RESIN COMPOSITION, MOLDED ARTICLE, LAMINATE, COATING MATERIAL, AND ADHESIVE

Abstract

A resin composition contains an epoxy compound and a smectite with partially immobilized lithium.

Claims

1. A resin composition comprising an epoxy compound and a smectite with partially immobilized lithium.

2. The resin composition according to claim 1, wherein the epoxy compound has an epoxy equivalent weight of 50 to 3000 g/eq.

3. The resin composition according to claim 1, wherein the epoxy compound has at least one structure of an aromatic ring structure and an aliphatic ring structure.

4. The resin composition according to claim 1, wherein the smectite with partially immobilized lithium has a cation exchange capacity of 1 to 70 meq/100 g.

5. The resin composition according to claim 1, further comprising at least one curing agent.

6. The resin composition according to claim 5, wherein the curing agent is at least one curing agent selected from the group consisting of acid anhydride-based curing agents, phenolic curing agents, and amide-based curing agents.

7. The resin composition according to claim 1, wherein the smectite with partially immobilized lithium is present in an amount of 3% to 70% by mass based on total nonvolatile content of the resin composition.

8. An article molded from a resin composition according to claim 1.

9. A laminate comprising a substrate and a molded article according to claim 8 on the substrate.

10. A gas barrier material comprising a resin composition according to claim 1.

11. A coating material comprising a resin composition according to claim 1.

12. An adhesive comprising a resin composition according to claim 1.

Description

EXAMPLES

[0083] The following describes the present invention in further detail by examples, but the present invention is not limited to these.

[0084] The filler to be contained in the resin composition was a smectite with partially immobilized lithium or a smectite without partially immobilized lithium. The smectite with partially immobilized lithium was a montmorillonite slurry available from Kunimine Industries Co., Ltd. (trade name, RCEC-W; cation exchange capacity, 39.0 meg/100 g). The amount (w/w%) of the smectite with partially immobilized lithium in this dispersion slurry was 20 w/w%. The smectite without partially immobilized lithium was natural montmorillonite (trade name, KUNIPIA-E; cation exchange capacity, 108 meq/100 g; Kunimine Industries Co., Ltd.) (KUNIPIA is a registered trademark).

[0085] The modifier was KBM-503, a silane coupling agent (3-methacryloxypropyltrimethoxysilane, trade name, Shin-Etsu Chemical Co., Ltd.), or KBM-3033, a silane compound (n-propyltrimethoxysilane, trade name, Shin-Etsu Chemical Co., Ltd.).

Example 1

[0086] To 100 parts by mass of a bisphenol-A liquid epoxy compound (trade name, EPICLON 850-S; DIC Corporation), 210 parts by mass of the slurry of a smectite with partially immobilized lithium, 384 parts by mass of acetonitrile, 43 parts by mass of water, and 93 parts by mass of 2-propanol as solvents, and 59.5 parts by mass of a modifier solution were added. The materials were kept under stirring for 8 hours. Then 90 parts by mass of methyltetrahydrophthalic anhydride (trade name, EPICLON B-570H; DIC Corporation) and 1 part by mass of N,N-dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.) were added. In this way, a resin composition of Example 1 was obtained. This composition was named liquid coating 1. The modifier solution was prepared by stirring for 2 hours a solution made with 2.8 parts by mass of KBM-503, 0.6 parts by mass of water, 56.0 parts by mass of 2-propanol, and 0.1 parts by mass of hydrochloric acid (concentration: 0.1 mol/1).

[0087] A 25-m polyimide film (Kapton film, Du Pont-Toray Co., Ltd.) (Kapton is a registered trademark; the same applies hereinafter) was coated with the resulting liquid coating 1 using a bar coater to a dry coating thickness of 2 m. Shorty after coating, the coated polyimide film was heated in a drying oven at 120 C. for 1 minute. The film was then heated in a drying oven at 120 C. for 3 hours and then heated in a drying oven at 175 C. for 5 hours. In this way, an article molded from the resin composition of Example 1 was formed on the polyimide film, and a film laminate of Example 1 was obtained.

[0088] In the resin composition and molded article of Example 1, the amount of the smectite with partially immobilized lithium (filler content) was 18% by mass of the total nonvolatile content.

Examples 2 to 10

[0089] Resin compositions of Examples 2 to 10 were obtained as in Example 1 except that EPICLON 850-S was replaced with the epoxy compound specified in Table 1, that the solvent acetonitrile and water were replaced with methyl ethyl ketone (MEK) in some examples (See Examples 5 and 6.), that the amounts of each ingredient were changed to the values given in Table 1, and that the modifier solution was a modifier solution prepared to the formula given in Table 1. These compositions were named liquid coatings 2 to 10, respectively. The amount of modifier solution used was the total of the amounts of each ingredient used to prepare the solution, specified in Table 1. In Examples 2 to 6 and 10, the epoxy compound was dissolved in a small amount of MEK before use. In Examples 2 to 4 and 10, 100 parts by mass of the epoxy compound was dissolved in 42.9 parts by mass of MEK. In Example 5, 100 parts by mass of the epoxy compound was dissolved in 78.6 parts by mass of MEK. In Example 6, 100 parts by mass of the epoxy compound was dissolved in 150 parts by mass of MEK.

[0090] Then articles molded from the resin compositions of Examples 2 to 10 were formed on 25-m polyimide films (Kapton film, Du Pont-Toray Co., Ltd.) as in Example 1 except that liquid coating 1 was replaced with liquid coatings 2 to 10, respectively. In this way, film laminates of Examples 2 to 10 were obtained.

[0091] In all of the resin compositions and molded articles of Examples 2 to 10, the amount of the smectite with partially immobilized lithium (filler content) was 18% by mass of the total nonvolatile content. [0091]

Examples 11 to 13

[0092] Resin compositions of Examples 11 to 13 were obtained as in Example 1 except that B-570H was replaced with the curing agent specified in Table 2, that the catalyst (curing accelerator) N,N-dimethylbenzylamine was not used, that the solvent water was not used in an example (See Example 12.), that the amounts of each ingredient were changed to the values given in Table 2, and that the modifier solution was a modifier solution prepared to the formula given in Table 2. These compositions were named liquid coatings 11 to 13, respectively. The amount of modifier solution used was the total of the amounts of each ingredient used to prepare the solution, specified in Table 2.

[0093] Then articles molded from the resin compositions of Examples 11 to 13 were formed on 25-m polyimide films (Kapton film, Du Pont-Toray Co., Ltd.) as in Example 1 except that liquid coating 1 was replaced with liquid coatings 11 to 13, respectively. In this way, film laminates of Examples 11 to 13 were obtained.

[0094] In all of the resin compositions and molded articles of Examples 11 to 13, the amount of the smectite with partially immobilized lithium (filler content) was 18% by mass of the total nonvolatile content.

Example 14

[0095] A resin composition of Example 14 was obtained as in Example 1 except that the modifier KBM-503 was replaced with KBM3033, that the amounts of each ingredient were changed to the values given in Table 2, and that the modifier solution was a modifier solution prepared to the formula given in Table 2. This composition was named liquid coating 14. The amount of modifier solution used was the total of the amounts of each ingredient used to prepare the solution, specified in Table 2.

[0096] Then an article molded from the resin composition of Example 14 was formed on a 25-m polyimide film (Kapton film, Du Pont-Toray Co., Ltd.) as in Example 1 except that liquid coating 1 was replaced with liquid coating 14. In this way, a film laminate of Example 14 was obtained.

[0097] In the resin composition and molded article of Example 14, the amount of the smectite with partially immobilized lithium (filler content) was 18% by mass of the total nonvolatile content.

Examples 15 to 18

[0098] Resin compositions of Examples 15 to 18 were obtained as in Example 1 except that the amounts of each ingredient were changed to the values given in Table 2 and that the modifier solution was a modifier solution prepared to the formula given in Table 2. These compositions were named liquid coatings 15 to 18, respectively. The amount of modifier solution used was the total of the amounts of each ingredient used to prepare the solution, specified in Table 2.

[0099] Then articles molded from the resin compositions of Examples 15 to 18 were formed on 25-m polyimide films (Kapton film, Du Pont-Toray Co., Ltd.) as in Example 1 except that liquid coating 1 was replaced with liquid coatings 15 to 18, respectively. In this way, film laminates of Examples 15 to 18 were obtained.

[0100] In the resin compositions and molded articles of Examples 15 to 18, the amounts of the smectite with partially immobilized lithium (filler content levels) were 5% by mass, 10% by mass, 30% by mass, and 70% by mass, respectively, of the total nonvolatile content.

Comparative Example 1

[0101] To 100 parts by mass of a bisphenol-A liquid epoxy compound (trade name, EPICLON 850-S; DIC Corporation), 446 parts by mass of the natural montmorillonite (KUNIPIA-F), 3841 parts by mass of acetonitrile, 427 parts by mass of water, and 64 parts by mass of 2-propanol as solvents, and 126.5 parts by mass of a modifier solution were added. The materials were kept under stirring for 8 hours. Then 90 parts by mass of methyltetrahydrophthalic anhydride (trade name, EPICLON B-570H; DIC Corporation) and 1 part by mass of N,N-dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.) were added. In this way, a resin composition of Comparative Example 1 was obtained. This composition was named liquid coating 19. The modifier solution was prepared by stirring for 2 hours a solution made with 24.2 parts by mass of KBM503, 5.3 parts by mass of water, 97.0 parts by mass of 2-propanol, and 0.1 parts by mass of hydrochloric acid (concentration: 0.1 mol/1).

[0102] An article molded from the resin composition of Comparative Example 1 was formed as in Example 1 except that liquid coating 1 was replaced with liquid coating 19. In this way, a film laminate of Comparative Example 1 was obtained.

[0103] In the resin composition and molded article of Comparative Example 1, the amount of the natural montmorillonite (filler content) was 70% by mass of the total nonvolatile content, and the modifier loading (modifier content) was 5% by mass of the whole amount of the natural montmorillonite (filler).

Comparative Example 2

[0104] To 100 parts by mass of a bisphenol-A liquid epoxy compound (trade name, EPICLON 850-S; DIC Corporation), 500 parts by mass of acetonitrile was added. The materials were kept under stirring for 8 hours. Then 90 parts by mass of methyltetrahydrophthalic anhydride (trade name, EPICLON B-570H; DIC Corporation) and 1 part by mass of N,N-dimethylbenzylamine (Wako Pure Chemical Industries, Ltd.) were added. In this way, a resin composition of Comparative Example 2 was obtained. This composition was named liquid coating 20.

[0105] An article molded from the resin composition of Comparative Example 2 was formed as in Example 1 except that liquid coating 1 was replaced with liquid coating 20. In this way, a film laminate of Comparative Example 2 was obtained.

<Testing>

[0106] The film laminates of Examples 1 to 18 and Comparative Examples 1 and 2 were tested for film formation, oxygen permeability, and water vapor permeability. The test results are presented in Tables 1 and 2. The tests for film formation, oxygen permeability, and water vapor permeability were performed as follows.

(Film Formation)

[0107] Film formation was graded A if the coated surface of the film laminate was smooth or B if the coated surface was not smooth.

(Oxygen Permeability)

[0108] The measurement of oxygen permeability was conducted in an atmosphere at a temperature of 23 C. and a humidity of 0% RH and in an atmosphere at a temperature 23 C. and a humidity of 90% RH using MOCON OX-TRAN 1/50 oxygen transmission rate test system in accordance with JIS-K7126 (equal-pressure method). RH stands for relative humidity.

(Water Vapor Permeability)

[0109] The measurement of water vapor permeability was conducted in an atmosphere at a temperature of 40 C. and a humidity of 90% RH using Systech Illinois 7001 water vapor permeation analyzer in accordance with JIS-K7129.

TABLE-US-00001 TABLE 1 Epoxy equivalent weight Example 1 Example 2 Example 3 Example 4 Example 5 Epoxy EP850S 185 100 compounds SP1050 500 100 SP2050 650 100 SP4050 1000 100 SP7050 2100 100 HM-091 2310 EP830 170 2021P 130 EX-212 116 EX-861 550 Fillers RCEC-W(NV20%) 210 152 140 130 121 KUNIPIA-F Solvents Methyl ethyl ketone 427 Acetonitrile 384 384 384 384 2-Propanol 93 133 136 138 141 Water 43 43 43 43 Modifier KBM-503 2.8 2.1 1.9 1.8 1.7 solution KBM-3033 Water 0.6 0.5 0.4 0.4 0.4 2-Propanol 56.0 86.0 86.0 86.0 85.0 0.1 mol/l HCl 0.1 0.1 0.1 0.1 0.1 Curing B-570H 90 37 26 18 9 agents DICY7 TD-2090 IPD Catalyst N,N-dimethylbenzylamine 1 1 1 1 1 Filler content (% by mass) 18 18 18 18 18 Film formation A A A A A Oxygen permeability 0% RH (cc/m.sup.2 .Math. day .Math. atm) 4 5 7 10 21 Oxygen permeability 90% RH (cc/m.sup.2 .Math. day .Math. atm) 8 10 10 12 18 Water vapor permeability (g/m.sup.2 .Math. day) 4 4 5 7 15 Epoxy equivalent Example weight Example 6 Example 7 Example 8 Example 9 10 Epoxy EP850S 185 compounds SP1050 500 SP2050 650 SP4050 1000 SP7050 2100 HM-091 2310 100 EP830 170 100 2021P 130 100 EX-212 116 100 EX-861 550 100 Fillers RCEC-W(NV20%) 119 221 250 268 144 KUNIPIA-F Solvents Methyl ethyl ketone 427 Acetonitrile 384 384 384 384 2-Propanol 141 112 108 104 135 Water 43 43 43 43 Modifier KBM-503 1.6 3.0 3.5 3.7 2.0 solution KBM-3033 Water 0,4 0.6 0.8 0.8 0.4 2-Propanol 85.0 59.0 85.0 85.0 86.0 0.1 mol/l HCl 0.1 0.1 0.1 0.1 0.1 Curing B-570H 7 100 127 143 30 agents DICY7 TD-2090 IPD Catalyst N,N-dimethylbenzylamine 1 1 1 1 1 Filler content (% by mass) 18 18 18 18 18 Film formation A A A A A Oxygen permeability 0% RH (cc/m.sup.2 .Math. day .Math. atm) 90 2 10 20 67 Oxygen permeability 90% RH (cc/m.sup.2 .Math. day .Math. atm) 56 3 11 22 88 Water vapor permeability (g/m.sup.2 .Math. day) 32 3 13 23 36

TABLE-US-00002 TABLE 2 Epoxy equivalent Example Example Example Example Example Example weight 11 12 13 14 15 16 Epoxy EP850S 185 100 100 100 100 100 100 compounds SP1050 500 SP2050 650 SP4050 1000 SP7050 2100 HM-091 2310 EP830 170 2021P 130 EX-212 116 EX-861 550 Fillers RCEC-W(NV20%) 115 170 137 210 50 106 KUNIPIA-F Solvents Methyl ethyl ketone Acetonitrile 384 427 384 384 384 384 2-Propanol 140 83 137 106 158 144 Water 43 43 43 43 43 Modifier KBM-503 1.6 2.4 1.9 0.7 1.5 solution KBM-3033 6.5 Water 0.3 0.5 0.4 2.2 0.2 0.3 2-Propanol 85.0 85.0 85.0 65.0 85.0 85.0 0.1 mol/l HCl 0.1 0.1 0.1 0.1 0.1 0.1 Curing B-570H 90 90 90 agents DICY7 5 TD-2090 55 IPD 24 Catalyst N,N-dimethylbenzylamine 1 1 1 Filler content (% by mass) 18 18 18 18 5 10 Film formation A A A A A A Oxygen permeability 0% RH (cc/m.sup.2 .Math. day .Math. atm) 16 5 72 19 15 8 Oxygen permeability 90% RH (cc/m.sup.2 .Math. day .Math. atm) 10 2 39 10 18 12 Water vapor permeability (g/m.sup.2 .Math. day) 12 4 18 8 14 10 Epoxy equivalent Example Example Comparative Comparative weight 17 18 Example 1 Example 2 Epoxy EP850S 185 100 100 100 100 compounds SP1050 500 SP2050 650 SP4050 1000 SP7050 2100 HM-091 2310 EP830 170 2021P 130 EX-212 116 EX-861 550 Fillers RCEC-W(NV20%) 409 2228 KUNIPIA-F 446 Solvents Methyl ethyl ketone Acetonitrile 384 3841 3841 500 2-Propanol 68 64 64 Water 43 427 427 Modifier KBM-503 5.7 24.2 24.2 solution KBM-3033 Water 1.2 5.3 5.3 2-Propanol 85.0 97.0 97.0 0.1 mol/l HCl 0.1 1.0 1.0 Curing B-570H 90 90 90 90 agents DICY7 TD-2090 IPD Catalyst N,N-dimethylbenzylamine 1 1 1 1 Filler content (% by mass) 30 70 70 Film formation A B B A Oxygen permeability 0% RH (cc/m.sup.2 .Math. day .Math. atm) 5 102 157 204 Oxygen permeability 90% RH (cc/m.sup.2 .Math. day .Math. atm) 7 70 90 99 Water vapor permeability (g/m.sup.2 .Math. day) 5 42 60 62

[0110] The details of the epoxy compounds and curing agents listed in Tables 1 and 2 are as follows.

[Aromatic Epoxy Compounds]

[0111] EP850S: A bisphenol-A liquid epoxy compound; trade name, EPICLON 850-S; DIC Corporation; epoxy equivalent weight, 185 g/eq [0112] EP1050: A bisphenol-A solid epoxy compound; trade name, EPICLON 1050; DIC Corporation; epoxy equivalent weight, 500 g/eq [0113] EP2050: A bisphenol-A solid epoxy compound; trade name, EPICLON 2050; DIC Corporation; epoxy equivalent weight, 650 g/eq [0114] EP4050: A bisphenol-A solid epoxy compound; trade name, EPICLON 4050; DIC Corporation; epoxy equivalent weight, 1000 g/eq [0115] E07050: A bisphenol-A solid epoxy compound; trade name, EPICLON 7050; DIC Corporation; epoxy equivalent weight, 2100 g/eq [0116] HM-091: A bisphenol-A solid epoxy compound; trade name, EPICLON HM-091; DIC Corporation; epoxy equivalent weight, 2310 g/eq [0117] EP830: A bisphenol-F epoxy compound; trade name, EPICLON 830; DIC Corporation; epoxy equivalent weight, 170 g/eq

[Alicyclic Epoxy Compound]

[0118] 2021P: 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate; trade name, CELLOXIDE 2021P; Daicel Corporation; epoxy equivalent weight, 130 g/eq

[Aliphatic Epoxy Compounds]

[0119] EX-212: 1,6 Hexanediol diglycidyl ether; trade name, Denacol EX-212; Nagase ChemteX Corporation; epoxy equivalent weight, 116 g/eq [0120] EX-861: Polyethylene glycol diglycidyl ether; trade name, Denacol EX-861; Nagase ChemteX Corporation; epoxy equivalent weight, 550 g/eq

[Acid Anhydride-Based Curing Agent]

[0121] H-570H: Methyltetrahydrophthalic anhydride; trade name, EPICLON B-570H; DIC Corporation

[Amide-Based Curing Agent]

[0122] DICY7: Dicyandiamide, trade name, Mitsubishi Chemical Corporation

[Phenolic Curing Agent]

[0123] TD-2090: A phenol novolac resin; trade name, PHENOLITE TD-2090; DIC Corporation

[Amine-Based Curing Agent]

[0124] IPD: Isophorone diamine; trade name, VESTAMIN IPD; EVONIK

INDUSTRIAL APPLICABILITY

[0125] The resin composition according to the present invention can be suitably used in various fields, including packaging materials and also electronic materials and building materials, by virtue of being superior in gas barrier properties, in particular water vapor and oxygen barrier properties.