SIZING AGENT FOR CARBON FIBER, CARBON FIBER WITH IMPROVED INTERFACIAL ADHESION, POLYMERIZATION REACTION TYPE CARBON FIBER-REINFORCED POLYMER COMPOSITE MATERIAL USING SAME, AND PRODUCTION METHOD THEREFOR

Abstract

The present invention relates to a sizing agent for carbon fibers, a carbon fiber with improved interfacial adhesion, a polymerization reaction type carbon fiber-reinforced polymer composite material using the same, and a production method therefor and, more specifically, to a sizing agent for carbon fibers, comprising a phenoxy resin and a block isocyanate compound prepared through a reaction of -caprolactam with one of two isocyanate groups of a diisocyanate compound, and the production of a carbon fiber with improved interfacial adhesion using the same, a polymerization reaction type carbon fiber-reinforced polymer composite material using the carbon fiber with improved interfacial adhesion, and a production method therefor.

Claims

1. (canceled)

2. A sizing agent for carbon fiber prepared by urethane bond formation between a compound represented by formula 1 below and a hydroxy group of a phenoxy resin: ##STR00012## (In formula 1, X is a C.sub.2-C.sub.20 aliphatic, aromatic, alicyclic, or aromatic aliphatic hydrocarbon.)

3. A production method of a sizing agent for carbon fiber comprising the following steps: preparing a block isocyanate compound by reacting -caprolactam with one of two isocyanate groups of a diisocyanate compound as shown in reaction formula 1 below; and ##STR00013## (In reaction formula 1, X is a C.sub.2-C.sub.20 aliphatic, aromatic, alicyclic, or aromatic aliphatic hydrocarbon.) preparing a phenoxy resin modified with caprolactam by reacting the remaining isocyanate group of block isocyanate with a hydroxy group of a phenoxy resin.

4. The production method of a sizing agent for carbon fiber according to claim 3, wherein the diisocyanate compound is an aliphatic, aromatic, alicyclic or aromatic aliphatic compound which contains two isocyanate groups in its molecular structure.

5. The production method of a sizing agent for carbon fiber according to claim 3, wherein the diisocyanate compound is one or more aliphatic isocyanates selected from the group consisting of ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, dodecamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, butane diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatemethylcaproate, bis(2-isocyanateethyl)fumarate, bis(2-isocyanateethyl)carbonate, bis(isocyanatoethyl) carbonate, bis(isocyanatoethyl)ether, and lysinediisocyanatomethylester.

6. The production method of a sizing agent for carbon fiber according to claim 3, wherein the diisocyanate compound is one or more aromatic isocyanates selected from the group consisting of 1,3-phenylene diisocyanate (C.sub.6H.sub.4(NCO).sub.2), 1,4-phenylene diisocyanate (C.sub.6H.sub.4(NCO).sub.2), toluene-2,4-diisocyanate (CH.sub.3C.sub.6H.sub.3(NCO).sub.2), toluene-2,6-diisocyanate (CH.sub.3C.sub.6H.sub.3(NCO).sub.2), toluene-2,5-diisocyanate (CH.sub.3C.sub.6H.sub.3(NCO).sub.2), toluene-3,5-diisocyanate (CH.sub.3C.sub.6H.sub.3(NCO).sub.2), 1,3-dimethylbenzene-2,4-diisocyanate ((CH.sub.3).sub.2C.sub.6H.sub.2(NCO).sub.2), 1,3-methylbenzene-4,6-diisocyanate ((CH.sub.3).sub.2C.sub.6H.sub.2(NCO).sub.2), 1,4-methylbenzene-2,5-diisocyanate ((CH.sub.3).sub.2C.sub.6H.sub.2(NCO).sub.2), 1-ethylbenzene-2,4-diisocyanate (C.sub.2H.sub.5.C.sub.6H.sub.3(NCO).sub.2), 1-isopropylbenzene-2,4-diisocyanate (i-C.sub.3H.sub.7C.sub.6H.sub.3(NCO).sub.2), 1-chlorobenzene-2,4-diisocyanate (ClC.sub.6H.sub.3(NCO).sub.2), 1-nitrobenzene-2,4-diisocyanate (O.sub.2NC.sub.6H.sub.3(NCO).sub.2), 1-methoxybenzene-2,4-diisocyanate (CH.sub.3OC.sub.6H.sub.3(NCO).sub.2), 1-methoxybenzene-2,5-diisocyanate (CH.sub.3OC.sub.6H.sub.3(NCO).sub.2), 1-ethoxybenzene-2,4-diisocyanate (C.sub.2H.sub.5OC.sub.6H.sub.3(NCO).sub.2), azobenzene-4,4-diisocyanate (OCNC.sub.6H.sub.4NNC.sub.6H.sub.4NCO), diphenylether-4,4-diisocyanate (OCNC.sub.6H.sub.4OC.sub.6H.sub.4NCO), naphthalene-1,4-diisocyanate (C.sub.10H.sub.6(NCO).sub.2), naphthalene-1,5-diisocyanate (C.sub.10H.sub.6(NCO).sub.2), naphthalene-2,6-diisocyanate (C.sub.10H.sub.6(NCO).sub.2), naphthalene-2,7-diisocyanate (C.sub.10H.sub.6(NCO).sub.2), biphenyl-4,4-diisocyanate (OCNC.sub.6H.sub.4C.sub.6H.sub.4NCO), 3,3-dimethyl-biphenyl-4,4-diisocyanate ([OCN(CH.sub.3)C.sub.6H.sub.3-].sub.2), 3,3-dimethoxybiohenyl-4,4-diisocyanate ([OCN(CH.sub.3O)C.sub.6H.sub.3-].sub.2), diphenylmethane-4,4-diisocyanate (OCNC.sub.6H.sub.4CH.sub.2C.sub.6H.sub.4NCO), diphenyldimethylmethane-4,4-diisocyanate ((CH.sub.3).sub.2C[C.sub.6H.sub.4NCO].sub.2), benzophenone-3, 3-diisocyanate (OC[C.sub.6H.sub.4NCO].sub.2), fluorene-2,7-diisocyanate (C.sub.13H.sub.8(NCO).sub.2), antraquinone-2,6-diisocyanate (C.sub.14H.sub.6O.sub.2(NCO).sub.2), 9-ethylcarbazole-3,6-diisocyanate (C.sub.14H.sub.11N(NCO).sub.2), pyrene-3,8-diisocyanate (C.sub.16H.sub.8(NCO).sub.2), and chrysene-2,8-diisocyanate (C.sub.18H.sub.10(NCO).sub.2).

7. A carbon fiber with improved interfacial adhesion, which is surface-treated with the sizing agent for carbon fiber of claim 2.

8. A carbon fiber reinforced polymer composite material comprising a carbon fiber with improved interfacial adhesion of claim 7; and a polymer matrix containing the carbon fiber above as a reinforcement.

9. The carbon fiber reinforced polymer composite material according to claim 8, wherein the carbon fiber is in the form of a dispersion comprising multiple monofilaments or a fibrous assembly selected from the group consisting of plain-woven, knit, braid, non-woven, satin, warp sating and twill.

10. The carbon fiber reinforced polymer composite material according to claim 8, wherein the polymer matrix is polyamide.

11. A production method of a polymerization reaction type carbon fiber-reinforced polymer composite material comprising the following steps: surface-treating a carbon fiber with the sizing agent for carbon fiber of claim 2; impregnating a monomer in which -caprolactam is impregnated in the carbon fiber surface-treated with the sizing agent above; and polymerizing a monomer in which the impregnated -caprolactam is polymerized.

12. The production method of a polymerization reaction type carbon fiber-reinforced polymer composite material according to claim 11, wherein the step of polymerizing a monomer is accomplished by the sizing agent coated on the surface of the carbon fiber playing a role of an initiator to induce polymerization of -caprolactam.

13. The production method of a polymerization reaction type carbon fiber-reinforced polymer composite material according to claim 11, wherein the step of polymerizing a monomer is accomplished with -caprolactam by using an additional initiator.

14. The production method of a polymerization reaction type carbon fiber-reinforced polymer composite material according to claim 11, wherein the carbon fiber is in the form of a dispersion comprising multiple monofilaments or a fibrous assembly selected from the group consisting of plain-woven, knit, braid, non-woven, satin, warp sating and twill.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG. 1 shows the FTIR spectrum of a sizing agent for carbon fiber according to an embodiment of the present invention.

[0029] FIG. 2 is a conceptual diagram illustrating the equipment for producing a polymerization reaction type carbon fiber-reinforced polymer composite material according to an embodiment of the present invention.

[0030] FIG. 3 is a conceptual diagram illustrating the improvement of surface adhesion between the carbon fiber treated with the sizing agent of the present invention and a polymer resin matrix according to an embodiment of the present invention.

[0031] FIG. 4 is a set of photographs illustrating the shapes of a composite material specimen and the states thereof before and after the test according to an embodiment of the present invention.

[0032] FIG. 5 is a set of photographs illustrating the shapes of a composite material specimen and the states thereof before and after the test according to an embodiment of the present invention.

[0033] FIG. 6 is a graph illustrating the results of shear test of the composite material according to an embodiment of the present invention.

[0034] FIG. 7 is a graph illustrating the results of shear test of the composite material according to an embodiment of the present invention.

[0035] FIG. 8 is a graph illustrating the comparison of the results of shear test of the composite materials according to an embodiment of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0036] Hereinafter, the present invention is described in detail.

[0037] The terms or words used in this description and claims are not limited to ordinary or dictionary meaning and can be interpreted as a meaning and notion in relation to the technical idea of the present invention, based on the principles that the terms can be defined properly to describe the present invention in the best way. In addition, the term contain an element in this description indicates including other elements additionally not excluding other elements, unless specifically stated otherwise.

[0038] The present invention provides a sizing agent for carbon fiber comprising a compound represented by formula 1 below and a phenoxy resin.

##STR00004##

[0039] In formula 1, X is a C.sub.2-C.sub.20 aliphatic, aromatic, alicyclic, or aromatic aliphatic hydrocarbon.

[0040] In the sizing agent for carbon fiber of the present invention, the compound represented by formula 1 is preferably included at the concentration appropriate for the reaction with a hydroxy group included in the phenoxy resin. More preferably, the ratio of the compound represented by formula 1 and the phenoxy resin is 2:1, but the amount of the compound represented by formula 1 can be increased higher than the equivalent of OH group included in the phenoxy resin.

[0041] The chemical structure of the phenoxy resin according to the present invention is shown in formula 2 below. The phenoxy resin preferably has a molecular weight of 25,000 to 60,000 g/mol and n is 88 to 211, and the content of OH group therein is preferably OH(EW) 130 to 405 mg KOH/g, which would be converted into 2.3210.sup.3 to 7.2210.sup.3 OH mol/(phenoxy resin g). Phenoxy resin has excellent adhesive strength, and accordingly demonstrates excellent interfacial adhesion between a carbon fiber and a polymer resin. Therefore, a carbon fiber sizing agent comprising the phenoxy resin can increase the interfacial adhesion between a carbon fiber and a polymer resin.

##STR00005##

[0042] The present invention also provides a sizing agent for carbon fiber prepared by urethane bond formation between a compound represented by formula 1 below and a hydroxy group of a phenoxy resin.

##STR00006##

[0043] In formula 1, X is a C.sub.2-C.sub.20 aliphatic, aromatic, alicyclic, or aromatic aliphatic hydrocarbon.

[0044] The present invention also provides sizing agent for carbon fiber prepared by urethane bond formation between a block isocyanate compound prepared according to reaction formula 1 below and a hydroxy group of a phenoxy resin.

##STR00007##

[0045] In reaction formula 1, X is a C.sub.2-C.sub.20 aliphatic, aromatic, alicyclic, or aromatic aliphatic hydrocarbon.

[0046] According to an embodiment of the present invention, the diisocyanate above is preferably toluene-2,4-diisocyanate (CH.sub.3C.sub.6H.sub.3 (NCO).sub.2) (2,4-TDI).

[0047] The present invention also provides a production method of a sizing agent for carbon fiber comprising the steps of preparing a block isocyanate compound by reacting -caprolactam with one of two isocyanate groups of a diisocyanate compound as shown in reaction formula 1 below; and preparing a phenoxy resin modified with caprolactam by reacting the remaining isocyanate group of block isocyanate with a hydroxy group of a phenoxy resin.

##STR00008##

[0048] In reaction formula 1, X is a C.sub.2-C.sub.20 aliphatic, aromatic, alicyclic, or aromatic aliphatic hydrocarbon.

[0049] The reaction to produce a phenoxy resin modified with caprolactam by reacting the remaining isocyanate group of block isocyanate with a hydroxy group of a phenoxy resin is described by reaction formula 2 below.

##STR00009##

[0050] In reaction formula 2, the reaction between the remaining isocyanate group of block isocyanate (4-CL-TDI) according to the present invention and the tertiary hydroxy group located in the middle of molecular chain of the phenoxy resin is shown as an example. However, according to the mixing ratio of the block isocyanate and the phenoxy resin in the course of the reaction, an additional reaction with the first and secondary hydroxy group of the phenoxy resin and the concentration thereof can be regulated. At this time, as the ratio of the block isocyanate to the phenoxy resin increases, the effect of a sizing agent becomes more efficient. Preferably, the ratio of the block isocyanate (4-CL-TDI) to the phenoxy resin for the reaction is 2:1.

[0051] In this invention, the diisocyanate compound can be an aliphatic, aromatic, alicyclic or aromatic aliphatic compound which can contain two isocyanate groups in its molecular structure.

[0052] In this invention, the diisocyanate compound can be one or more aliphatic isocyanates selected from the group consisting of ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, dodecamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, decamethylene diisocyanate, butane diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatemethylcaproate, bis(2-isocyanateethyl)fumarate, bis(2-isocyanateethyl) carbonate, 2-isocyanateethyl-2,6-diisocyanatehexanoate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 2,5,7-trimethyl-1,8-diisocyanato-5-isocyanatomethyloctane, bis(isocyanatoethyl) carbonate, bis(isocyanatoethyl)ether, 1,4-butyleneglycoldipropylether-diisocyanate, lysinediisocyanatomethylester, lysinetriisocyanate, 2 isocyanatoethyl-2,6-diisocyanatoethyl-2,6-diisocyanatohexanoate, and 2-isocyanatopropyl-2,6-diisocyanatohexanoate.

[0053] In this invention, the diisocyanate compound can be one or more aromatic isocyanates selected from the group consisting of 1,3-phenylene diisocyanate (C.sub.6H.sub.4(NCO).sub.2), 1,4-phenylene diisocyanate (C.sub.6H.sub.4(NCO).sub.2), toluene-2,4-diisocyanate (CH.sub.3C.sub.6H.sub.3(NCO).sub.2), toluene-2,6-diisocyanate (CH.sub.3C.sub.6H.sub.3(NCO).sub.2), toluene-2,5-diisocyanate (CH.sub.3C.sub.6H.sub.3(NCO).sub.2), toluene-3,5-diisocyanate (CH.sub.3C.sub.6H.sub.3(NCO).sub.2), 1,3-dimethylbenzene-2,4-diisocyanate ((CH.sub.3).sub.2C.sub.6H.sub.2 (NCO).sub.2), 1,3-methylbenzene-4,6-diisocyanate ((CH.sub.3).sub.2C.sub.6H.sub.2 (NCO).sub.2), 1,4-methylbenzene-2,5-diisocyanate ((CH.sub.3).sub.2C.sub.6H.sub.2 (NCO).sub.2), 1-ethylbenzene-2,4-diisocyanate (C.sub.2H.sub.5.C.sub.6H.sub.3(NCO).sub.2), 1-isopropylbenzene-2,4-diisocyanate (i-C.sub.3H.sub.7C.sub.6H.sub.3(NCO).sub.2), 1-chlorobenzene-2,4-diisocyanate (ClC.sub.6H.sub.3 (NCO).sub.2), 1-nitrobenzene-2,4-diisocyanate (O.sub.2NC.sub.6H.sub.3 (NCO).sub.2), 1-methoxybenzene-2,4-diisocyanate (CH.sub.3OC.sub.6H.sub.3 (NCO).sub.2), 1-methoxybenzene-2,5-diisocyanate (CH.sub.3OC.sub.6H.sub.3 (NCO).sub.2), 1-ethoxybenzene-2,4-diisocyanate (C.sub.2H.sub.5OC.sub.6H.sub.3 (NCO).sub.2), azobenzene-4,4-diisocyanate (OCNC.sub.6H.sub.4NNC.sub.6H.sub.4NCO), diphenylether-4,4-diisocyanate (OCNC.sub.6H.sub.4OC.sub.6H.sub.4NCO), naphthalene-1,4-diisocyanate (C.sub.10H.sub.6 (NCO).sub.2), naphthalene-1,5-diisocyanate (C.sub.10H.sub.6 (NCO).sub.2), naphthalene-2,6-diisocyanate (C.sub.10H.sub.6 (NCO).sub.2), naphthalene-2,7-diisocyanate (C.sub.10H.sub.6 (NCO).sub.2), biphenyl-4,4-diisocyanate (OCNC.sub.6H.sub.4C.sub.6H.sub.4NCO), 3,3-dimethyl-biphenyl-4,4-diisocyanate ([OCN(CH.sub.3) C.sub.6H.sub.3].sub.2), 3,3-dimethoxybiohenyl-4,4-diisocyanate ([OCN(CH.sub.3O)C.sub.6H.sub.3].sub.2), diphenylmethane-4,4-diisocyanate (OCNC.sub.6H.sub.4CH.sub.2C.sub.6H.sub.4NCO), diphenyldimethylmethane-4,4-diisocyanate ((CH.sub.3).sub.2C [C.sub.6H.sub.4NCO].sub.2), benzophenone-3,3-diisocyanate (OC[C.sub.6H.sub.4NCO].sub.2), fluorene-2,7-diisocyanate (C.sub.13H.sub.8 (NCO).sub.2), antraquinone-2,6-diisocyanate (C.sub.14H.sub.6O.sub.2 (NCO).sub.2), 9-ethylcarbazole-3,6-diisocyanate (C.sub.14H.sub.11N(NCO).sub.2), pyrene-3,8-diisocyanate (C.sub.16H.sub.8 (NCO).sub.2), and chrysene-2,8-diisocyanate (C.sub.18H.sub.10 (NCO).sub.2).

[0054] The present invention also provides a carbon fiber with improved interfacial adhesion, which is surface-treated with the sizing agent for carbon fiber above.

[0055] The carbon fiber of the present invention can be surface-treated with the mixture of the compound represented by formula 1 and the phenoxy resin, or with the reactant of the compound represented by formula 1 and the phenoxy resin.

[0056] The present invention also provides a carbon fiber reinforced polymer composite material comprising a carbon fiber with improved interfacial adhesion; and a polymer matrix containing the carbon fiber above as a reinforcement.

[0057] In this invention, the polymer matrix can be polyamide. The carbon fiber can be in the form of a dispersion comprising multiple monofilaments or a fibrous assembly selected from the group consisting of plain-woven, knit, braid, non-woven, satin, warp sating and twill.

[0058] The present invention also provides a production method of a polymerization reaction type carbon fiber-reinforced polymer composite material comprising the steps of surface-treating a carbon fiber with a sizing agent for carbon fiber; impregnating a monomer in which -caprolactam is impregnated in the carbon fiber surface-treated with the sizing agent above; and polymerizing a monomer in which the impregnated -caprolactam is polymerized.

[0059] In the step of polymerizing a monomer in this invention, the sizing agent coated on the surface of the carbon fiber plays a role of an initiator to induce polymerization of -caprolactam or an additional initiator can be added to induce the polymerization of -caprolactam.

[0060] Particularly, referring to FIG. 3, the polymerization of caprolactam is initiated by the sizing agent coated on the carbon fiber or the additional initiator, in which the polymer polymerized in the sizing agent coated on the carbon fiber binds to the sizing agent through covalent bond to form a strong interfacial adhesion. At this time, the sizing agent modifies the surface characteristics of the carbon fiber so that the interfacial adhesion can be improved, compared with the conventional carbon fiber using an additional initiator for the polymerization, and further demonstrates better linkage of the polymerized polymer due to the same chemical structure.

[0061] Practical and presently preferred embodiments of the present invention are illustrative as shown in the following Examples.

[0062] However, it will be appreciated that those skilled in the art, on consideration of this disclosure, may make modifications and improvements within the spirit and scope of the present invention.

Preparative Example 1: Preparation of Block Isocyanate (4-CL-TDI)

[0063] First, the reaction of producing the block isocyanate according to an embodiment of the present invention is shown in reaction formula 1 below.

##STR00010##

[0064] 5.13 g of 2,4-toluenediisocyanate (2,4-TDI, Sigmaaldrich Inc.) was added to a three-necked flask, which was heated at 80 C. in of nitrogen and argon atmosphere. A caprolactam solution was prepared by dissolving 3.33 g of caprolactam in 10 g of cyclohexanone. The prepared caprolactam solution was added to the flask drop by drop. After the addition of caprolactam was completed, the reaction was continued for at least 12 hours to prepare a block isocyanate (4-CL-TDI) solution.

Preparative Example 2: Preparation of Sizing Agent for Carbon Fiber: Phenoxy Resin Modified with Caprolactam (CL-TDI Phenoxy Resin)

[0065] Next, the reaction of preparing the phenoxy resin modified with caprolactam by reacting the remaining isocyanate group of the block isocyanate prepared in Preparative Example 1 with a hydroxyl group of the phenoxy resin is shown in reaction formula 2 below.

##STR00011##

[0066] 2.5 g of phenoxy resin (PKHA, InChem Corp., OH e.g. 284 mg KOH/g on solid, 5.06210.sup.3 mol/g) phenoxy resin was dissolved in 50 g of cyclohexanone (SAMCHUN chemical/Shinyo Pure Chemical Co., Ltd.), resulting in the 5 weight % solution. The prepared solution was heated at 80 C. 7.27 g of the block isocyanate (4-CL-TDI) solution prepared in Preparation Example 1 was added thereto drop by drop at the concentration of 2 times equivalent. One hour later, all the reactants were collected, followed by precipitation in excessive toluene. The compound obtained through filtering was vacuum-dried at room temperature to prepare a caprolactam-modified phenoxy resin (CL-TDI Phenoxy resin). The chemical structure of the caprolactam-modified phenoxy resin prepared above was confirmed by FTIR analysis (2930 cm.sup.1: CH.sub.2. CH.sub.3, bonded OH in carboxylic acid, 2270 cm.sup.1: CN, NCO, 1700 cm.sup.1: ester(-COO), ketone(CO), CHO, COOH, 1592 cm.sup.1: COO, benzene ring, 1507 cm.sup.1: benzene ring, 1397 cm.sup.1: COO, CHCH.sub.2, 1361 cm.sup.1: CCH3, CO, 1180 cm.sup.1: ester(-COO), phenol), and the resultant FTIR absorption spectrum was shown in FIG. 1. The production of the phenoxy resin modified with caprolactam, the sizing agent for carbon fiber, (CL-TDI Phenoxy resin) was confirmed by confirming the characteristic peaks of the reactants caprolactam, phenoxy resin and 2,4-toluenediisocyanate and the urethane bond, which is an additional chemical bond, in the product.

Example 1: Preparation of Carbon Fiber Surface-Treated with Sizing Agent

[0067] The block isocyanate (4-CL-TDI) prepared in Preparative Example 1 was simply mixed with phenoxy resin. A TR30 (MITSUBISHI RAYON CO., LTD.) sheet prepared in the form of a plain-woven fabric was coated with the sizing agent by dipping the sheet in the sizing agent solution (0.5 weight % of block isocyanate (4-CL-TDI)/phenoxy resin mixture, 99.5 weight % of cyclohexane/tetrahydrofuran (1:1) mixture). The coated sizing agent was dried in a convection oven at 60 C. for 2 hours, resulting in the preparation of a carbon fiber surface-treated with the sizing agent.

Example 2: Preparation of Carbon Fiber Surface-Treated with Sizing Agent

[0068] A TR30 (MITSUBISHI RAYON CO., LTD.) sheet prepared in the form of a plain-woven fabric was coated with the sizing agent by dipping the sheet in the sizing agent solution (0.5 weight % of the sizing agent for carbon fiber (a chemical reactant of the block isocyanate (4-CL-TDI) prepared according to the Preparative Example 2 and phenoxy resin), 99.5 weight % of cyclohexane/tetrahydrofuran (1:1) mixture). The coated sizing agent was dried in a convection oven at 60 C. for 2 hours, resulting in the preparation of a carbon fiber surface-treated with the sizing agent.

Preparative Example 3: Preparation of Carbon Fiber-Reinforced Polymer Composite Material

[0069] A carbon fiber-reinforced polymer composite material was prepared by polymerization of -caprolactam in the presence of -caprolactam monomers and a catalyst in the carbon fiber surface-treated with the sizing agents prepared in Example 1 and Example 2. In addition, another carbon fiber-reinforced polymer composite material was prepared using the carbon fiber without surface treatment with the sizing agent of the present invention in Comparative Example 1. An apparatus for producing a polymerization reaction type carbon fiber-reinforced polymer composite material according to an embodiment of the present invention is schematically shown in FIG. 2. In the apparatus for producing a polymerization reaction type carbon fiber-reinforced polymer composite material, the melted caprolactam and the solution (22) prepared by dissolving an initiator and a catalyst separately supplied from the reactor (21) was supplied to the mold (24) positioned between the hot press (23) transferring the pressure and heat, and the air capable of generating air bubbles in the mold was eliminated by the vacuum pump (25). In addition, the concept of improving interfacial adhesion between resin and carbon fiber mediated by the sizing agent playing a role as a reaction initiator is illustrated in FIG. 3.

[0070] The method above is illustrated in more detail hereinafter. A carbon fiber was layered in the mold equipped in the hot press (23), followed by heating.

[0071] Caprolactam, an additional initiator and a catalyst were all dissolved in a separate reactor (21) and the prepared mixed solution (22) was provided to the mold (24). The carbon fiber was impregnated in the solution and reaction was induced by the heat in the mold, leading to polymerization. Then, the carbon fiber-reinforced polymer composite material was prepared by demolding the composite material from the mold. At this time, as shown in FIG. 3, the phenoxy resin (32) of the sizing agent was located on the surface of the carbon fiber (31) and the block isocyanate (4-Cl-TDI) included in the phenoxy resin began to act as an initiator (33) to induce the polymerization of caprolactam, resulting in the formation of polyamide-6 (34) growing from the phenoxy resin. Separately, the initiator induced the polymerization of caprolactam to form polyamide-6 (35) capable of forming another matrix outside the carbon fiber treated with the sizing agent. At this time, the polymer polymerized in the sizing agent coated on the carbon fiber was combined with the sizing agent through covalent bond to form strong interfacial adhesion. Since the sizing agent modified the surface properties of the carbon fiber, the polymer polymerized by the separate initiator also formed improved interfacial adhesion with the carbon fiber, compared with the conventional polymer. In addition, the chemical structure was the same between the polymerized polymers, so that they were well combined with each other.

Analytical Example 1: Shear Test of Carbon Fiber-Reinforced Polymer Composite Material

[0072] Shear test (ILSS, ASTM-D2344) was performed to confirm the interfacial adhesion of the carbon fiber-reinforced polymer composite material prepared according to Preparation Example 3 of the present invention using the carbon fibers of Example 1, Example 2 and Preparative Example 1. The size of the specimen was as follows: specimen length=thickness x 6, specimen width=thickness x 2. The total thickness was 3.2 mm. The test speed was set at a crosshead speed of 1.0 mm/min.

[0073] FIG. 4 is a set of photographs illustrating the shapes of a composite material specimen prepared according to Example 1 of the present invention and the states thereof before and after the test. FIG. 4(a) is the shape of the specimen after the specimen processing and after the test, FIG. 4(b) is the shape before the test, and FIG. 4(c) is the shape after the test. Table 1 below shows the test results of the composite material prepared according to Example 1, and FIG. 6 is a graph presenting the test results.

TABLE-US-00001 TABLE 1 Specimen Width Thickness Max load Strength No. (mm) (mm) (N) (MPa) 1 2 6.63 3.36 1460.00 49.10 3 6.63 3.35 1476.00 49.80 4 6.62 3.40 1544.00 51.50 5 6.65 3.38 1527.00 51.00 6 6.63 3.36 1469.00 49.50 7 6.64 3.34 1486.00 50.20 8 6.61 3.38 1459.00 49.00 9 6.63 3.34 1426.00 48.30 Ave. 6.63 3.36 1480.88 49.80 St. Dev. 0.010 0.019 38.227 1.066 St. Dev(%) 0.198 0.736 3.356 2.784

[0074] FIG. 5 is a set of photographs illustrating the shapes of a composite material specimen prepared according to Example 2 of the present invention and the states thereof before and after the test. FIG. 5(a) is the shape of the specimen after the specimen processing and after the test, FIG. 5(b) is the shape before the test, and FIG. 5(c) is the shape after the test. Table 2 below shows the test results of the composite material prepared according to Example 2, and FIG. 7 is a graph presenting the test results.

TABLE-US-00002 TABLE 2 Specimen Width Thickness Max load Strength No. (mm) (mm) (N) (MPa) 1 6.72 3.31 1520.00 51.20 2 6.71 3.26 1430.00 49.00 3 6.73 3.30 1490.00 50.30 4 6.72 3.28 1442.00 49.00 5 6.72 3.31 1525.00 51.50 6 6.72 3.27 1466.00 50.00 7 6.72 3.30 1460.00 49.40 8 6.71 3.25 1436.00 49.40 9 6.71 3.25 1445.00 49.60 Ave. 6.72 3.28 1468.22 49.93 St. Dev. 0.007 0.023 35.668 0.910 St. Dev(%) 0.140 0.923 3.158 2.368

[0075] The results of the test above and the result of the interlaminar shear strength test performed in Comparative Example 1, are shown in FIG. 8. The ILSS shear strength of the composite material prepared by using the carbon fiber surface-treated with the sizing agent prepared by simply mixing block isocyanate (4-CL-TDI) and phenoxy resin of Example 1 was 49.8 MPa, and the ILSS shear strength of the composite material prepared by using the carbon fiber surface-treated with the sizing agent, the chemical reactant of block isocyanate (4-CL-TDI) and phenoxy resin of Example 2 was 49.9 MPa, proving the ILSS (interlaminar shear strength) between the two materials was similar. In the meantime, the ILSS (interlaminar shear strength) of the carbon fiber reinforced polymer composite material prepared by using the carbon fiber of Comparative Example 1 whose surface was not treated was 37.3 MPa.

[0076] The results above proved that the composite material prepared by using the carbon fiber surface-treated with the sizing agent prepared by using block isocyanate (4-CL-TDI) and phenoxy resin according to the present invention had significantly improved ILSS (interlaminar shear strength) of 33% or more as compared with the other composite materials prepared by using the conventional carbon fiber.

[0077] The ILSS (interlaminar shear strength) is a mechanical strength that is significantly affected by the interfacial adhesion between the fiber and the resin. Therefore, as shown in FIG. 3, it was confirmed that the sizing agent improved the interfacial adhesion by increasing the ILSS value.