LIQUID CRYSTAL POLYESTER RESIN COMPOSITION, LAMINATE, LIQUID CRYSTAL POLYESTER RESIN FILM, AND PRODUCTION METHOD THEREOF

Abstract

A liquid crystal polyester resin composition includes a liquid crystal polyester resin (A); a solvent (B) in which the liquid crystal polyester resin (A) is dissolved; a fluorine resin (C); and an inorganic filler (D), wherein 100 to 5,000 parts by weight of the solvent (B), 5 to 300 parts by weight of the fluorine resin (C) and 1 to 300 parts by weight of the inorganic filler (D) are included relative to 100 parts by weight of the liquid crystal polyester resin (A).

Claims

1-12. (canceled)

13. A liquid crystal polyester resin composition comprising: a liquid crystal polyester resin (A); a solvent (B) in which the liquid crystal polyester resin (A) is dissolved; a fluorine resin (C); and an inorganic filler (D), wherein 100 to 5,000 parts by weight of the solvent (B), 5 to 300 parts by weight of the fluorine resin (C) and 1 to 300 parts by weight of the inorganic filler (D) are included relative to 100 parts by weight of the liquid crystal polyester resin (A).

14. The liquid crystal polyester resin composition according to claim 13, wherein the weight ratio (C/D) of the fluorine resin (C) to the inorganic filler (D) is 0.1 to 10.

15. The liquid crystal polyester resin composition according to claim 13, which includes, as the solvent (B), 50 to 3,000 parts by weight of a phenol (B1) in which three or more hydrogen atoms bonded to the benzene ring are substituted with fluorine atoms, and 1 to 2,000 parts by weight of a protic solvent (B2) having a melting point of 30° C. or lower and an acid dissociation constant (pKa) of 4 to 12, relative to 100 parts by weight of the liquid crystal polyester resin.

16. The liquid crystal polyester resin composition according to claim 13, wherein the fluorine resin (C) is polytetrafluoroethylene.

17. The liquid crystal polyester resin composition according to claim 13, wherein the mean particle size of the fluorine resin (C) is 0.1 to 20 μm.

18. The liquid crystal polyester resin composition according to claim 13, wherein the mean particle size of the inorganic filler (D) is 0.1 to 20 μm.

19. The liquid crystal polyester resin composition according to claim 13, wherein the liquid crystal polyester resin (A) includes 3 to 40 mol % of a structural unit derived from an aliphatic diol having 2 to 4 carbon atoms relative to 100 mol % of the total structural unit of the liquid crystal polyester resin.

20. A liquid crystal polyester resin film comprising: a liquid crystal polyester resin (A); a fluorine resin (C); and an inorganic filler (D), wherein 5 to 300 parts by weight of the fluorine resin (C) and 1 to 300 parts by weight of the inorganic filler (D) are included relative to 100 parts by weight of the liquid crystal polyester resin (A).

21. A liquid crystal polyester resin film obtained from the liquid crystal polyester resin composition according to claim 13.

22. A laminate comprising a support and a resin layer that are mutually laminated, wherein the support is laminated on at least one surface of the resin layer obtained from the liquid crystal polyester resin composition according to claim 13.

23. A method of producing a laminate comprising applying the liquid crystal polyester resin composition according to claim 13 onto a support and removing the solvent (B).

24. A method of producing a liquid crystal polyester resin film comprising removing the support from the laminate obtained by the method according to claim 23 to obtain a liquid crystal polyester resin film.

Description

EXAMPLES 1 TO 14, COMPARATIVE EXAMPLES 1 TO 5

[0097] The liquid crystal polyester resin (A) was crushed into powders using a coarse crusher and mixed with a solvent (B1) in the amount shown in Table 1, followed by heating to 130° C. to completely dissolve each liquid crystal polyester resin. Thereafter, the solution was cooled to 50° C., mixed with a solvent (B2) in the amount shown in Table 1, followed by stirring and defoam to obtain a brown transparent solution. Subsequently, a fluorine resin (C) and an inorganic filler (D) were mixed in each amount shown in Table 1, followed by cooling to 25° C. to obtain a liquid crystal polyester resin composition, and then evaluations (4) and (5) were performed.

[0098] Regarding Examples 6 and 9 and Comparative Examples 3 and 4, since the liquid crystal polyester resin was solidified at 25° C., it was heated to 50° C. to be liquefied, and then evaluations (4) and (5) were performed.

[0099] The phenol (B1) in which three or more hydrogen atoms bonded to the benzene ring are substituted with fluorine atoms, the protic solvent (B2) having a melting point of 30° C. or lower, the fluorine resin (C) and the inorganic filler (D) used in each of Examples and Comparative Examples are as shown below. Regarding the melting point, the boiling point and the acid dissociation constant (pKa), literature values were cited.

[0100] (B1-1) Pentafluorophenol (melting point of 34° C., boiling point of 143° C., pKa of 5.5)

[0101] (B2-1) o-Chlorophenol (melting point of 8° C., boiling point of 175° C., pKa of 8.5)

[0102] (B2-2) Hexafluoroisopropanol (melting point of −4° C., boiling point of 59° C., pKa of 9.3)

[0103] (C-1) Polytetrafluoroethylene micropowder (“Dyneon” TF 9207Z manufactured by 3M Company, mean particle size of 4 μm)

[0104] (D-1) Plate-like boron nitride (WU-BN-002 manufactured by LONG TON Co., Ltd., mean particle size of 0.6 μm)

[0105] (D-2) Clay (S-BEN NX manufactured by HOJUN Co., Ltd., mean particle size of 2 μm)

[0106] (D-3) Aluminum oxide(SPECTRAL51 manufactured by Cabot Corporation, mean particle size of 5 μm)

[0107] (D-4) Mesoporous silica (MCM-48 manufactured by Sigma-Aldrich Co. LLC, mean particle size of 15 μm).

(4) Evaluation of Aggregates of Fluorine Resin (C) and Inorganic Filler (D)

[0108] The thus obtained liquid crystal polyester resin composition was applied onto an aluminum foil (12 μm in thickness) using a film applicator, heated to 55° C. on a hot plate to remove a part of the solvent and heated to a temperature of 80° C. to remove the remaining solvent, and then a heat treatment was further performed at a temperature of 100° C. for one hour to fabricate a laminate of a liquid crystal polyester resin film of 200 mm x 300 mm (average thickness of 50 μm) and the aluminum foil. The thus obtained liquid crystal polyester resin film was peeled off from the aluminum foil, and regarding the thus obtained film, the number of aggregates of 100 μm or more observed at any 50 points in the field with a magnification of 150 times using a digital microscope VHX-500F manufactured by Shimadzu Corporation was evaluated. The smaller the number of aggregates is, the more excellent dispersibility of the fluorine resin (C) and the inorganic filler (D) the film has.

(5) Evaluation of Deformation after Heat Treatment

[0109] In the same manner as in (4) above, 30 laminates each of the liquid crystal polyester resin film and the aluminum foil were fabricated, and when the melting point of the liquid crystal polyester resin is 260° C. or more, a heat treatment was performed for 3 hours at 260° C., and then a heat treatment was further performed at 300° C. for 1 minute. When the melting point of the liquid crystal polyester resin is less than 260° C., a heat treatment was performed for 3 hours at a temperature of the melting point of the liquid crystal polyester resin −10° C. Regarding the laminate after heat treatment, the number of occurrences of deformation such as wrinkles, cracks or curls was evaluated. The smaller the number of occurrences of deformation is, the more excellent the film is in which deformation does not occur after a heat treatment.

[0110] Table 1 shows the evaluation results of the measurement by the methods mentioned in (1) to (3) above regarding the pellets obtained in Production Examples 1 to 4, and the evaluation results of the measurement of each property by the methods mentioned in (4) and (5) above regarding Examples 1 to 10 and Comparative Examples 1 to 4.

TABLE-US-00001 TABLE 1 Liquid Weight ratio Aggregates crystal Solvent (B) (C/D) of of fluorine polyester Solvent Solvent Fluorine Inorganic fluorine resin (C) and Deformation resin (A) (B1) (B2) resin (C) filler (D) resin (C) to inorganic after heat (Parts by (Parts by (Parts by (Parts by (Parts by inorganic filler (D) treatment weight) weight) weight) weight) weight) filler (D) (aggregate) (laminate) Example 1 A-1(100) B1-1(900) B2-2(500) C-1(130) D-1(40) 3.25 0 0 Example 2 A-2(100) B1-1(900) B2-2(500) C-1(130) D-1(40) 3.25 0 0 Example 3 A-2(100) B1-1(900) B2-2(500) C-1(130) D-2(40) 3.25 1 0 Example 4 A-2(100) B1-1(900) B2-2(500) C-1(130) D-3(40) 3.25 3 2 Example 5 A-2(100) B1-1(900) B2-2(500) C-1(130) D-4(40) 3.25 3 2 Example 6 A-2(100) B1-1(900) B2-1(500) C-1(130) D-1(40) 3.25 1 0 Example 7 A-2(100) B1-1(900) B2-2(500) C-1(160) D-1(20) 8 0 1 Example 8 A-2(100) B1-1(900) B2-2(500) C-1(30) D-1(150) 0.2 4 1 Example 9 A-3(100) B1-1(900) B2-2(500) C-1(130) D-1(40) 3.25 2 2 Example 10 A-4(100) B1-1(900) B2-2(500) C-1(130) D-1(40) 3.25 0 0 Example 11 A-2(100) B1-1(900) B2-2(500) C-1(5) D-1(40) 0.13 5 5 Example 12 A-2(100) B1-1(900) B2-2(500) C-1(13) D-1(4) 3.25 0 5 Example 13 A-2(100) B1-1(900) B2-2(500) C-1(130) D-1(280) 0.46 5 3 Example 14 A-2(100) B1-1(900) B2-2(500) C-1(280) D-1(40) 7 4 4 Example 15 A-2(100) B1-1(900) B2-2(500) C-1(80) D-1(40) 2 0 0 Example 16 A-2(100) B1-1(900) B2-2(500) C-1(130) D-1(30) 4.33 0 0 Example 17 A-2(100) B1-1(400) B2-2(80) C-1(130) D-1(40) 3.25 2 4 Example 18 A-2(100) B1-1(2700) B2-2(1500) C-1(130) D-1(40) 3.25 2 4 Comparative Example 1 A-2(100) B1-1(900) B2-2(500) C-1(130) — — 32 27 Comparative Example 2 A-2(100) B1-1(900) B2-2(500) — D-1(40) 0 10 15 Comparative Example 3 A-2(100) B1-1(900) B2-2(500) C-1(330) D-1(20) 16.5 48 29 Comparative Example 4 A-2(100) B1-1(900) B2-2(500) C-1(30) D-1(330) 0.09 42 26 Comparative Example 5 A-2(100) B1-1(900) B2-2(500) C-1(2) D-1(40) 0.05 9 14

[0111] As is apparent from the results in Table 1, it is possible to obtain a film in which occurrence of aggregates and deformation after a heat treatment are suppressed by using the liquid crystal polyester resin composition that is used in combination with the fluorine resin (C) and the inorganic filler (D).

INDUSTRIAL APPLICABILITY

[0112] According to the liquid crystal polyester resin composition, it is possible to obtain a film in which occurrence of aggregates and deformation after a heat treatment are suppressed. The liquid crystal polyester resin film and the laminate are suitably used for circuit boards such as flexible printed wiring boards and rigid printed wiring boards, and semiconductor packages, which use a laminate characterized in that a plurality of resin films or laminates are laminated.