POLYCARBONATE RESIN COMPOSITION

Abstract

The present application provides a polycarbonate-based coating resin composition which exhibits high adhesiveness. The above are achieved by a polycarbonate resin composition which contains (A) a polycarbonate resin that contains a constituent unit represented by general formula (1) and a terminal structure represented by general formula (2) and (B) a polyisocyanate compound, wherein 0.1% by mass or more of the polyisocyanate compound (B) is contained on the basis of the total mass of the polycarbonate resin (A) and the polyisocyanate compound (B). (In formula (1) and formula (2), R.sub.1 to R.sub.3, X, m and n are as defined in the description.)

##STR00001##

Claims

1. A polycarbonate resin composition comprising: a polycarbonate resin (A) containing a structural unit represented by General formula (1) below and a terminal structure represented by General formula (2) below; and a polyisocyanate compound (B), wherein the polyisocyanate compound (B) is contained in an amount of not less than 0.1% by mass relative to the total mass of the polycarbonate resin (A) and the polyisocyanate composition (B): ##STR00010## (in Formula (1), R.sub.1 and R.sub.2 are each independently a C1-C4 alkyl group, n are each independently an integer of 0-4 (provided that not all of n are zero), and X is —O—, —S—, —SO—, —SO.sub.2—, —CO— or a divalent group represented by any of General formulae (3)-(8) below), (in Formula (2), R.sub.3 each independently represent a C1-C8 alkyl group which may be substituted with a hydroxy group, and m is an integer of 0-5), ##STR00011## (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 C1-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-C5 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 General formula (1) above, R.sub.1 and R.sub.2 are methyl groups, and n are all 1.

3. The polycarbonate resin composition according to claim 2, wherein, in General formula (4) above, R.sub.18 and R.sub.19 are methyl groups, and c is 1.

4. The polycarbonate resin composition according to claim 1, wherein the structural unit represented by General formula (1) above is contained in an amount of not less than 40 mol % relative to the number of moles of all structural units contained in the polycarbonate resin (A).

5. The polycarbonate resin composition according to claim 1, wherein R.sub.3 in General formula (2), as the terminal group of the polycarbonate resin (A), is a C1-C4 alkyl group which may be substituted with one hydroxy group.

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

7. The polycarbonate resin composition according to claim 1, which is a mixture of the polycarbonate resin (A) and the polyisocyanate compound (B).

8. The polycarbonate resin composition according to claim 1, wherein the polyisocyanate compound (B) comprises at least either one of hexamethylene diisocyanate and xylylene diisocyanate.

9. A resin solution comprising the polycarbonate resin composition according to claim 1, and an organic solvent.

10. The resin solution according to claim 9, wherein the organic solvent comprises at least any one of a non-halogenated solvent, an ester-based solvent, an ether-based solvent, a carbonate ester-based solvent and a ketone-based solvent.

11. A print ink, in which the resin solution according to claim 1 is used as a binder resin solution.

12. A substrate film applied with the print ink according to claim 11.

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

14. The film or coating according to claim 13, wherein the film comprises a film laminate.

Description

EXAMPLES

Example 1

[0186] In 600 ml of a 9 w/w % aqueous sodium hydroxide solution and 200 ml of pure water, 100.6 g (0.39 mol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter, simply referred to as “BPC”: manufactured by Honshu Chemical Industry Co., Ltd.), 1.39 g (0.009 mol, content of terminal structure: 2.4 mol %) of PTBP (p-tert-butylphenol) and 0.3 g of hydrosulfite were dissolved.

[0187] To this, 200 ml of methylene chloride and 0.08 g of benzyltriethyl ammonium (hereinafter, simply referred to as “TEBAC”) were added, and 55.1 g of phosgene was blown into the resultant by spending about 30 minutes while stirring and maintaining the temperature at 15-20° C.

[0188] 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.

[0189] 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.

[0190] The resulting polycarbonate resin (hereinafter, simply referred to as “PC-1′”) had Mv of 32,400.

[0191] A resin composition composed of 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 dried at 110° C. for 5 hours to give a test piece. Due to the drying process, the resin composition was considered to partially contain crosslinked polymers generated via the reaction between the hydroxy group or the like of the compound contained as impurities and the isocyanate group of HDI.

[0192] According to the cross-cut test following JIS K5600-5-6, the test piece was rated 1.

Example 2

[0193] Assessment was carried out in the same manner as Example 1 except that xylylene diisocyanate (hereinafter, simply referred to as “XDI”) was used instead of HDI to prepare a paint solution.

Example 3

[0194] Polymerization was conducted in the same manner as Example 1 except that the amount of BPC was changed to 65.3 g (0.26 mol), the amount of PTBP was changed to 2.01 g (0.013 mol %, content of terminal structure: 3.0 mol %), and 43.5 g (0.19 mol) of 2,2-bis(4-hydroxyphenyl)propane (hereinafter, simply referred to as “BPA”: manufactured by Mitsubishi Chemical Corporation) was used to give a polycarbonate resin (Mv: 26,000; hereinafter, referred to as “PC-2”).

[0195] 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.

Example 4

[0196] Assessment was carried out in the same manner as Example 3 except that tolylene diisocyanate (hereinafter, simply referred to as “TDI”) was used instead of HDI to prepare a paint solution.

Example 5

[0197] Polymerization was conducted in the same manner as Example 3 except that the amount of PTBP was changed to 0.86 g (0.006 mol, content of terminal structure: 1.3 mol %) to give a polycarbonate resin (Mv: 51,400; hereinafter, referred to as “PC-3′”).

[0198] 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 3.

Example 6

[0199] A paint solution was prepared and assessed in the same manner as Example 1 except that 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).

Example 7

[0200] In 600 ml of a 9 w/w % aqueous sodium hydroxide solution and 200 ml of pure water, 65.3 g (0.26 mol) of 2,2-bis(4-hydroxy-3-methylphenyl-)propane (hereinafter, simply referred to as “BPC”: manufactured by Honshu Chemical Industry Co., Ltd.), 43.5 g (0.19 mol) of 2,2-bis(4-hydroxyphenyl)propane (hereinafter, simply referred to as “BPA”: manufactured by Mitsubishi Chemical Corporation), 3.06 g (0.022 mol, content of terminal structure: 5.0 mol %) of PHEP (p-hydroxyphenethyl alcohol) and 0.3 g of hydrosulfite were dissolved.

[0201] 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.

[0202] 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.

[0203] 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.

[0204] The obtained precipitate was filtered and dried at 105° C. for 24 hours, thereby obtaining polymer powder.

[0205] The resulting polycarbonate resin (hereinafter, simply referred to as “PC-4”) had My of 25,500, Mw of 57,000 (with respect to PS) and 32,000 (with respect to PC). 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 65,700 (with respect to PS) and 37,000 (with respect to PC). Due to the drying process, a crosslinked polymer was generated via the reaction between the hydroxy group from PHEP and the isocyanate group of HDI in the resin composition.

Example 8

[0206] 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 9

[0207] A paint solution was prepared and assessed in the same manner as Example 3 except that the amount of HDI was changed to 0.8 parts by mass (8 parts by mass relative to 100 parts by mass of the polycarbonate resin).

Comparative example 1

[0208] Assessment was conducted in the same manner as Example 1 except that a paint solution was prepared without HDI.

Comparative example 2

[0209] Assessment was conducted in the same manner as Example 3 except that a paint solution was prepared without HDI.

Comparative example 3

[0210] Polymerization was conducted in the same manner as Example 1 except that 100.3 g (0.35 mol) of 1,1-bis(4-hydroxyphenyl)-1-phenylethane (hereinafter, simply referred to as “BPAP”: manufactured by Honshu Chemical Industry Co., Ltd.) was used instead of BPC, and the amount of PTBP was changed to 2.01 g (0.013 mol, content of terminal structure: 3.9 mol %)) to give a polycarbonate resin (Mv: 20,000; hereinafter, simply referred to as “PC-5”). PC-5 (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.

Comparative example 4

[0211] A paint solution was prepared and assessed in the same manner as Example 3 except that 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).

Comparative example 5

[0212] Polymerization was conducted in the same manner as Example 1 except that 100.5 g (0.38 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 BPC, and the amount of PTBP was changed to 1.13 g (0.008 mol, content of terminal structure: 2.0 mol %)) to give a polycarbonate resin (Mv: 32,500; hereinafter, simply referred to as “PC-6”). A paint solution was prepared and assessed in the same manner as Example 4 except that PC-6 was used instead of PC-2.

Comparative example 6

[0213] Polymerization was conducted in the same manner as Example 1 except that 90.3 g (0.33 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 BPC, and the amount of PTBP was changed to 0.63 g (0.004 mol, content of terminal structure: 1.3 mol %)) to give a polycarbonate resin (Mv: 50,000; hereinafter, simply referred to as “PC-7”). A paint solution was prepared and assessed in the same manner as Example 1 except that PC-7 was used instead of PC-1.

[0214] The compositions and 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 Poly- isocyanate (Amount added Example/ relative Comp- PC resin to PC Durability arative Abbrevi- Main Terminal resin/ against example ation backbone structure Content) peeling Example PC-1 BPC PTBP HDI 1 1 (10 parts by mass/9.1% by mass) Example PC-1 BPC PTBP XDI 1 2 (10 parts by mass/9.1% by mass) Example PC-2 BPC/BPA PTBP HDI 1 3 (10 parts by mass/9.1% by mass) Example PC-2 BPC/BPA PTBP TDI 2 4 (10 parts by mass/9.1% by mass) Example PC-3 BPC/BPA PTBP HDI 1 5 (10 parts by mass/9.1% by mass) Example PC-1 BPC PTBP HDI 1 6 (30 parts by mass/23.0% by mass) Example PC-4 BPC/BPA PHEP HDI 0 7 (10 parts by mass/9.1% by mass) Example PC-4 BPC/BPA PHEP HDI 1 8 (0.1 parts by mass/0.1% by mass) Example PC-2 BPC/BPA PTBP HDI 4 9 (8 parts by mass/7.4% by mass) Comp- PC-1 BPC PTBP — 5 arative example 1 Comp- PC-2 BPC/BPA PTBP — 5 arative example 2 Comp- PC-5 BPAP PTBP HDI 5 arative (10 parts by example mass/9.1% 3 by mass) Comp- PC-5 BPAP PTBP HDI 5 arative (30 parts by example mass/23.0% 4 by mass) Comp- PC-6 BPZ PTBP HDI 5 arative (10 parts by example mass/9.1% 5 by mass) Comp- PC-7 MIBK PTBP HDI 5 arative (10 parts by example mass/9.1% 6 by mass)

[0215] 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 a polycarbonate resin and other resin.

INDUSTRIAL APPLICABILITY

[0216] 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.