Title:
HOLLOW MOLDED PRODUCT COMPRISING ETHYLENE-2,6-NAPHTHALENE DICARBOXYLATE POLYMER AND ULTRAVIOLET ABSORBER AND PRODUCTION PROCESS THEREFOR
Document Type and Number:
WIPO Patent Application WO/2000/055255
Kind Code:
A2
Abstract:
A hollow molded product which contains a polyester composition containing an ethylene-2,6-naphthalene dicarboxylate polymer and at least one ultraviolet absorber in an amount of 0.01 to 5.0 wt% based on the ethylene-2,6-naphthalene dicarboxylate polymer, and which has a birefringence factor ($g(D)n) of the barrel portion of 0.17 or more, and a process for preparation thereof.
Inventors:
Yoshida, Yoichi (Teijin Limited, Matsuyama Factory 77, Kitayoshida-cho Matsuyama-shi Ehime, 791-8041, JP)
Suzuki, Minoru (Teijin Limited, Matsuyama Factory 77, Kitayoshida-cho Matsuyama-shi Ehime, 791-8041, JP)
Nagano, Hiroki (Teijin Limited, Matsuyama Factory 77, Kitayoshida-cho Matsuyama-shi Ehime, 791-8041, JP)
Application Number:
PCT/JP2000/001644
Publication Date:
September 21, 2000
Filing Date:
March 17, 2000
Assignee:
TEIJIN LIMITED (6-7 Minamihommachi 1-chome Chuo-ku Osaka-shi Osaka, 541-0054, JP)
Yoshida, Yoichi (Teijin Limited, Matsuyama Factory 77, Kitayoshida-cho Matsuyama-shi Ehime, 791-8041, JP)
Suzuki, Minoru (Teijin Limited, Matsuyama Factory 77, Kitayoshida-cho Matsuyama-shi Ehime, 791-8041, JP)
Nagano, Hiroki (Teijin Limited, Matsuyama Factory 77, Kitayoshida-cho Matsuyama-shi Ehime, 791-8041, JP)
International Classes:
B65D1/02; B29C49/02; B32B27/36; B65D1/00; B65D65/02; B65D65/20; B65D65/40; B65D81/30; C08J3/22; C08J5/00; C08K5/00; C08K5/3475; C08K5/3492; C08K5/357; C08L67/02; B29K67/00; B29K105/16; B29L22/00; (IPC1-7): C08L67/00
Attorney, Agent or Firm:
Ohshima, Masataka (Ohshima Patent Office Fukuya Building 3, Yotsuya 4-chome Shinjuku-ku Tokyo, 160-0004, JP)
Claims:
CLAIMS
| 1. |
A hollow molded product (A1) which comprises a polyester composition comprising an ethylene2,6 naphthalene dicarboxylate polymer which has 2,6 naphthalenedicarboxylic acid component in an amount of at least 80 mol% based on the total of all the dicarboxylic acid components and ethylene glycol component in an amount of at least 80 mol% based on the total of all the glycol components and at least one ultraviolet absorber selected from the group consisting of a benzotriazole compound, triazine compound, benzophenone compound, cyanoacrylate compound and benzooxazinone compound in an amount of 0.01 to 5.0 wt% based on the ethylene2,6naphthalene dicarboxylate polymer, and (B1) which has a birefringence factor (An) of the barrel portion of 0.17 or more. |
| 2. |
The hollow molded product of claim 1, wherein the barrel portion has a haze of 15 % or less. |
| 3. |
The hollow molded product of claim 1, wherein the barrel portion has a refractive index (nZ) in a thickness direction of 1.54 or less. |
| 4. |
The hollow molded product of claim 1 which has a b value of 5 or less. |
| 5. |
The hollow molded product of claim 1, wherein the ethylene2,6naphthalene dicarboxylate polymer has a carboxyl terminal group concentration of 32 equivalents/106 g of the polymer or less. |
| 6. |
The hollow molded product of claim 1, wherein the ethylene2,6naphthalene dicarboxylate polymer has an aldehyde content of 30 ppm or less. |
| 7. |
The hollow molded product of claim 1, wherein the ethylene2,6naphthalene dicarboxylate polymer has at least one glycol component selected from the group consisting of cyclohexane dimethanol and neopentyl glycol in an amount of 20 mol% or less based on the total of all the glycol components. |
| 8. |
The hollow molded product of claim 1, wherein the polyester composition further comprises an hindered amine antioxidant in an amount of 0.1 to 5.0 wt% based on the ethylene2,6naphthalene dicarboxylate polymer. |
| 9. |
The hollow molded product of claim 1 which is a bottle. |
| 10. |
A preform for producing the hollow molded product of claim 1. |
| 11. |
A hollow molded product which has a laminate structure consisting of an outer layer of the polyester composition of claim 1 and an inner layer of an ethylene2,6naphthalene dicarboxylate polymer which does not contain an ultraviolet absorber or contains at least one ultraviolet absorber selected from the group consisting of the ultraviolet absorbers specified in claim 1 andhas abirefringence factor of the barrel portion of 0.17 or more. |
| 12. |
The hollow molded product of claim 11, wherein the inner layer contains an ultraviolet absorber which is the same compound as the ultraviolet absorber contained in the outer layer and the content of the ultraviolet absorber in the inner layer is lower than the content of the ultraviolet absorber in the outer layer. |
| 13. |
The hollow molded product of claim 11, wherein the outer layer has a thickness of 10 to 100 pm. |
| 14. |
The hollow molded product of claim 11 which is a bottle. |
| 15. |
A preform for producing the hollow molded product of claim 11. |
| 16. |
A process for producing a hollow molded product comprising the steps of: (1) dry blending an ethylene2,6naphthalene dicarboxylate polymer which comprises 2,6 naphthalenedicarboxylic acid component in an amount of at least 80 mol% based on the total of all the dicarboxylic acid components and ethylene glycol component in an amount of at least 80 mol% based on the total of all the glycol components <BR> <BR> <BR> <BR> with at least one ultraviolet absorber selected from the group consisting of a benzotriazole compound, triazine compound, benzophenone compound, cyanoacrylate compound and benzooxazinone compound in an amount of 0.01 to 5.0 wt% based on the ethylene2,6naphthalene dicarboxylate polymer, or dry blending the above ethylene2,6naphthalene dicarboxylate polymer with a master polymer which contains both the above ethylene2,6naphthalene dicarboxylate polymer and at least one of the above ultraviolet absorbers in an amount of 1 to 10 wt% based on the ethylene2,6 naphthalene dicarboxylate polymer to ensure that the content of the ultraviolet absorber should become 0.01 to 5.0 wt% based on the ethylene2,6naphthalene dicarboxylate polymer; (2) melt molding the obtained dry blend into a preform; and (3) blow molding the obtained preform into the hollow molded product having a birefringence factor of the barrel portion of 0.17 or more. |
| 17. |
A hollow molded product (A2) which comprises a polyester composition comprising an ethylene2,6 naphthalene dicarboxylate polymer which has 2,6 naphthalenedicarboxylic acid component in an amount of at least 80 mol% based on the total of all the dicarboxylic acid components and ethylene glycol component in an amount of at least 80 mol% based on the total of all the glycol components and at least one pigment selected from the group consisting of an oxide pigment, ferrocyanide pigment, silicate pigment, phosphate pigment, carbon black, condensation polycyclic pigment and phthalocyanine pigment in an amount of 10 to 2,000 ppm, and (B2) which has a haze of the barrel portion of 10 % or less. |
| 18. |
The hollow molded product of claim 17, wherein a polymerization catalyst for the ethylene2,6naphthalene dicarboxylate polymer is an antimony compound or a germanium compound. |
| 19. |
The hollow molded product of claim 17, wherein the ethylene2,6naphthalene dicarboxylate polymer has an acetaldehyde content of 30 ppm or less. |
| 20. |
The hollow molded product of claim 17, wherein the ethylene2,6naphthalene dicarboxylate polymer has at least one glycol component selected from the group consisting of cyclohexane dimethanol and neopentyl glycol in an amount of 20 mol% or less based on the total of all the glycol components. |
| 21. |
The hollow molded product of claim 17 which is a bottle. |
| 22. |
A preform for producing the hollow molded product of claim 17. |
| 23. |
A process for producing a hollow molded product comprising the steps of: (1) dry blending an ethylene2,6naphthalene dicarboxylate polymer which comprises 2,6 naphthalenedicarboxylic acid component in an amount of at least 80 mol% based on the total of all the dicarboxylic acid components and ethylene glycol component in an amount of at least 80 mol% based on the total of all the glycol components with at least one pigment selected from the group consisting of an oxide pigment, ferrocyanidepigment, silicate pigment, phosphate pigment, carbon black, condensation polycyclic pigment and phthalocyanine pigment in an amount of 10 to 2,000 ppm, or dry blending the above ethylene2,6naphthalene dicarboxylate polymer with a master polymer which contains both the above ethylene2,6naphthalene dicarboxylate polymer and at least one of the above pigments in an amount of 0.01 to 1.0 wt% based on the ethylene2,6naphthalene dicarboxylate polymer to ensure that the content of the pigment should become 10 to 2,000 ppm; (2) melt molding the obtained dry blend into a preform; and (3) blow molding the obtained preform into the hollow molded product having a haze of the barrel portion of 10 % or less. |
| 24. |
The process of claim 23, wherein the master polymer has been prepared by melt mixing the ethylene2,6naphthalene dicarboxylate polymer and the pigment with an extruder. |
| 25. |
The process of claim 23, wherein the master polymer has been produced by adding a pigment at any point from an ester exchange rection to the end of a polycondensation rection for the production of the ethylene2,6naphthalene dicarboxylate polymer or any point from a direct esterification rection to the end of the polycondensation rection. |
| 26. |
The process of claim 23, wherein the master polymer is used in an amount of 0.5 to 10 wt% based on the ethylene2,6naphthalene dicarboxylate polymer. |
| 27. |
A hollow molded product (A3) which comprises a polyester composition comprising an ethylene2,6 naphthalene dicarboxylate polymer which has 2,6 naphthalenedicarboxylic acid component in an amount of at least 80 mol% based on the total of all the dicarboxylic acid components and ethylene glycol component in an amount of at least 80 mol% based on the total of all the glycol components, at least one ultraviolet absorber selected from the group consisting of a benzotriazole compound, triazine compound, benzophenone compound, cyanoacrylate compound and benzooxazinone compound in an amount of 0.01 to 5.0 wt% based on the ethylene2,6naphthalene dicarboxylate polymer, and at least one pigment selected from the group consisting of an oxide pigment, ferrocyanide pigment, silicate pigment, phosphate pigment, carbon black, condensation polycyclic pigment and phthalocyanine pigment in an amount of 10 to 2,000 ppm, (B3) which has a birefringence factor (An) of the barrel portion of 0.17 or more and (B4) which has a haze of the barrel portion of 10 % or less. |
Description:
INTERNATIONAL SEARCH REPORT Inte. onal Application No PCT/JP 00/01644 C. (Continuation) DOCUMENTS CONSIDERED TO BE RELEVANT Category ° Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. Y US 4 983 653 A (FUKUDA YUJIRO ET AL) 1-7,9, 8 January 1991 (1991-01-08) 10,16 claim 2 column 2, paragraph 1 column 4, line 23-line 28 A GB 2 025 842 A (EASTMAN KODAK CO) 1-16 30 January 1980 (1980-01-30) claims 1,11-16 page 1, paragraphs 4,5,8 page 1, line 31-34 X EP 0 822 213 A (MITSUI PETROCHEMICAL IND) 1-7, 4 February 1998 (1998-02-04) 9-11, 14-16,27 claims 1,4,8,13-15 page 6, line 22-line 23 A EP 0 870 797 A (AGFA GEVAERT NV) 1-16 14 October 1998 (1998-10-14) claims 1,4 page 15, line 28-line 31 A PATENT ABSTRACTS OF JAPAN 1-16 vol. 1998, no. 09, 31 July 1998 (1998-07-31) & JP 10 086213 A (TEIJIN LTD), 7 April 1998 (1998-04-07) abstract A EP 0 653 461 A (KIRIN BREWERY ; MITSUI 1-16 PETROCHEMICAL IND (JP)) 17 May 1995 (1995-05-17) claim 1 page 3, line 28-line 29 page 5, line 27-page 10, line 58 Y EP 0 884 365 A (HNA HOLDINGS INC) 17-27 16 December 1998 (1998-12-16) page 4, line 3; claim 1 page 4, line 23 page 4, paragraph 7 page 7, line 26,27 Y US 4 250 078 A (MCFARLANE FINLEY E ET AL) 17-27 10 February 1981 (1981-02-10) claim 1 column 1, paragraphs 3,4 examples 4,5 4 INTERNATIONAL SEARCH REPORT Inte ional Application No PCT/JP 00/01644 C. (Continuation) DOCUMENTS CONSIDERED TO BE RELEVANT Category Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. Y US 4 535 118 A (PENGILLY BRIAN W) 17-27 13 August 1985 (1985-08-13) column 3, line 65-line 68; claims 1,12,20 column 4, paragraph 2 column 6, paragraph 1 A DE 195 03 055 A (ZIMMER AG) 17-27 8 August 1996 (1996-08-08) claims 2,9,11 page 2, line 29 Y EP 0 399 797 A (HOECHST CELANESE CORP) 17-27 28 November 1990 (1990-11-28) claim 15 page 5, line 38-line 44 Y DATABASE WPI 17-27 Section Ch, Week 199812 Derwent Publications Ltd., London, GB; Class A23, AN 1998-125046 XP002145571 & JP 10 006387 A (MITSUI PETROCHEM IND CO LTD), 13 January 1998 (1998-01-13) abstract Y DATABASE WPI 17-27 Section Ch, Week 198236 Derwent Publications Ltd., London, GB; Class A23, AN 1982-75519E XP002145572 & JP 57 123253 A (KANEBO GOSEN KK), 31 July 1982 (1982-07-31) abstract A WO 97 28223 A (KATONO HIROKI; OGIHARA 17-27 TAKEO (JP); SAKAGAMI TERUO (JP); SHOUJI MAS) 7 August 1997 (1997-08-07) A & epodoc abstract 17-27 Y US 4 476 272 A (PENGILLY BRIAN W) 17-27 9 October 1984 (1984-10-09) claims 1,3,9-12 column 3, line 60-line 64 column 4, paragraph 2 4 liernational application No. PCT/JP 00/01644 INTERNATIONAL SEARCH T/JP 00/01644 Box I Observations where certain claims were found unsearchable (Continuation of item 1 of first sheet) This International Search Report has not been established in respect of certain claims under Article 17 (2) (a) for the following reasons: 1.1-1 Claims Nos.: because they relate to subject matter not required to be searched by this Authority, namely: 2. Claims Nos.: because they relate to parts of the International Application that do not comply with the prescribed requirements to such an extent that no meaningful International Search can be carried out, specifically: 3. Claims Nos.: because they are dependent claims and are not drafted in accordance with the second and third sentences of Rule 6.4 (a). Box 11 Observations where unity of invention is lacking (Continuation of item 2 of first sheet) This International Searching Authority found multiple inventions in this international application, as follows: see additional sheet 1. As all required additional search fees were timely paid by the applicant, this International Search Report covers all searchable claims. 2. as ait searchable claims coutd be searched without effort justifying an additional fee, this Authority did not invite payment of any additional fee. 3. As only some of the required additional search fees were timely paid by the applicant, this International Search Report covers only those claims for which fees were paid, specifically claims Nos.: 4. No required additional search fees were timely paid by the applicant. Consequently, this International Search Report is restricted to the invention first mentioned in the claims; it is covered by claims Nos.: Remark on Protest ! The additional search fees were accompanied by the applicant's protest. u , No protest accompanied the payment of additional search fees. au FURTHER INFORMATION CONTINUED FROM PCT/ISA/210<BR> <BR> This International Searching Authority found multiple (groups of)<BR> inventions in this international application, as follows:<BR> <BR> 1. Claims: 1-16,27<BR> <BR> Claims 1-16 and claim 27 relate to hollow molded products<BR> containing PEN in combination with specific (organic) UV<BR> absorbers. The technical problem solved by addition of the<BR> afore-mentioned UV absorbers is to prevent decrease of<BR> transparency under UV light and recycling conditions (cf.<BR> description, page 3, first full paragraph).<BR> <BR> <BR> <P> 2. Claims: 17-26<BR> <BR> Claims 17 - 26 relate to hollow molded PEN products<BR> containing specific pigments. The technical problems solved<BR> by the afore-mentioned additives are to protect the contents<BR> of the hollow article from visible radiation, shorten the<BR> molding cycle, etc (cf. description, page 18, first<BR> paragraph). INTERNATIONAL SEARCH -----------------, Inte lonal Application No Information on patent tamily members PCT/JP 00/01644 Patent document Publication Patent family Publication cited in search report date member (s) date JP 5008283 A 19-01-1993 NONE JP 5008283 A 19-01-1993 NONE EP 0363839 A 18-04-1990 JP 2188581 A 24-07-1990 US 5071995 A 10-12-1991 US 4983653 A 08-01-1991 JP 2566568 B 25-12-1996 JP 63202429 A 22-08-1988 JP 63222845 A 16-09-1988 JP 1258935 A 16-10-1989 JP 7029376 B 05-04-1995 JP 63309424 A 16-12-1988 JP 63122519 A 26-05-1988 JP 1110931 A 27-04-1989 JP 7077757 B 23-08-1995 JP 63146940 A 18-06-1988 JP 63150331 A 23-06-1988 DE 3751722 D 04-04-1996 DE 3751722 T 11-07-1996 DE 3787075 A 23-09-1993 DE 3787075 T 09-12-1993 EP 0267799 A 18-05-1988 EP 0409288 A 23-01-1991 KR 9600590 B 09-01-1996 US 4985538 A 15-01-1991 GB 2025842 A 30-01-1980 US 4265804 A 05-05-1981 CA 1135920 A 23-11-1982 DE 2928055 A 31-01-1980 FR 2430959 A 08-02-1980 CA 1144328 A 12-04-1983 CA 1135919 A 23-11-1982 JP 55027296 A 27-02-1980 EP 0822213 A 04-02-1998 JP 9227663 A 02-09-1997 JP 9277358 A 28-10-1997 JP 10045886 A 17-02-1998 BR 9704619 A 09-06-1998 CA 2215035 A 28-08-1997 WO 9731050 A 28-08-1997 EP 0870797 A 14-10-1998 JP 10279785 A 20-10-1998 US 5824465 A 20-10-1998 JP 10086213 A 07-04-1998 NONE EP 0653461 A 17-05-1995 JP 7133357 A 23-05-1995 DE 69422690 D 24-02-2000 DE 69422690 T 21-06-2000 US 5714220 A 03-02-1998 EP 0884365 A 16-12-1998 US 5925710 A 20-07-1999 BR 9806497 A 14-12-1999 CA 2235486 A 23-10-1998 US 4250078 A 10-02-1981 US 4420581 A 13-12-1983 US 4535118 A 13-08-1985 US 4408004 A 04-10-1983 BR 8300753 A 16-11-1983 INTERNATIONAL SEARCH REPORT Inte. onal Application No tnteona) on patent family members PCT/JP 00/01644 Patent document Publication cited in search report date member (s) date US 4535118 A CA 1210548 A 26-08-1986 DE 3362136 D 27-03-1986 EP 0087383 A 31-08-1983 ES 520011 D 01-10-1984 ES 8500306 A 01-01-1985 JP 1871663 C 06-09-1994 JP 5021938 B 26-03-1993 JP 58157853 A 20-09-1983 US 4476272 A 09-10-1984 ZA 8300921 A 30-11-1983 DE 19503055 A 08-08-1996 NONE EP 0399797 A 28-11-1990 US 4959449 A 25-09-1990 BR 9002408 A 06-08-1991 CA 2014746 A 25-11-1990 JP 3024125 A 01-02-1991 JP 7074267 B 09-08-1995 JP 10006387 A 13-01-1998 NONE JP 57123253 A 31-07-1982 NONE WO 9728223 A 07-08-1997 JP 9208863 A 12-08-1997 US 4476272 A 09-10-1984 US 4408004 A 04-10-1983 BR 8300753 A 16-11-1983 CA 1210548 A 26-08-1986 DE 3362136 D 27-03-1986 EP 0087383 A 31-08-1983 ES 520011 D 01-10-1984 ES 8500306 A 01-01-1985 JP 1871663 C 06-09-1994 JP 5021938 B 26-03-1993 JP 58157853 A 20-09-1983 US 4535118 A 13-08-1985 ZA 8300921 A 30-11-1983
