Abstract: Provided is a means by which pultrusion can be continuously performed at high speed and the generation of resin residues that adhere to the inner surface of a mold can be suppressed. The present invention also provides a method for producing a fiber-reinforced molded article, wherein a resin-impregnated fibrous base material obtained by impregnating a reinforcing fiber aggregate of reinforcing fiber bundles with an epoxy resin composition is passed through a pultrusion region and pultruded into a predetermined shape by heat-curing the epoxy resin composition, and the epoxy resin composition contains at least components A to D below. A: An aminophenol-type epoxy resin. B: An acid anhydride having a nadic anhydride structure and an acid anhydride having a hydride structure of a phthalic anhydride. C: At least one filler selected from among a silicon compound, a magnesium compound, a calcium compound, an aluminum compound, and inorganic carbon, and having a Mors hardness of 3 or less. D: A release agent.
1. A fiber-reinforced shaped article in which a reinforcing fiber bundle aggregate formed of a plurality of reinforcing fiber bundles converged is impregnated with an epoxy resin composition and the epoxy resin composition is cured,
wherein the epoxy resin composition contains at least components [A], [B], [C], and [D] below, and
a quantity of [A] is 60 to 100 parts by mass per 100 parts by mass of all epoxy resin contained in the epoxy resin composition:
[A]: aminophenol type epoxy resin; [B]: two kinds of acid anhydrides of
[B1]: acid anhydride having a nadic anhydride structure, and
[B2]: acid anhydride having a hydrogenated structure of phthalic anhydride;
[C]: at least one filler having a Mohs hardness of 3 or less, selected from a silicon compound, a magnesium compound, a calcium compound, an aluminum compound, and inorganic carbon; [D]: a release agent.
2. The fiber-reinforced shaped article according to claim 1, wherein the phthalic anhydride in the component [B2] has a hydrogenated structure which is a tetrahydrophthalic anhydride structure or a hexahydrophthalic anhydride structure.
3. The fiber-reinforced shaped article according to claim 1 or 2, wherein the component [B1] is methylnadic anhydride, and the component [B2] is tetrahydromethylphthalic anhydride or hexahydromethylphthalic anhydride.
4. The fiber-reinforced shaped article according to any one of claims 1 to 3, wherein in the epoxy resin composition,
in 100 parts by mass of the component [B], 50 to 90 parts by mass of the component [B1] and 50 to 10 parts by mass of the component [B2] are contained, and
a content of the component [B] per 100 parts by mass of the component [A] is 50 to 200 parts by mass.
5. The fiber-reinforced shaped article according to any
one of claims 1 to 4, wherein in the epoxy resin
composition, the component [C] is particulate talc, and has
an average particle diameter defined by a result measured
with a laser diffraction type particle size distribution analyzer of 2 to 7 um.
6. The fiber-reinforced shaped article according to any one of claims 1 to 5, wherein in the epoxy resin composition, the component [D] is contained in an amount of 0.1 to 8 parts by mass per 100 parts by mass of the component [A].
7. The fiber-reinforced shaped article according to any one of claims 1 to 6, wherein in the epoxy resin composition, an imidazole derivative as a component [E] is further contained in an amount of 0.1 to 5 parts by mass per 100 parts by mass of the component [A].
8. A method for producing a fiber-reinforced shaped article, wherein a resin-impregnated fiber base material in which a reinforcing fiber bundle aggregate formed of converged reinforcing fiber bundles is impregnated with an epoxy resin composition is passed through a pultrusion region and simultaneously the epoxy resin composition is heat-cured, whereby the resin-impregnated fiber base material is pultruded into a prescribed shape,
wherein the epoxy resin composition contains at least components [A], [B], [C], and [D] below, and
a quantity of [A] is 60 to 100 parts by mass per 100 parts by mass of all epoxy resin contained in the epoxy resin composition:
[A]: aminophenol type epoxy resin; [B]: two kinds of acid anhydrides of
[B1]: acid anhydride having a nadic anhydride structure, and
[B2]: acid anhydride having a hydrogenated structure of phthalic anhydride;
[C]: at least one filler having a Mohs hardness of 3 or less, selected from a silicon compound, a magnesium compound, a calcium compound, an aluminum compound, and inorganic carbon; [D]: a release agent.
9. A method for producing a fiber-reinforced shaped article, wherein a resin-impregnated fiber base material in which a reinforcing fiber bundle aggregate formed of converged reinforcing fiber bundles is impregnated with a thermosetting resin composition is passed through a pultrusion region and simultaneously the thermosetting resin composition is heat-cured, whereby the resin-impregnated fiber base material is pultruded into a prescribed shape,
wherein in the pultrusion region, at least a
pultrusion die having an inlet part and an outlet part, and an after-cure furnace are arranged,
in the pultrusion region, a process in which the resin-impregnated fiber base material is introduced from the inlet part of the pultrusion die, passed through the inside of the die, pulled out from the outlet part of the die, and then passed through the after-cure furnace is carried out, and
conditions (i) to (v) below are satisfied in the pultrusion region:
(i) Formulae (1) to (3) below are satisfied where the pultrusion die temperature is denoted by Tp (°C) and the in-die residence time calculated by dividing the path length of the resin-impregnated fiber base material in the die (hereinafter referred to as die path length) (m) by a shaping speed (m/min) is denoted by H (min),
230 - 100H < Tp < 252 - 80H ... Formula (1)
180 < Tp < 245 ... Formula (2)
0.1 < H < 0.9 ... Formula (3);
(ii) the thermosetting resin composition is kept in a liquid state at the inlet part of the pultrusion die;
(iii) the thermosetting resin composition transitions from a liquid state to a gelled state in the die;
(iv) the thermosetting resin composition maintains a gelled state with a degree of cure of 33 to 80% at the die
outlet part;
(v) the thermosetting resin composition is in a cured state with a degree of cure of 95% or more in the after-cure furnace.
10. The method for producing a fiber-reinforced shaped article according to claim 9, wherein in the die, a region where the thermosetting resin composition starts to transition to a gelled state lies within a region distancing from the die outlet part by a length of 10 to 50% of the die path length.
11. The method for producing a fiber-reinforced shaped article according to any one of claims 8 to 10, wherein the resin-impregnated fiber base material is heated in the after-cure furnace while being in non-contact with a heating element.
12. The method for producing a fiber-reinforced shaped article according to any one of claims 1 to 11, wherein the fiber-reinforced shaped article is used for an electric cable core application.
| # | Name | Date |
|---|---|---|
| 1 | 202047036105-STATEMENT OF UNDERTAKING (FORM 3) [21-08-2020(online)].pdf | 2020-08-21 |
| 2 | 202047036105-PRIORITY DOCUMENTS [21-08-2020(online)].pdf | 2020-08-21 |
| 3 | 202047036105-FORM 1 [21-08-2020(online)].pdf | 2020-08-21 |
| 4 | 202047036105-DRAWINGS [21-08-2020(online)].pdf | 2020-08-21 |
| 5 | 202047036105-DECLARATION OF INVENTORSHIP (FORM 5) [21-08-2020(online)].pdf | 2020-08-21 |
| 6 | 202047036105-COMPLETE SPECIFICATION [21-08-2020(online)].pdf | 2020-08-21 |
| 7 | 202047036105-FORM-26 [04-09-2020(online)].pdf | 2020-09-04 |
| 8 | 202047036105-Proof of Right [08-09-2020(online)].pdf | 2020-09-08 |
| 9 | 202047036105-FORM 3 [09-02-2021(online)].pdf | 2021-02-09 |
| 10 | 202047036105.pdf | 2021-10-18 |
| 11 | 202047036105-Correspondence, Form-1_18-10-2021.pdf | 2021-10-18 |
| 12 | 202047036105-FORM 18 [06-01-2022(online)].pdf | 2022-01-06 |
| 13 | 202047036105-FER.pdf | 2022-01-19 |
| 14 | 202047036105-OTHERS [11-07-2022(online)].pdf | 2022-07-11 |
| 15 | 202047036105-Information under section 8(2) [11-07-2022(online)].pdf | 2022-07-11 |
| 16 | 202047036105-FORM 3 [11-07-2022(online)].pdf | 2022-07-11 |
| 17 | 202047036105-FER_SER_REPLY [11-07-2022(online)].pdf | 2022-07-11 |
| 18 | 202047036105-COMPLETE SPECIFICATION [11-07-2022(online)].pdf | 2022-07-11 |
| 19 | 202047036105-CLAIMS [11-07-2022(online)].pdf | 2022-07-11 |
| 20 | 202047036105-Correspondence_Form-26_19-07-2022.pdf | 2022-07-19 |
| 21 | 202047036105-PatentCertificate13-12-2022.pdf | 2022-12-13 |
| 22 | 202047036105-IntimationOfGrant13-12-2022.pdf | 2022-12-13 |
| 1 | SearchHistory(1)E_14-01-2022.pdf |