Shaped article of liquid crystalline polymer

• US 5,830,940 A
• Filed: 07/18/1996
• Issued: 11/03/1998
• Est. Priority Date: 12/28/1993
• Status: Expired due to Term

• Current Assignee: Toray Industries Incorporated
• Original Assignee: Toray Industries Incorporated
• Inventors: Kitajima, Norio, Nakamura, Kiyokazu, Inoue, Toshihide
• Primary Examiner(s): Short, Patricia A.
• Application Number:
  US08/683,246
• Time in Patent Office: 838 Days
• Field of Search: 525/132, 525/133, 525/152, 524/449, 524/451, 524/513, 524/514, 524/404, 524/413, 524/406, 524/415, 524/425, 524/445, 524/452, 524/456
• US Class Current: 524/404
• CPC Class Codes: B29C 45/0001 characterised by the choice of material
• CPC Class Codes: B29K 2105/0079 Liquid crystals
• CPC Class Codes: C08L 23/00 Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 2666/04 Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
• CPC Class Codes: C08L 2666/06 Homopolymers or copolymers of unsaturated hydrocarbons; Derivatives thereof
• CPC Class Codes: C08L 67/00 Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain of polyester-amides C08L77/12; of polyester-imides C08L79/08; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 77/12 Polyester-amides

Abstract

The present invention relates to a shaped article of a liquid crystalline polymer containing (A) 100 parts by weight of a liquid crystalline polyester and/or liquid crystal polyesteramide capable of forming an anisotropic melt and (B) 0.01 to 2 parts of an olefinic polymer and having a retention rate of a weld strength of 15% to 100%, which has excellent heat stability, mechanical properties, dimensional stability and mold releasability and is suitable for various application uses such as electrical and electronical related devices, accurate machine related devices, office related devices, automobile related parts.

Claims

1. A shaped article of a liquid crystalline polymer having a weld, which is provided by plural melted resin flows encountering in a mold, obtained by melt molding a composition comprising (A) 100 parts by weight of at least one liquid crystalline polymer capable of forming an anisotropic melt selected from the group consisting of liquid crystalline polyesters and liquid crystalline polyester amides and (B) 0.01 to 2 parts by weight of at least one olefinic polymer, having a weight-average molecular weight of 10,000 to 600,000, selected from the group consisting of (a) polyethylene, (b) polypropylene, (c) copolymers of ethylene and α

-olefin having 3 or more carbon atoms, (d) copolymers of propylene and α

-olefin having 4 or more carbon atoms, (e) copolymers of ethylene, α

-olefin having 3 or more carbon atoms and a non-conjugated diene and (f) copolymers of propylene, α

-olefin having 4 or more carbon atoms and a non-conjugated diene, and (C) 400 parts by weight or less of a filler selected from the group consisting of carbon fiber, aromatic polyamide fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, asbestos fiber, mica, talc, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, titanium oxide, calcium polyphosphate, graphite, granular and plate fillers, based upon 100 parts by weight of the liquid crystalline polymer (A), said composition having a retention rate of a weld strength of 15% to 100% obtained by the following formula (1), based upon flexural strengths determined from a weld shaped article (X) having a weld, which is provided by plural melted resin flows encountering in the mold, at substantially the center portion thereof and a non-weld shaped article (Y) having no weld therein, both obtained by injection molding the composition under the following conditions;

space="preserve" listing-type="equation">Retention rate of weld strength (%)=(Flexural strength of shaped article (X) having weld/Flexural strength of shaped article (Y) having no weld)×

100 (1)

Injection molding condition;

Cylinder temperature;

Melting point (°

C.) of liquid crystalline polymer+10°

C.

Mold temperature;

90°

C.

Size of shaped article;

6.0 mm (width)×

127 mm (length)×

1 mm (thickness).

2. A shaped article as claimed in claim 1, having the weld portion with a retention rate of a weld strength is 20% to 100%.

3. A shaped article as claimed in claim 1, wherein the liquid crystalline polymer (A) is at least one polymer selected from the group consisting of fully aromatic liquid crystalline polyesters, fully aromatic liquid crystalline polyesteramides, liquid crystalline polyesters having an ethylenedioxy unit, and liquid crystalline polyesteramides having an ethylenedioxy unit.

4. A shaped article as claimed in claim 3, wherein the liquid crystalline polymer (A) is at least one polymer selected from the group consisting of liquid crystalline polyesters having an ethylenedioxy unit and liquid crystalline polyesteramides having an ethylenedioxy unit.

5. A shaped article as claimed in claim 4, wherein the liquid crystalline polyester (A) is at least one liquid crystalline polyesters composed of the following structural units (I), (III) and (IV), liquid crystalline polyesters composed of the following structural units (I), (II) and (IV), and liquid crystalline polyesters having the following structural units (I), (II), (III) and (IV):

##STR10## wherein R₁ represents at least one group selected from the group consisting of;

##STR11## and R₂ represents at least one group selected from the group consisting of;

##STR12## wherein X represents a hydrogen atom or chlorine atom, and the total number of moles of structural unit (II) and structural (III) are substantially equal to the total of the number of moles of structural unit (IV).

6. A shaped article as claimed in claim 1, wherein said fillers are surface treated with a silane or titanate coupling agent.

7. A shaped article as claimed in claim 1, wherein said composition contains 70 to 200 parts by weight of said filler, based upon 100 parts by weight of the liquid crystalline polymer (A).

8. A shaped article as claimed in claim 1, wherein the weight-average molecular weight of the olefinic polymer is 30,000 to 600,000.

9. A shaped article as claimed in claim 1 further comprising 0.5 to 60 parts by weight of an organic bromine compound selected from the group consisting of hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromobiphenylether, octabromodiphenylether, hexabromodiphenylether, bis(pentabromophenoxy)ethane, ethylene-bis(tetrabromophthalimide), tetrabromobisphenol A, brominated polycarbonate oligomers, copolymers of brominated polycarbonate oligomers with bisphenol A that are manufactured using brominated bisphenol A as a raw material, brominated diepoxy compounds obtained by reaction of brominated bisphenol A and epichlorohydrin, monoepoxy compounds obtained by reaction of brominated phenols and epichlorohydrin, condensation products of poly(brominated benzylacrylate), brominated polyphenylene ether, brominated bisphenol A, cyanuryl chloride, brominated phenol, halogenated polymers and halogenated oligomers, based upon 100 parts by weight of the liquid crystalline polymer (A).

10. A shaped article of a liquid crystalline polymer having a weld, which is provided by plural melted resin flows encountering in a mold, obtained by melt molding a composition comprising (A) 100 parts by weight of at least one liquid crystalline polymer capable of forming an anisotropic melt selected from the group consisting of liquid crystalline polyesters and liquid crystalline polyester amides and (B) 0.01 to 2 parts by weight of at least one olefinic polymer, having a weight-average molecular weight of 10,000 to 600,000, selected from the group consisting of (a) polyethylene, (b) polypropylene, (c) copolymers of ethylene and α

-olefin having 3 or more carbon atoms, (d) copolymers of propylene and α

-olefin having 4 or more carbon atoms, (e) copolymers of ethylene, α

-olefin having 3 or more carbon atoms and a non-conjugated diene and (f) copolymers of propylene, α

-olefin having 4 or more carbon atoms and a non-conjugated diene, and (C) 0.5 to 60 parts by weight of an organic bromine compound selected from the group consisting of hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromobiphenylether, octabromodiphenylether, hexabromodiphenylether, bis(pentabromophenoxy)ethane, ethylene-bis(tetrabromophthalimide), tetrabromobisphenol A, brominated polycarbonate oligomers, copolymers of brominated polycarbonate oligomers with bisphenol A that are manufactured using brominated bisphenol A as a raw material, brominated diepoxy compounds obtained by reaction of brominated bisphenol A and epichlorohydrin, monoepoxy compounds obtained by reaction of brominated phenols and epichlorohydrin, condensation products of poly(brominated benzylacrylate), brominated polyphenylene ether, brominated bisphenol A, cyanuryl chloride, brominated phenol, halogenated polymers and halogenated oligomers, based upon 100 parts by weight of the liquid crystalline polymer (A), said composition having a retention rate of a weld strength of 15% to 100% obtained by the following formula (1), based upon flexural strengths determined from a weld shaped article (X) having a weld, which is provided by plural melted resin flows encountering in a mold, at substantially the center portion thereof and a non-weld shaped article (Y) having no weld therein, both obtained by injection molding the composition under the following conditions;

space="preserve" listing-type="equation">Retention rate of weld strength (%)=(Flexural strength of shaped article (X) having weld/Flexural strength of shaped article (Y) having no weld)×

100 (1)

Injection molding condition;

Cylinder temperature;

Melting point (°

C.) of liquid crystalline polymer+10°

C.

Mold temperature;

90°

C.

Size of shaped article;

6.0 mm (width)×

127 mm (length)×

1 mm (thickness).

11. A shaped article as claimed in claim 10, wherein said organic bromine compound is included in an amount in the composition at a bromine content of 20% by weight or more.

12. A shaped article as claimed in claim 10, wherein said composition contains 1 to 30 parts by weight of said organic bromine compound, based upon 100 parts by weight of the liquid crystalline polymer (A).

13. A shaped article as claimed in claim 10, wherein said organic bromine compound is dispersed in the composition at an average diameter of 25 μ

m or less.

14. A shaped article as claimed in claim 10, having the weld portion with a retention rate of a weld strength is 20% to 100%.

15. A shaped article as claimed in claim 10, wherein the liquid crystalline polymer (A) is at least one polymer selected from the group consisting of fully aromatic liquid crystalline polyesters, fully aromatic liquid crystalline polyesteramides, liquid crystalline polyesters having an ethylenedioxy unit, and liquid crystalline polyesteramides having an ethylenedioxy unit.

16. A shaped article as claimed in claim 15, wherein the liquid crystalline polymer (A) is at least one polymer selected from the group consisting of liquid crystalline polyesters having an ethylenedioxy unit and liquid crystalline polyesteramides having an ethylenedioxy unit.

17. A shaped article as claimed in claim 16, wherein the liquid crystalline polyester (A) is at least one liquid crystalline polyesters composed of the following structural units (I), (III) and (IV), liquid crystalline polyesters composed of the following structural units (I), (II) and (IV), and liquid crystalline polyesters having the following structural units (I), (II), (III) and (IV):

##STR13## wherein R₁ represents at least one group selected from the group consisting of;

##STR14## and R₂ represents at least one group selected from the group consisting of;

##STR15## wherein X represents a hydrogen atom or chlorine atom, and the total number of moles of structural unit (II) and structural unit (III) are substantially equal to the total of the number of moles of structural unit (IV).

18. A shaped article as claimed in claim 10, wherein the weight-average molecular weight of the olefinic polymer is 30,000 to 600,000.

19. A shaped article as claimed in claim 10, wherein said brominated diepoxy compound is represented by the general formula (i):

##STR16## wherein n is 15 or more.

20. A shaped article as claimed in claim 10, wherein the brominated polycarbonate oligomer is represented by formula (iv):

##STR17## wherein R³ and R⁴ represent substituted or unsubstituted aryl groups, and n is 4 or more.

21. A shaped article as claimed in claim 10, wherein the composition further contains 0.01 to 10 parts by weight of carbon black, based upon 100 parts by weight of the liquid crystalline polymer (A).