JP2007131699A - Method for producing carbon resin composite material-molded article of which surface is hydrophilized - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a carbon resin composite material having a more stable bonding property and hydrophilicity. <P>SOLUTION: This method for producing the carbon resin composite material-molded article of which surface is hydrophilized, is characterized by applying the liquid of a (meth)acrylic monomer having a hydrophilic group on at least one side surface of a preliminary molded material consisting of a thermosetting resin or thermoplastic resin, laminating a polymer film on it, then irradiating electron beam on the obtained laminated material, then heating the laminated material and peeling off the polymer film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a method for producing a carbon resin composite material having improved surface hydrophilicity. In particular, the present invention relates to a technology applicable to a fuel cell separator.

Composite materials and molded articles comprising carbon-based fillers such as carbon fibers and carbon powder and thermosetting resins or thermoplastic resins are extremely useful as industrial members. For example, it can be used as an aircraft, a vehicle member, or a battery member. In some cases, it is necessary to modify the surface of these molded articles to improve adhesion or hydrophilicity. Conventionally, plasma treatment, UV treatment, ozone treatment, and the like have been studied in order to modify the surface of the resin molded product. However, it has been difficult to maintain good adhesion and hydrophilicity for a long time after the treatment. It was. This is thought to be because the polar functional groups generated on the surface of the molded product are decomposed, or the number of the functional functional groups that enter the interior due to thermal motion of the resin decreases.
On the other hand, it is possible to apply a primer, paint, or the like to the surface of the molded product, but elution of the components may adversely affect the molded product or other members. It also has technical problems such as peeling of the coating film.

  When the carbon resin composite material molded product is used as a fuel cell member, particularly a fuel cell separator, a separator that quickly discharges generated water during power generation and does not block the gas flow path is desired. In that case, it is desirable that the separator surface, particularly the gas flow path portion, be hydrophilic. When the hydrophobicity of the flow path portion of the separator is high, the gas flow path is easily clogged with humidified water and generated water, leading to a decrease in power generation performance.

  Therefore, conventionally, a hydrophilic treatment is applied to a predetermined portion of a member such as a fuel cell separator, thereby improving the discharge of generated water. In particular, by performing hydrophilic treatment on the flow path portion, the generated water does not stay as water droplets, and the generated water can be prevented from inhibiting the diffusion of gas.

As a method for hydrophilic treatment of this separator, in the past, a porous carbon member having a water absorption rate of 30 to 80% was provided at the inlet or outlet of the fuel flow path, or the fuel gas flow path. A hydrophilic film such as polyacrylamide is formed on the surface and preferably on the surface of the oxidizing gas channel (see, for example, Patent Document 1), and the surface of the conductive separator made of various materials is cooled at low temperature in the hydrophilizing gas. There is a method of imparting hydrophilicity by performing hydrophilic treatment such as plasma treatment (for example, see Patent Document 2).
However, these methods have practical problems such as poor long-term durability and low productivity due to the treatment under vacuum.
Japanese Patent Laid-Open No. 8-138692 WO99 / 40642 pamphlet

As described above, there has been a demand for providing a method for stably modifying the surface of a molded article of a carbon resin composite material so as to stably develop adhesiveness or hydrophilicity over a long period of time.
In view of such a demand, an object of the present invention is to provide a method for producing a carbon resin composite material having more stable adhesiveness and hydrophilicity.

As a result of earnestly examining the above problems, the present inventor applied a (meth) acrylic monomer to the surface of a preform of resin and graphite, and laminated a polymer film having a predetermined thickness thereon. The polymer having a hydrophilic group can be stably applied to the surface of the molded body by performing a step of radical polymerization by irradiating with an electron beam and then heating the molded body in a state where the polymer film is laminated. In order to find out what can be done, the present invention has been completed.
In the present invention, a (meth) acrylic monomer liquid having a hydrophilic group is applied to at least one surface of a preform formed of a thermosetting resin or a thermoplastic resin and a carbon material, and a polymer film is applied thereon. Of the carbon resin composite material having a hydrophilic surface, wherein the resulting laminate is irradiated with an electron beam, and then the laminate is heated, and then the polymer film is peeled off. A manufacturing method is provided.

  Since the carbon resin composite material molded product obtained from the production method of the present invention is surface-modified without impairing material properties such as mechanical strength, it is excellent in adhesiveness and hydrophilicity. In addition, in the case of a rib-shaped object such as a fuel cell separator, excellent hydrophilicity is exhibited even at the groove bottom where the amount of electron beams reached decreases. That is, the inside of the groove shows high wettability with the generated water, and the water can flow and be discharged without staying in the groove, so that the fuel gas can be supplied by excess water. There is no hindrance and the electromotive force is stabilized. A fuel cell stack using this separator can stably generate power over a long period of time.

Hereinafter, the production method of the present invention will be described in detail.
The preform used in the production method of the present invention is obtained by molding a thermosetting resin or a mixture containing a thermoplastic resin and a carbon material. Examples of the carbon material include artificial graphite, flake shaped natural graphite, massive natural graphite, expanded graphite, carbon black, acetylene black, ketjen black, and amorphous carbon. One kind of these or a mixture of two or more kinds can be used. Particularly when used as a fuel cell separator, graphite having an average particle diameter of 100 to 400 μm is preferable, and graphite having an aspect ratio of 1 to 5 and an average particle diameter of 200 to 300 μm is more preferable. Further, as the carbon material, fibers made of the above carbon raw materials, for example, carbon fibers having a fiber length of 1 to 15 mm, mats, sheets, papers, and the like can be used.

Examples of the thermosetting resin include polycarbodiimide resin, phenol resin, furfuryl alcohol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, vinyl ester resin, bismaleimide triazine resin, polyamino bismaleimide resin, Examples include diallyl phthalate resin. Of these, vinyl ester resins are preferred. This thermosetting resin is used in the form of a powder or a viscous liquid, or is used in a liquid state by mixing with a liquid reactive diluent such as styrene.
Examples of the thermoplastic resin include polyphenylene sulfide, polyolefin, polyamide, polyimide, polysulfone, polyphenylene oxide, liquid crystal polymer, and polyester. Of these, polyphenylene sulfide is particularly preferable because of excellent heat resistance and acid resistance. These resins are appropriately selected according to the intended use and required performance.

  Furthermore, it is desirable to add various compounding agents suitable for the resin used. For example, in the case of a vinyl ester resin, a polymerization initiator such as an organic peroxide, a thickening agent that imparts a preferable viscosity during compression molding, a low shrinkage agent that relieves shrinkage stress during the curing reaction, and a mold release agent as necessary , A polymerization regulator or the like is used. Moreover, when using polyphenylene sulfide, a mold release agent, antioxidant, etc. are used if necessary. A composition containing such a resin, a carbon material, and various compounding agents is used as a molding material.

  The obtained molding material is formed into a preform as a base through various molding methods such as compression molding and injection molding using a mold having a desired shape. This preform is used for electron beam processing.

Next, the manufacturing method of a preform is described.
When a thermosetting resin is used as the resin, an uncured molding material composed of the resin and a carbon material is put into a molding die having a predetermined shape, and is heated and compressed to produce a preform. be able to. The heating temperature at this time is different depending on the thermosetting resin to be used, but is usually 100 to 200 ° C., and the pressure is usually 15 to 60 MPa.

  When a thermoplastic resin is used as the resin, after producing a sheet made of the resin and a carbon material, the sheet is heated to a temperature not lower than the melting point and not lower than the glass transition point of the resin, and then molded into a predetermined shape. After putting this heating sheet into a mold and heating it above the melting point, compression molding is performed, and then the preform is cooled to produce a preform. In this case, the pressure is usually 10 to 50 MPa.

  Even when the carbon resin composite material molded article is a fuel cell separator, a preform can be produced by performing compression molding or injection compression molding using a separator-shaped mold in the same manner as described above. .

In the present invention, a (meth) acrylic monomer liquid having a hydrophilic group is first applied to at least one surface of the preform.
The (meth) acrylic monomer having a hydrophilic group used here forms a polymer having a (meth) acryloyl group that reacts with a radical generated by electron beam irradiation, and has a hydrophilic functional group. It is a compound that has. Among them, a compound having at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, and an epoxy group as a hydrophilic group in one molecule is preferable. Specifically, for example, (meth) acrylic acid and salts thereof, hydroxyl group-containing (meth) acrylic acid ester, polyoxyalkylene group-containing (meth) acrylic acid ester, sulfonic acid group-containing (meth) acrylic acid ester, sulfonic acid Examples thereof include group-containing (meth) acrylic acid amides and glycidyl group-containing (meth) acrylic acid esters.
Alternatively, it may be a (meth) acrylic acid monomer that generates a hydrophilic functional group such as a carboxylic acid group, a sulfonic acid group, or a hydroxyl group by hydrolysis after contact with water.

  Among these, (meth) acrylic acid and a salt thereof, a hydroxyl group-containing (meth) acrylic acid ester, and a glycidyl group-containing (meth) acrylic acid ester are particularly preferable from the viewpoints of expression of a hydrophilic effect and hydrolysis resistance. These can be used alone or in admixture of two or more. Other monomers can also be mixed and used. Further, a hydrophobic (meth) acrylic monomer or the like may be used in combination as long as the hydrophilic performance is not impaired. In addition, the kind of monomer to be used is not limited to these, and is appropriately selected and used in consideration of the balance of surface hydrophilicity and water resistance. Although other radically polymerizable monomers can be used in combination, care must be taken because they adversely affect the polymerizability and may have poor hydrophilicity.

The (meth) acrylic monomer liquid (hereinafter referred to as “hydrophilic treatment liquid”) having a hydrophilic group used in the present invention is obtained by diluting a (meth) acrylic monomer with a solvent such as water or a lower alcohol. Those are preferred. For example, when diluted with a mixed solvent of water and methanol, the wettability of the molded article of the carbon resin composite material is improved, and a good hydrophilic surface can be obtained after electron beam irradiation.
In addition, the use of a diluent has the effect of reducing the gelation of the coexisting homopolymer component and facilitating cleaning.

The dilution concentration varies depending on the type of monomer used, the dilution solvent composition, and the surface state of the preform, but is preferably 10 to 80% by mass. More preferably, it is 20-60 mass%.
About a solvent composition, although it changes with the kind of monomer used similarly to the above, and the surface state of a preforming body, Preferably it is water / water-soluble organic solvent = 0 / 100-60 / 40 (mass%).
In addition to the diluting solvent, a polymerization regulator such as copper chloride or hydroquinone can be added to the monomer, if necessary. If there is no problem in performance, an additive such as a surfactant may be used.
The hydrophilization treatment liquid may be applied once to the preform or a plurality of times if necessary.

Before applying the hydrophilic treatment liquid, it is preferable to process the surface of the preform in order to improve the affinity between the preform and the hydrophilic treatment liquid. Specific examples of the processing method include blast treatment, UV treatment, UV ozone treatment, plasma treatment, corona treatment, acid treatment, and alkali treatment. These methods are appropriately selected and used depending on the purpose.
As a coating method, a method suitable for the shape of the molded product is appropriately selected. The application is preferably performed in an inert gas atmosphere. As a result, dissolved oxygen can be reduced, and the hydrophilic effect can be further increased. It is desirable that the hydrophilization treatment liquid reduce the dissolved oxygen by ventilating an inert gas such as nitrogen immediately before use. .

  In the present invention, a polymer film is then laminated on a preformed body to which a hydrophilization treatment liquid has been applied, and then irradiated with an electron beam.

  Such a polymer film is preferably free from elution of a plasticizer or the like, has no alteration such as swelling, deformation, and dissolution with respect to the above-described hydrophilic treatment solution, and preferably has heat resistance in the heating process. Furthermore, the thing with low radical production | generation by electron beam irradiation is preferable. For example, a film made of polyethylene terephthalate (PET), a film made of polyethylene naphthalate, a film made of polypropylene terephthalate, a film made of polycarbonate, a film made of polystyrene, a film made of polyphenylene sulfide, etc. are excellent in electron beam resistance and are suitable. Of these, polyester films such as polyethylene terephthalate films are preferred from the viewpoints of workability and cost. The thickness of the film is preferably 0.001 to 0.1 mm, and more preferably 0.01 to 0.05 mm. If it is less than 0.001 mm, handling becomes difficult. On the other hand, if the thickness exceeds 0.1 mm, the amount of electron beams reaching the preform is reduced and grafting is hindered. It also leads to an increase in the amount of waste. The role of this film is to prevent volatilization of the hydrophilic treatment liquid in addition to blocking oxygen during grafting. Therefore, it can be said that the lamination of the polymer film contributes to stabilizing the grafting.

In the present invention, after applying a hydrophilization treatment liquid to a preform and laminating a polymer film, the resulting laminate is irradiated with an electron beam.
Electron beam irradiation is usually performed using an electron beam irradiation apparatus.
In the electron beam irradiation apparatus, the accelerating voltage is proportional to the penetrating power of the electron beam, and is usually determined as appropriate depending on the shape of the preform, the total thickness of the polymer film to be laminated, and the hydrophilization treatment liquid. However, in practice, the hydrophilic effect may not be obtained due to the acceleration voltage, so that it is determined from experimental results such as contact angle measurement and XPS surface analysis so as to obtain the expected hydrophilic effect. The acceleration voltage is preferably 100 to 1000 kilovolts (hereinafter referred to as “kV”). More preferably, it is 200-800 kV.

  In addition, the irradiation dose of the electron beam is appropriately determined in consideration of the intended hydrophilic performance and a decrease in physical properties of the preform formed by irradiation. Usually about 10 to 1000 kiloGray (hereinafter referred to as “kGy”) is appropriate. Preferably it is 50-800 kGy. When the irradiation dose is less than 50 kGy, sufficient graft polymerization does not occur. If it exceeds 1000 kGy, the physical properties of the substrate are lowered, which is not preferable. The electron beam irradiation may be performed by irradiating a predetermined dose at a time or by dividing into two or more. In any case, it is desirable that a single dose is 50 to 400 kGy. If the single dose is too high, the preform and the hydrophilization liquid may become high temperature and thermally deteriorate. The atmosphere during electron beam irradiation may be either air or an inert gas atmosphere such as nitrogen because oxygen is blocked by the polymer film. When ozone generation by an electron beam is not desirable, it is more desirable to perform the treatment in a nitrogen atmosphere.

In the present invention, the laminate is heated after being irradiated with an electron beam. This heating is performed in a state where a polymer film is laminated after applying a hydrophilic treatment liquid to the preform. As heating conditions at this time, it is preferable that it is 1 to 120 minutes at 40 to 120 ° C. If the temperature is less than 40 ° C., sufficient hydrophilicity cannot be achieved. If the temperature exceeds 120 ° C., problems such as volatilization of the hydrophilization solution occur. The shorter the heat treatment time, the better in terms of the process, but a treatment of 1 minute or more is desirable for homogenization of the hydrophilic treatment, and it is desirable to finish within 60 minutes from productivity. It does not specifically limit as a heating method, The method suitable for a process and an installation is selected suitably, and is performed.
When it is difficult to graft onto the resin in the preform, when the polymerization reaction of the monomer in the hydrophilization liquid is slow, the temperature is increased and the time is set longer.

The present invention peels a polymer film from a heat-treated laminate.
The polymer film is preferably peeled after the laminated body is slowly cooled. Moreover, it is preferable that the carbon resin composite material molded product obtained after peeling is washed with water or a solvent. Further, boiling cleaning may be performed in order to completely remove the adsorbed polymer and the like. The washing step is performed by appropriately selecting a method suitable for the preform and the homopolymer. Thereafter, by drying, a carbon resin composite material molded product having a hydrophilic surface can be obtained.
In addition, the hydrophilicity and adhesiveness may be further enhanced by adding a chemical treatment to the hydrophilized carbon resin composite molded article. As this chemical treatment, a method suitable for the hydrophilic (meth) acrylic acid monomer to be used is selected. Examples thereof include acid treatment such as sulfuric acid and alkali treatment such as sodium hydrogen carbonate water.

The carbon resin composite material molded article obtained by the present invention has a hydrophilic polymer layer formed on the surface by electron beam irradiation. This polymer layer is chemically bonded to the preform, and the hydrophilicity hardly changes when stored at room temperature.
Further, even in the evaluation of the boiling test and the like by the present inventor, it is clear that the performance is maintained for a long time and it is not a coating film by simple adsorption or the like.

  The obtained carbon resin composite material molded article having a hydrophilic surface can be bonded with an adhesive to produce a structure or used as a battery member. An example of the battery member is a fuel cell separator. This fuel cell separator is used in a fuel cell stack by combining a plurality of single cells joined via a gas diffusion membrane (GDL). Examples of such a fuel cell include a polymer electrolyte fuel cell.

[Preparation of <carbon resin molding material> used as a raw material for the preform used in the present invention]
(Preparation Example 1) (Preparation of thermosetting molding material)
Stirring capacity 2L kneader, carbon powder (average particle size 250 microns) 1235g, bisphenol A type vinyl ester resin 315g, organic peroxide (t-butylperoxyisopropyl carbonate) 3.2g, low shrinkage agent (polyethylene powder) 4.8 g and a thickener (diphenylmethane diisocyanate) 43.2 g were charged and stirred and mixed at room temperature.
Then, it took out to the bag made from a gas barrier multilayer film, and sealed it. The bag was allowed to stand for 24 hours in a 45 ° C. storage, then taken out and allowed to cool at room temperature. This is designated as thermosetting resin molding material A-1.

[Production of <carbon resin composite material molded product> of the preform used in the present invention]
(Preparation Example 2)
133 g of the thermosetting resin molding material A-1 obtained in Preparation Example 1 was weighed and charged into a mold. Using a compression molding machine, molding was performed under conditions of a surface pressure of 30 MPa, an upper mold of 140 ° C., a lower mold of 150 ° C., and a molding time of 5 minutes, to produce a molded product of 130 mm × 190 mm and a thickness of 3 mm. This is designated as preform B-1.

[<Manufacture of hydrophilization treatment liquid used in the present invention]]
(Preparation Example 3)
40 g of acrylic acid, 30 g of methanol, 30 g of ion exchange water, and 0.02 g of cuprous chloride were mixed with stirring at room temperature to obtain a light green solution. The monomer concentration was 40%. This is designated as hydrophilic treatment liquid C-1.

(Preparation Example 4)
30 g of glycidyl methacrylate and 70 g of methanol were stirred and mixed at room temperature to obtain a transparent solution. The monomer concentration was 30%. This is designated as hydrophilic treatment liquid C-2.

Example 1
The molded product B-1 obtained in Preparation Example 1 was pretreated by blasting the surface with a blasting apparatus. A hydrophilization treatment liquid C-1 subjected to nitrogen gas blow treatment was uniformly applied to the molded article, and a 25 μm PET film was laminated thereon. Next, an electron beam was irradiated at an acceleration voltage of 250 kV and an irradiation dose of 200 kGy in a nitrogen atmosphere at room temperature. Immediately after irradiation, heat treatment was performed at 85 ° C. for 15 minutes. After cooling to room temperature, the PET film was peeled off, washed with ion-exchanged water at room temperature twice to remove unreacted components, and then boiled and washed with ion-exchanged water at 95 ° C. for 2 hours. Finally, it was washed with ion exchange water at room temperature and then dried at room temperature for 24 hours.
In this way, a carbon resin composite material molded product D-1 having a hydrophilic surface was obtained. The molded product was evaluated for water wettability and hot water resistance. The evaluation results are shown in Table 1.

Example 2
In the same manner as in Example 1, the molded product B-1 was pretreated by blasting the surface with a blasting apparatus. A hydrophilization treatment liquid C-2 subjected to nitrogen gas blowing treatment was uniformly applied to this molded article, and a 25 μm PET film was laminated thereon. Next, an electron beam was irradiated at an acceleration voltage of 250 kV and an irradiation dose of 200 kGy in a nitrogen atmosphere at room temperature. Immediately after irradiation, heat treatment was performed at 85 ° C. for 15 minutes. After cooling to room temperature, the PET film was peeled off and washed twice with acetone at room temperature to remove unreacted components, and then treated in a 2N aqueous sulfuric acid solution at 60 ° C. for 2 hours. Further, boiling washing with 95 ° C. ion exchange water was performed for 2 hours, and finally, washing with room temperature ion exchange water was performed, followed by drying at room temperature for 24 hours.
In this way, a carbon resin composite material molded product D-2 having a hydrophilic surface was obtained. This molded product was evaluated for water wettability and hot water resistance in the same manner as in Example 1. The evaluation results are shown in Table 1.

<< Comparative Example 1 >>
The surface of the molded product B-1 obtained in Preparation Example 2 was blasted with a blasting apparatus. Thereafter, the grafting treatment was not performed, and washing and drying were performed in the same manner as in Example 1. In this way, a comparative carbon resin composite material molded product E-1 was obtained. This molded product was evaluated for water wettability and hot water resistance in the same manner as in Example 1. The evaluation results are shown in Table 1.

<< Comparative Example 2 >>
In the same manner as in Example 1, the molded product B-1 was pretreated by blasting the surface with a blasting apparatus. Without applying the hydrophilic treatment liquid, an electron beam was irradiated at an accelerating voltage of 250 kV and an irradiation dose of 200 kGy at room temperature in a nitrogen atmosphere. Immediately after the irradiation, the hydrophilic treatment liquid C-1 subjected to the nitrogen gas blow treatment was uniformly applied in the air, and a 25 μm PET film was laminated thereon. Thereafter, heat treatment was performed at 85 ° C. for 15 minutes. After cooling to room temperature, the PET film was peeled off and washed twice with room temperature ion exchange water to remove unreacted components, followed by boiling washing with 95 ° C. ion exchange water for 2 hours. Finally, it was washed with ion-exchanged water at room temperature and then dried at room temperature for 24 hours.
In this way, a comparative carbon resin composite material molded article E-2 irradiated with an electron beam was obtained. This molded product was evaluated for water wettability and hot water resistance in the same manner as in Example 1. The evaluation results are shown in Table 1.

  The measurement method and evaluation criteria used in the present invention are described below.

[Evaluation of hydrophilicity of molded products]
The contact angle of the surface of the molded product was measured by a droplet method using ion-exchanged water using a CA-Z type manufactured by Kyowa Interface Science. The average value of 8 measurements was taken as the result. The measurement atmosphere is 22 ° C. and humidity 60%.

[Evaluation of hydrophilicity of molded product after hot water test]
The molded product was cut into a size of 25 mm × 50 mm to prepare a specimen. The specimen was put in a fluororesin container containing ion-exchanged water, and the container was put in a 95 ° C. drier and boiled for 500 hours. Thereafter, the sample was slowly cooled to room temperature and the specimen was taken out. The surface contact angle at that time was measured in the same manner. The sample was left to dry at room temperature for 24 hours after removal.

As is clear from the results shown in Table 1, Example 1 and Example 2 have good hydrophilicity, good hot water resistance, and maintain hydrophilicity. Therefore, the carbon resin composite material molded article manufactured by applying this manufacturing method can be used as a high-performance fuel cell separator with excellent drainage.
On the other hand, Comparative Example 1 and Comparative Example 2 have low hydrophilicity. Therefore, when the carbon resin composite material molded article manufactured by applying this manufacturing method is used as a separator for a fuel cell, it is inferior in drainage and it is difficult to obtain stable power generation characteristics.

As a result of hydrophilization treatment similar to Example 1 performed on a molded article having an actual fuel cell separator shape with a groove width of 1 mm and a depth of 0.8 mm, the hydrophilicity in the groove is greatly improved. confirmed. The water droplet did not become spherical and developed along the groove.
In the molded article having the separator shape for a fuel cell that was treated in the same manner as in Comparative Example 1, the water droplets were spherical and water did not expand in the groove.

Claims (7)

  After applying a (meth) acrylic monomer liquid having a hydrophilic group to at least one surface of a preform made of a thermosetting resin or a thermoplastic resin and a carbon material, and laminating a polymer film thereon A method for producing a molded article of a carbon resin composite material having a hydrophilic surface, wherein the obtained laminate is irradiated with an electron beam, and then the laminate is heated, and then the polymer film is peeled off.   The method for producing a molded article of a carbon resin composite material having a hydrophilic surface according to claim 1, wherein the polymer film is a polyester film having a thickness of 0.001 to 0.1 mm.   The method for producing a molded article of a carbon resin composite material having a hydrophilic surface according to claim 1 or 2, wherein the heating condition is 40 to 120 ° C for 1 to 120 minutes.   The (meth) acrylic monomer has a (meth) acryloyl group as a polymerizable functional group, and at least one selected from the group consisting of a carboxyl group, a hydroxyl group, and an epoxy group as a hydrophilic group in one molecule. The method for producing a molded article of a carbon resin composite material having a hydrophilic surface according to any one of claims 1 to 3, which is a compound having two functional groups.   The method for producing a carbon resin composite material molded article having a hydrophilic surface according to any one of claims 1 to 4, wherein the electron beam irradiation is performed under a condition of an acceleration voltage of 100 to 1000 kilovolts.   The (meth) acrylic monomer is at least one compound selected from the group consisting of (meth) acrylic acid and salts thereof, hydroxyl group-containing (meth) acrylic acid esters, and glycidyl group-containing (meth) acrylic acid esters. The method for producing a molded article of a carbon resin composite material according to any one of claims 1 to 5, wherein the surface is hydrophilized. The carbon resin composite material molding according to any one of claims 1 to 6, wherein the (meth) acrylic monomer liquid is obtained by diluting a (meth) acrylic monomer in a solvent. Product manufacturing method.