of a Group A metal carbonate (C). 5. The weight composition ratio (B) / (C) of the organopolysiloxane (B) and the carbonate of a metal of Group 1A and / or the carbonate of a metal of Group 2A (C) is 2/1. ~
It is 1/3, The liquid crystalline resin composition of Claim 4 characterized by the above-mentioned. 6. The liquid crystal resin (A) according to claim 1, further comprising 25 to 300 parts by weight of the filler (D) with respect to 100 parts by weight of the liquid crystalline resin (A). The liquid crystalline resin composition of. 7. A molded article for electric / electronic parts, which has a thinnest portion of 0.5 mm or less and is obtained by injection-molding the liquid crystalline resin composition according to claim 1.