POLYCARBONATE RESIN COMPOSITION

Abstract

The present application provides a polycarbonate-based coating resin composition having high adhesiveness, more specifically provides a polycarbonate resin composition that contains not less than 0.1 parts by mass of a polyisocyanate compound and 100 parts by mass of a terminal-modified polycarbonate resin (A) having a structural unit (2) and a terminal structure represented by structural formula (1). [In formula (1) and formula (2), R.sub.1-R.sub.7, X, Y, Z, and a are as described in the description.]

##STR00001##

Claims

1. A polycarbonate resin composition comprising: 100 parts by mass of a terminal-modified polycarbonate resin (A) having a terminal structure represented by Structural formula (1) below and a structural unit (2) below; and not less than 0.1 parts by mass of a polyisocyanate compound, ##STR00016## (in Formula (1), R.sub.1 represents an optionally substituted C1-C20 alkylene group or C2-C20 alkenylene group, R.sub.2 and R.sub.3 each independently represent hydrogen, a C1-C20 alkyl group, a C1-C10 alkoxy group or a C6-C12 aryl group, Z represents an ether bond, a carbonyl group, an ester bond or a single bond, a is an integer of 1-3, and Y represents an ether bond or an ester group), ##STR00017## (in Formula (2), R.sub.4-R.sub.7 each independently represent hydrogen, fluorine, chlorine, bromine, iodine, or an optionally substituted C1-C20 alkyl group, C6-C12 aryl group, C2-C12 alkenyl group, C1-05 alkoxy group or C7-C17 aralkyl group, and X is —O—, —S—, —SO—, —SO.sub.2—, —CO— or a divalent group represented by any of General formulae (3)-(8) below) ##STR00018## (in General formula (3), R.sub.8-R.sub.17 each independently represent hydrogen or a C1-C3 alkyl group, and at least one of R.sub.8-R.sub.17 represents a Cl -C3 alkyl group; and in General formulae (4)-(8), R.sub.18 and R.sub.19 each independently represent hydrogen, a halogen, an optionally substituted C1-C20 alkyl group, an optionally substituted C1-05 alkoxy group, an optionally substituted C6-C12 aryl group, an optionally substituted C7-C17 aralkyl group or an optionally substituted C2-C15 alkenyl group, or R.sub.18 and R.sub.19 bind to each other to form a C3-C20 carbocyclic ring or a C1-C20 heterocyclic ring, R.sub.20 is an optionally substituted C1-C9 alkylene group, c represents an integer of 0-20, and d represents an integer of 1-500).

2. The polycarbonate resin composition according to claim 1, wherein, in Structural formula (1) above, Z represents a single bond, R.sub.1 is a C1-C2 alkylene group, and R.sub.2-R.sub.3 are hydrogen.

3. The polycarbonate resin composition according to claim 1, wherein, in the structural unit (2), X is —O—, —S— or a divalent group represented by either one of General formulae (3)-(4) above.

4. The polycarbonate resin composition according to claim 1, wherein the structural unit (2) is any one or more kinds selected from the group consisting of Formulae (9)-(22) below: ##STR00019## ##STR00020##

5. The polycarbonate resin composition according to claim 1, wherein the structural unit (2) is derived from a bisphenol compound.

6. The polycarbonate resin composition according to claim 5, wherein the bisphenol compound is selected from the group consisting of bisphenol A, bisphenol AP, bisphenol Z, bisphenol CD, bisphenol C, bisphenol IOTD, bisphenol IBTD, bisphenol MIBK and bisphenol AF.

7. The polycarbonate resin composition according to claim 1, wherein the terminal structure represented by Structural formula (1) above is p-hydroxyphenethyl alcohol (PHEP).

8. The polycarbonate resin composition according to claim 1, wherein the terminal structure represented by Structural formula (1) is contained in an amount of not less than 0.5 mol % relative to the amount of the structural unit (2).

9. The polycarbonate resin composition according to claim 1, wherein the polyisocyanate compound is an isocyanate compound containing two or more isocyanate groups per molecule.

10. The polycarbonate resin composition according to claim 9, wherein the isocyanate compound is a diisocyanate compound.

11. The polycarbonate resin composition according to claim 1, wherein the viscosity average molecular weight of the polycarbonate resin composition is 10,000-60,000.

12. A crosslinked polymer composition, wherein at least a part of the polycarbonate resin composition according to claim 1 is crosslinked.

13. A resin solution comprising the polycarbonate resin composition according to claim 1, and a non-halogenated organic solvent.

14.-16. (canceled)

17. A resin solution comprising the crosslinked polymer composition according to claim 12, and a non-halogenated organic solvent.

18. A print ink, which uses the resin solution according to claim 13 as a binder resin solution.

19. A print ink, which uses the resin solution according to claim 14 as a binder resin solution.

20. A substrate film applied with the print ink according to claim 15.

21. A substrate film applied with the print ink according to claim 16.

22. A film or coating, comprising the polycarbonate resin composition according to claim 1.

23. A film or coating, comprising the crosslinked polymer composition according to claim 12.

Description

EXAMPLES

[0172] Hereinafter, examples of the present invention will be described along with comparative examples to describe the invention in detail, although the present invention is not limited to these examples.

Example 1

[0173] In 600 ml of a 9 w/w % aqueous sodium hydroxide solution and 200 ml of pure water, 108 g (0.37 mol) of 1,1-bis(4-hydroxyphenyl)-1-phenylethane (hereinafter, simply referred to as “BPAP”: manufactured by Honshu Chemical Industry Co., Ltd.), 2.88 g (0.021 mol, content of terminal structure: 5.6 mol %) of p-hydroxyphenethyl alcohol (hereinafter, simply referred to as “PHEP”: manufactured by Otsuka Chemical Co., Ltd.) and 0.3 g of hydrosulfite were dissolved.

[0174] To this, 200 ml of methylene chloride was added and 51.6 g of phosgene was blown into the resultant by spending about 30 minutes while stirring and maintaining the temperature at 15-20° C.

[0175] At the end of phosgene blowing, 100 ml of a 9 w/w% aqueous sodium hydroxide solution was added and vigorously stirred to emulsify the reaction solution, to which 0.5 ml of triethylamine was added as a polymerization catalyst to allow polymerization by stirring at 20-30° C. for about 40 minutes.

[0176] At the end of polymerization, the reaction solution was separated into an aqueous phase and an organic phase. The organic phase was neutralized with phosphoric acid, and repeatedly washed with water until the conductivity of the rinsing liquid (aqueous phase) became 10 μS/cm or lower. The obtained polymer solution was dropped into warm water kept at 60° C. to evaporate the solvent away, thereby obtaining a white powdery precipitate. The obtained precipitate was filtered and dried at 105° C. for 24 hours, thereby obtaining polymer powder.

[0177] The resulting polycarbonate resin (hereinafter, simply referred to as “PC-1”) had Mv of 19,700, Mw of 54,000 (with respect to PS) and 30,300 (with respect to PC), and a hydroxyl value of 11 mg KOH/g.

[0178] A resin composition containing PC-1 (10 parts by mass) and 1 part by mass (10 parts by mass relative to 100 parts by mass of the polycarbonate resin) of hexamethylene diisocyanate (hereinafter, simply referred to as “HDI”) was dissolved in 55 parts by mass of toluene to prepare a paint solution (resin solution). This paint solution was applied to (painted on) a stainless steel plate, air-dried, and then heated to 110° C. to dry for 5 hours to give a test piece. The dried polycarbonate resin composition (crosslinked polymer) had Mw of 58,900 (with respect to PS) and 33,100 (with respect to PC). According to the cross-cut test following JIS K5600-5-6, the test piece was rated 0.

Example 2

[0179] Polymerization was conducted in the same manner as Example 1 except that 103.8 g (0.39 mol) of 1,1-bis(4-hydroxyphenyl)cyclohexane (hereinafter, simply referred to as “BPZ”: manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPAP and that the amount of PHEP was changed to 1.53 g (0.011 mol, content of terminal structure: 2.9 mol %) to give a polycarbonate resin (Mv: 30,600, Mw: 89,100 (with respect to PS) and 50,400 (with respect to PC), hydroxyl value: 5 mg KOH/g; hereinafter, referred to as “PC-2”). PC-2 (10 parts by mass) and 1 part by mass (10 parts by mass relative to 100 parts by mass of the polycarbonate resin) of HDI were dissolved in 55 parts by mass of toluene to prepare and assess a paint solution in the same manner as Example 1. The dried polycarbonate resin composition had Mw of 95,900 (with respect to PS) and 54,300 (with respect to PC).

Example 3

[0180] Polymerization was conducted in the same manner as Example 1 except that 101.7 g (0.38 mol) of 2,2-bis(4-hydroxyphenyl)-4-methylpentane (hereinafter, simply referred to as “MIBK”: manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPAP and the amount of PHEP was changed to 0.79 g (0.006 mol, content of terminal structure: 1.5 mol %) to give a polycarbonate resin (Mv: 43,500, Mw: 124,200 (with respect to PS) and 70,600 (with respect to PC), hydroxyl value: 3 mg KOH/g; hereinafter, simply referred to as “PC-3”). PC-3 (10 parts by mass) and 1 part by mass (10 parts by mass relative to 100 parts by mass of the polycarbonate resin) of HDI were dissolved in 55 parts by mass of toluene to prepare and assess a paint solution in the same manner as Example 1. The dried polycarbonate resin composition had Mw of 130,300 (with respect to PS) and 74,100 (with respect to PC).

Example 4

[0181] In 600 ml of a 9 w/w % aqueous sodium hydroxide solution and 200 ml of pure water, 48.0 g (0.19 mol) of 2,2-bis(4-hydroxy-3-methylphenyl-)propane (hereinafter, simply referred to as “BPC”: manufactured by Honshu Chemical Industry Co., Ltd.), 32.0 g (0.14 mol) of 2,2-bis(4-hydroxyphenyl)propane (hereinafter, simply referred to as “BPA”: manufactured by Mitsubishi Chemical Corporation), 2.25 g (0.016 mol, content of terminal structure: 4.7 mol %) of PHEP and 0.3 g of hydrosulfite were dissolved.

[0182] To this, 200 ml of methylene chloride and 0.08 g of benzyltriethylammonium chloride (hereinafter, simply referred to as “TEBAC”) were added and then 46.9 g of phosgene was blown into the resultant by spending about 30 minutes while stirring and maintaining the temperature at 15-20° C.

[0183] At the end of phosgene blowing, 100 ml of a 9 w/w % aqueous sodium hydroxide solution was added and vigorously stirred to emulsify the reaction solution. At the end of emulsification, 0.5 ml of triethylamine was added to the resultant to allow polymerization by stirring at 20-30° C. for about an hour.

[0184] At the end of polymerization, the reaction solution was separated into an aqueous phase and an organic phase. The organic phase was neutralized with phosphoric acid, and repeatedly washed with water until the conductivity of the rinsing liquid (aqueous phase) became 10 μS/cm or lower. The obtained polymer solution was dropped into warm water kept at 60° C. to evaporate the solvent away, thereby obtaining a white powdery precipitate.

[0185] The obtained precipitate was filtered and dried at 105° C. for 24 hours, thereby obtaining polymer powder.

[0186] The resulting polycarbonate resin (hereinafter, simply referred to as “PC-4”) had Mv of 25,500, Mw of 57,000 (with respect to PS) and 32,000 (with respect to PC), and a hydroxyl value of 8 mg KOH/g. PC-4 (10 parts by mass) and 1 part by mass (10 parts by mass relative to 100 parts by mass of the polycarbonate resin) of xylylene diisocyanate (XDI) were dissolved in 55 parts by mass of toluene to prepare and assess a paint solution in the same manner as Example 1. The dried polycarbonate resin composition had Mw of 65,700 (with respect to PS) and 37,000 (with respect to PC).

Example 5

[0187] PC-4 (10 parts by mass) and 0.01 parts by mass (0.1 parts by mass relative to 100 parts by mass of the polycarbonate resin) of HDI were dissolved in 55 parts by mass of toluene to prepare and assess a paint solution in the same manner as Example 1. The dried polycarbonate resin composition had Mw of 58,400 (with respect to PS) and 32,800 (with respect to PC).

Example 6

[0188] PC-4 (10 parts by mass) and 1 part by mass (10 parts by mass relative to 100 parts by mass of the polycarbonate resin) of HDI were dissolved in 55 parts by mass of toluene to prepare and assess a paint solution in the same manner as Example 1. The dried polycarbonate resin composition had Mw of 69,900 (with respect to PS) and 39,400 (with respect to PC).

Example 7

[0189] Polymerization was conducted in the same manner as Example 4 except that 71.4 g (0.21 mol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane (hereinafter, simply referred to as “BPAF”: manufactured by Central Glass Co., Ltd.) was used instead of BPC, and the amounts of BPA and PHEP were changed to 20.4 g (0.09 mol) and 0.833 g (0.006 mol, content of terminal structure: 2.0 mol %), respectively, to give a polycarbonate resin (Mv: 27,300, Mw: 84,200 (with respect to PS) and 47,600 (with respect to PC), hydroxyl value: 6 mg KOH/g; hereinafter, simply referred to as “PC-A”). PC-A (10 parts by mass) and 0.25 parts by mass (2.5 parts by mass relative to 100 parts by mass of the polycarbonate resin) of HDI were dissolved in 55 parts by mass of toluene to prepare and assess a paint solution in the same manner as Example 1. The dried polycarbonate resin composition had Mw of 91,700 (with respect to PS) and 51,900 (with respect to PC).

Comparative Example 1

[0190] Polymerization was conducted in the same manner as Example 1 except that PHEP was changed to 2.21 g (0.015 mol, content of terminal structure: 4.0 mol %) of PTBP to give a polycarbonate resin (Mv: 20,000, Mw: 56,600 (with respect to PS) and 31,800 (with respect to PC), hydroxyl value: 0 mg KOH/g; hereinafter, simply referred to as “PC-5”). A paint solution was prepared and assessed in the same manner as Example 1 except that HDI was not used and PC-5 was used instead of PC-1. The dried polycarbonate resin composition had Mw of 56,600 (with respect to PS) and 31,800 (with respect to PC).

Comparative Example 2

[0191] A paint solution was prepared and assessed in the same manner as Example 1 except that PC-5 was used instead of PC-1. The dried polycarbonate resin composition had Mw of 56,600 (with respect to PS) and 31,800 (with respect to PC).

Comparative Example 3

[0192] A paint solution was prepared and assessed in the same manner as Example 1 except that PC-5 was used instead of PC-1 and the amount of HDI was changed to 3 parts by mass (30 parts by mass relative to 100 parts by mass of the polycarbonate resin). The dried polycarbonate resin composition had Mw of 56,600 (with respect to PS) and 31,800 (with respect to PC).

Comparative Example 4

[0193] Polymerization was conducted in the same manner as Example 2 except that PHEP was changed to 1.17 g (0.008 mol, content of terminal structure: 2.0 mol %) of PTBP to give a polycarbonate resin (Mv: 32,500, Mw: 98,900 (with respect to PS) and 56,000 (with respect to PC), hydroxyl value: 0 mg KOH/g; hereinafter, simply referred to as “PC-6”). A paint solution was prepared and assessed in the same manner as Example 2 except that PC-6 was used instead of PC-2. The dried polycarbonate resin composition had Mw of 98,900 (with respect to PS) and 56,000 (with respect to PC).

Comparative Example 5

[0194] Polymerization was conducted in the same manner as Example 3 except that PHEP was changed to 0.71 g (0.005 mol, content of terminal structure: 1.3 mol %) of PTBP to give a polycarbonate resin (Mv: 50,000, Mw: 149,900 (with respect to PS) and 85,400 (with respect to PC), hydroxyl value: 0 mg KOH/g; hereinafter, simply referred to as “PC-7”). A paint solution was prepared and assessed in the same manner as Example 3 except that PC-7 was used instead of PC-3. The dried polycarbonate resin composition had Mw of 149,900 (with respect to PS) and 85,400 (with respect to PC).

Comparative Example 6

[0195] Polymerization was conducted in the same manner as Example 4 except that PHEP was changed to 1.47 g (0.013 mol, content of terminal structure: 3.0 mol %) of PTBP to give a polycarbonate resin (Mv: 26,000, Mw: 61,500 (with respect to PS) and 34,600 (with respect to PC), hydroxyl value: 0 mg KOH/g; hereinafter, simply referred to as “PC-8”). A paint solution was prepared and assessed in the same manner as Example 4 except that HDI was not used and PC-8 was used instead of PC-4. The dried polycarbonate resin composition had Mw of 61,500 (with respect to PS) and 34,600 (with respect to PC).

Comparative Example 7

[0196] A paint solution was prepared and assessed in the same manner as Example 1 except that HDI was not used. The dried polycarbonate resin composition had Mw of 54,000 (with respect to PS) and 30,300 (with respect to PC).

Comparative Example 8

[0197] A paint solution was prepared and assessed in the same manner as Example 2 except that HDI was not used. The dried polycarbonate resin composition had Mw of 89,100 (with respect to PS) and 50,400 (with respect to PC).

Comparative Example 9

[0198] A paint solution was prepared and assessed in the same manner as Example 4 except that HDI was not used. The dried polycarbonate resin composition had Mw of 57,000 (with respect to PS) and 32,000 (with respect to PC).

[0199] The durability against peeling measured for the paint solutions of the above-described examples and comparative examples are shown in the following table.

TABLE-US-00001 TABLE 1 Polyisocyanate Durability Example/ Main Terminal (Amount added against Comparative example PC backbone structure relative to PC) peeling Example 1 PC-1 BPAP PHEP HDI 0 (10 parts by mass) Example 2 PC-2 BPZ PHEP HDI 0 (10 parts by mass) Example 3 PC-3 MIBK PHEP HDI 0 (10 parts by mass) Example 4 PC-4 BPC/BPA PHEP XDI 0 (10 parts by mass) Example 5 PC-4 BPC/BPA PHEP HDI 1 (0.1 parts by mass) Example 6 PC-4 BPC/BPA PHEP HDI 0 (10 parts by mass) Example 7 PC-A BPAF/BPA PHEP HDI 0 (2.5 parts by mass) Comparative example 1 PC-5 BPAP PTBP — 5 Comparative example 2 PC-5 BPAP PTBP HDI 5 (10 parts by mass) Comparative example 3 PC-5 BPAP PTBP HDI 5 (30 parts by mass) Comparative example 4 PC-6 BPZ PTBP HDI 5 (10 parts by mass) Comparative example 5 PC-7 MIBK PTBP HDI 5 (10 parts by mass) Comparative example 6 PC-8 BPC/BPA PTBP — 5 Comparative example 7 PC-1 BPAP PHEP — 5 Comparative example 8 PC-2 BPZ PHEP — 5 Comparative example 9 PC-4 BPC/BPA PHEP — 3

[0200] Here, the polycarbonate resins used in the above-described examples and comparative examples were as follows.

TABLE-US-00002 TABLE 2 Mw Mw Hydroxyl (with (with value Main Terminal respect respect [mg backbone structure Mv to PS) to PS) KOH/g] PC-1 BPAP PHEP 19,700 54,000 30,300 11 PC-2 BPZ PHEP 30,600 89,100 50,400 5 PC-3 MIBK PHEP 43,500 124,200 70,600 3 PC-4 BPC/BPA PHEP 25,500 57,000 32,000 8 PC-5 BPAP PTBP 20,000 56,600 31,800 0 PC-6 BPZ PTBP 32,500 98,900 56,000 0 PC-7 MIBK PTBP 50,000 149,900 85,400 0 PC-8 BPC/BPA PTBP 26,000 61,500 34,600 0 PC-A BPAF/ PHEP 27,300 84,200 47,600 6 BPA

[0201] As described above, the resin composition of the present invention had improved adhesiveness between the coating and a substrate and thus was demonstrated to be useful as a resin blend composition comprising the polycarbonate resin and other resin.

[0202] The resin composition of the present invention can be used as a coating resin solution for protecting objects. In particular, the resin composition of the present invention is favorable in the fields that require durability of coating in daily life, like IC cards and security cards.