JP2013209510A - Fiber-reinforced resin molding coating composition, fiber-reinforced resin molding obtained by applying the coating composition, and method for producing the fiber-reinforced resin molding - Google Patents

Abstract

The present invention provides a fiber reinforced resin molded body coating composition that conceals the fiber mesh and pinholes on the surface of a molded body and further satisfies excellent adhesion.
(A) at least one selected from the group consisting of urethane oligomers having (meth) acryloyl groups, epoxy oligomers, polyester oligomers and polyether oligomers, and unsaturated polyesters;
(B) an unsaturated monomer copolymerizable with the component (A), which is styrene, α-methylstyrene, vinyltoluene, N-vinyl-2-pyrrolidone, benzyl (meth) acrylate, and ethoxylated phenyl (meth) acrylate At least one unsaturated monomer selected from the group consisting of:
(C) A fiber-reinforced resin molded article coating composition comprising a polymerization initiator.
[Selection] Figure 1

Description

  The present invention relates to a fiber reinforced resin molded article coating composition excellent in adhesion to a fiber reinforced resin molded article, a fiber reinforced resin molded article excellent in light weight, rigidity and surface smoothness, and production of the fiber reinforced resin molded article. For providing a method.

  Paint is applied to the surface of molded products for the purpose of adding added value such as decorativeness to resin molded products used in automobiles, home appliances, building materials, etc., or increasing the weather resistance and extending the product life. This has been done widely. As these resin molded products, FRP molding materials called SMC (Sheet Molding Compound) and BMC (Bulk Molding Compound) are particularly useful and widely used as fiber-reinforced plastics that are lightweight and have excellent rigidity.

  Further, in-mold coating (IMC) is widely used for surface modification of glass fiber reinforced thermosetting molding materials such as SMC molded products and BMC molded products. Examples of the in-mold coating method include the methods disclosed in Patent Documents 1 to 5.

  In Patent Document 1, a first part is formed between separable molds in which one mold is fitted in the other mold, and after the first part is cured, one of the molds is fitted into the mold. And the calculated amount of coating material is injected, molding pressure is applied to the one mold, the coating material adheres to the surface of the first part, and the formed composite article is made of gold. A method of forming a composite polymer that is removed from a mold is disclosed.

  In Patent Document 2, in a method of molding and coating a molding material in a molding die, a molded body is formed between two separable molds until reaching a state where the molding material is cured to a point where it can be coated. Molding with a mold cavity pressure and temperature suitable for the above, and injecting a coating material into the mold cavity at a pressure significantly exceeding the mold cavity pressure just before injection while holding the mold in place. Disclosed is a method for molding and coating a molded body, which includes a step of covering the surface of the molded body with an agent and allowing the coating agent to compress the molded body, and a step of curing the formed and formed molded body. . The mold cavity pressure during molding is in the range of 3.52 to 14.1 MPa. Alternatively, a pressure of 0.703 to 1.05 MPa is used as the pressure in the mold cavity immediately before the coating agent is injected. That is, at the time of coating agent injection, the mold cavity is in a closed state. However, there is no description about the pressure in the cavity after the coating agent is injected. As the molding material, any thermosetting or thermoplastic plastic can be used. Representative examples of thermosetting plastics include compression and injection molded plastics such as unsaturated polyester resins, epoxy resins, phenolic resins, silicon resins, or polyurethane resins. Representative examples of useful thermoplastic resins include polyethylene, ABS, PVC, polystyrene, polypropylene, and acrylic resins.

  In Patent Document 3, in the in-mold coating method, a method of degassing the inside of a mold cavity under reduced pressure includes, for example, a shape of a molded product, a tab portion that is in contact with the outside of the molded product, and serves as a paint inlet, and vacuum suction. Using a mold provided on the lower mold of the split mold with the tab part serving as a mouth as the molding part, the plastic is compression-molded, and the paint is injected at a high pressure by vacuum suction inside the mold while the mold is closed. Then, a plastic in-mold coating method is disclosed, wherein the injected paint is flowed into the mold by increasing the molding pressure, and then the paint is cured.

  In Patent Document 4, a step of obtaining a molded product in a cavity formed between a first molding die and a second molding die, and vacuum suction into the cavity after the molded product is obtained. While performing, the fluid resin material is discharged to the surface of the molded article disposed in the cavity, the fluid resin material is cured, and at least a part of the surface of the molded article is subjected to in-mold coating. And an in-mold molding method characterized by including a process. Furthermore, in the examples, it is described that the pressure at the time of SMC molding is 8 MPa, the mold is opened when the coating agent is injected, and re-clamping is performed at a pressure of 6 MPa after the injection.

  U.S. Patent No. 6,057,031 relates to a device and method for molding and coating a substrate in a mold having at least two cavities: (a) molding the substrate in the first cavity of the mold; Introducing the substrate molded in a) into the second cavity of the mold, and coating the substrate molded in step (a) with paint in the second cavity, and the coating is high A method of performing under pressure is disclosed.

  Moreover, as an in-mold coating composition used for said in-mold coating method, it is shown by patent documents 6-9, for example.

  In recent years, a lighter and stronger FRP member has been demanded due to an increase in demand for electric vehicles and the like. Therefore, an RTM (Resin Transfer Molding) molding method that is easy to mold a lightweight FRP member because of its low specific gravity and high strength compared to SMC and BMC has attracted attention. The RTM molding method is a molding method that is suitable for medium-sized and small-quantity production, especially for large parts. In order to uniformly impregnate the matrix resin quickly and evenly into the reinforcing fiber material arranged in the mold, It is necessary to set the viscosity of the matrix resin low. Therefore, pinholes due to air bubbles and poor impregnation in molded products, thermal expansion coefficient difference between matrix resin and reinforced fiber material, and swell of molded product due to large curing shrinkage rate of matrix resin, and continuous fibers are used. The surface smoothness of the RTM molded product is considerably inferior to that of SMC, because unevenness due to the crossing of fibers due to this and the meandering of the fibers are likely to occur. Therefore, for parts that require a smooth appearance, such as automotive outer panels, a large number of man-hours such as sanding, padding, sealing, primer surfacer, intermediate coating, and top coating are required. Yes, the cost is high.

  Many matrix resins mainly used for epoxy resin have been proposed as matrix resins used for RTM molding (see, for example, Patent Documents 10 to 12).

  However, since these epoxy resins have high adhesion to the mold, a large amount of release agent is blended in the matrix resin mainly composed of epoxy resin, and the surface coating material to be injected into the mold is There arises a problem that it is difficult to adhere.

  Examples of the coating on the RTM molded body include a sandwich molding method (Patent Document 13) and a gel coat coating method (Patent Documents 14 and 15).

  In Patent Document 13, for the purpose of preventing the occurrence of resin sink in an RTM molded product and improving the surface quality, a reinforcing fiber laminate not impregnated with a resin is formed with a sheet called a prepreg impregnated with a resin in advance. There has been proposed a method of sandwiching sandwich molds, mold clamping, injecting resin, impregnating the reinforcing fiber laminate, and heat curing. However, performance such as surface smoothness of the molded product is not sufficient, and there is a problem in terms of cost.

  In Patent Document 14, in order to improve the surface smoothness, RTM molding is performed after applying a coating called gel coat on the mold surface in advance. For example, when a FRP molded product is molded by an RTM molding method using a dicyclopentadiene-based unsaturated polyester resin, a preformed fiber reinforcing material is set in a mold having a gel coat layer formed on the mold surface in advance. The mold is clamped and a resin composition in which a curing agent and a curing accelerator are mixed is injected. This method is industrially effective because it can be expected to reduce the number of times of sanding and coating on the surface of the molded product. However, in this method, it takes 30 minutes until the gel coat layer is cured to some extent (tack-free), and RTM molding is performed thereon, so that the molding cycle is extremely long.

  In Patent Document 15, when an FRP molded product is molded by an RTM molding method using an epoxy resin composition as a matrix, for example, an unsaturated polyester gel coat is spray-coated on a mold surface, dried for about 2 minutes, and then glass fiber A method is disclosed in which a reinforcement mat preform is placed in a mold, the mold is closed, and an epoxy resin mixture is injected. In this method, it takes 22 minutes to remove the mold, and the total molding cycle is as long as 30 minutes or more. Moreover, since such a gel coat composition is spray-coated on the surface of the mold, there is a problem that bubbles and pinholes are easily generated in the gel coat layer.

  Therefore, the application of the gel coat to the molds exemplified in Patent Documents 14 and 15 is stopped, and instead, a surface coating material is injected into the mold to cover the voids and pinholes generated on the surface of the molded product, and molding is performed. An in-mold coating method that attempts to eliminate product defects has been proposed (see Patent Documents 16 and 17). However, when the surface coating material is injected with the mold structure shown in Patent Document 16, the injection pressure in the vicinity of the injection port is high, and the injection pressure of the surface coating material decreases with increasing distance from the injection port. Therefore, it is difficult to form a coating material having a uniform film thickness. Also, since the injection pressure of the coating material varies depending on the temperature, viscosity, injection speed, etc. of the coating material, it is not easy to control them. In the mold structure shown in Patent Document 17, when the mold is closed, the vertical distance between the molding parts is defined by the stopper, and the amount of cure shrinkage in the thickness direction of the molding resin is equal to or greater than the film thickness of the surface coating material. In some cases, sufficient clamping pressure is not applied to the surface coating material, and defects such as wrinkles, cracks, dents, glossiness, and color unevenness occur on the surface of the cured coating material.

  On the other hand, in-mold coating compositions applicable to RTM molded bodies are disclosed in Patent Documents 18 to 24, for example. In addition, an attempt to apply the in-mold coating method to an injection molding method of a thermoplastic resin or the like (see Patent Document 25 to Patent Document 27) or an attempt to apply to an RIM molding method (Reaction Injection Molding). (See Patent Documents 28 to 30). However, in these Patent Documents 18 to 30, there is no description of specific examples of the coating method for the RTM molding method or the in-mold coating composition for the RTM molded product. There is no description of the in-mold coating composition that conceals pinholes and further satisfies excellent adhesion to an RTM molded product.

Japanese Patent Publication No.55-9291 JP-A 61-273921 JP-A-2-258319 Japanese Patent Laid-Open No. 3-164218 Special table 2008-525212 gazette JP-A-1-126316 JP-A-5-104554 JP-A-5-156175 JP-A-5-70712 JP 2006-265434 A JP 2010-163573 A JP 2010-195886 A JP 2010-2221489 A JP 2001-2739 A Special table 2010-530022 JP-A-4-226726 JP-A-4-348922 JP-A-6-326881 JP 2003-137944 A JP 2006-257368 A JP 2006-257369 A JP 2006-257370 A JP 2009-51124 A JP 2010-138248 A JP 08-142119 A JP 08-258080 A JP 2001-038770 A JP-A-8-113761 JP 2001-038783 A JP 2003-094454 A

As described above, the fiber reinforced RTM molded product is, for example, compared with a glass fiber reinforced SMC molded product widely used for an automobile outer plate or the like.
1. Matrix resin cure shrinkage is large,
2. Since it is necessary to impregnate the reinforcing fiber material in a mold in a short time in the mold, the matrix resin is required to have a low viscosity and cannot contain a large amount of inorganic filler.
3. Difference in thermal expansion coefficient between matrix resin and reinforcing fiber material,
4). The present condition is that the surface smoothness of the RTM molded product is considerably inferior due to unevenness caused by crossing of fibers due to the use of continuous fibers. In addition, since the reinforcing fiber material is impregnated with the matrix resin in the mold cavity, many voids (nesting holes) due to poor impregnation exist as surface defects in the RTM molded product.

  Therefore, for parts that require a smooth appearance such as an automobile outer plate, before the matrix resin is injected into the mold, a gel coat is applied to the mold surface and there are several times until the adhesiveness of the surface is lost. It needs to be left unattended, resulting in poor productivity and high costs. Alternatively, when finishing with after-coating after molding, to correct unevenness due to pinholes and fibers on the surface of the molded product, or to remove the release agent adhering to the surface of the molded product, sanding of the molded product substrate, At present, a great deal of man-hours and costs are required such as degreasing of molded articles, filling of putty, sealing, primer surfacer, intermediate coating and top coating.

  In view of the above problems, an object of the present invention is to provide an in-mold coating composition having excellent adhesion to an RTM molded article and moisture resistance in a very short molding cycle.

  Another object of the present invention is to provide a fiber-reinforced resin molded body that can conceal the fibers and pinholes on the surface of the RTM molded body, has a small surface undulation, and has an excellent surface appearance of the RTM molded body, and the fiber-reinforced resin molded body It is to provide a method.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be achieved with the following configuration, and have reached the present invention.

According to the present invention, (A) a urethane oligomer having an (meth) acryloyl group, an epoxy oligomer, a polyester oligomer and a polyether oligomer, and at least one selected from the group consisting of unsaturated polyesters,
(B) an unsaturated monomer copolymerizable with the component (A), which is styrene, α-methylstyrene, vinyltoluene, N-vinyl-2-pyrrolidone, benzyl (meth) acrylate, and ethoxylated phenyl (meth) acrylate At least one unsaturated monomer selected from the group consisting of:
(C) A fiber-reinforced resin molded article coating composition comprising a polymerization initiator is provided.

Further, according to the present invention, a mold that can be divided into at least two mold parts, provided with a heating means and provided with an inlet for injecting a matrix resin and an inlet for injecting a fiber-reinforced resin molded body coating composition is used. In a method for producing a fiber reinforced resin molded article by an RTM (Resin Transfer Molding) molding method,
The mold is preheated to a temperature at which the matrix resin and the fiber reinforced resin molded article coating composition are cured, a fiber reinforcing material is disposed in a cavity formed by the mold, and the mold is clamped. After that, the matrix resin is injected into the cavity and impregnated in the fiber reinforcement, until the matrix resin can withstand the injection pressure and flow pressure of the fiber-reinforced resin molding coating composition. Curing the matrix resin to obtain a fiber-reinforced resin impregnated body;
Injecting the fiber reinforced resin molded article coating composition between the fiber reinforced resin impregnated body surface and the mold surface so as to have a film thickness of 20 to 600 μm;
A step of re-clamping at a pressure of 0.5 to 7 MPa immediately after completion of injection;
Curing the fiber-reinforced resin molded article coating composition;
After the fiber reinforced resin molded body coating composition is cured, the mold is opened, and the fiber reinforced resin molded body formed by curing the fiber reinforced resin molded body coating composition on the surface of the fiber reinforced resin impregnated body A method for producing a fiber-reinforced resin molded body comprising a step of removing from a mold.

Further, according to the present invention, a gold that can be divided into at least two mold parts, provided with a heating means and a cooling means, provided with an injection port for injecting a matrix resin and an injection port for injecting a fiber-reinforced resin molded body coating composition. In a method for producing a fiber reinforced resin molded article by an RTM molding method using a mold,
The mold is preheated to a temperature at which the matrix resin and the fiber reinforced resin molded article coating composition are cured, a fiber reinforcing material is disposed in a cavity formed by the mold, and the mold is clamped. After that, the matrix resin is injected into the cavity and impregnated in the fiber reinforcement, until the matrix resin can withstand the injection pressure and flow pressure of the fiber-reinforced resin molding coating composition. Curing the matrix resin to obtain a fiber-reinforced resin impregnated body;
Injecting the fiber reinforced resin molded article coating composition between the fiber reinforced resin impregnated body surface and the mold surface so as to have a film thickness of 20 to 600 μm;
A step of re-clamping at a pressure of 0.5 to 7 MPa immediately after completion of injection;
Curing the fiber-reinforced resin molded article coating composition;
A step of cooling the surface of the mold part provided with an injection port for injecting at least the fiber-reinforced resin molded body coating composition after curing the fiber-reinforced resin molded body coating composition;
And a step of opening the mold and taking out the fiber reinforced resin molded body obtained by curing the fiber reinforced resin molded body coating composition on the surface of the fiber reinforced resin impregnated body from the mold. A method for producing a resin molded body is provided.

Further, according to the present invention, a gold that can be divided into at least two mold parts, provided with a heating means and a cooling means, provided with an injection port for injecting a matrix resin and an injection port for injecting a fiber-reinforced resin molded body coating composition In a method for producing a fiber reinforced resin molded article by an RTM molding method using a mold,
The mold is adjusted in advance to a temperature at which the matrix resin does not cure, a fiber reinforcing material is disposed in the cavity formed by the mold, the mold is clamped, and the matrix is then placed in the cavity. Injecting resin to impregnate the fiber reinforcement;
The mold is heated to a temperature at which the matrix resin can withstand the injection pressure and flow pressure of the fiber-reinforced resin molded article coating composition, and the matrix resin is cured to obtain a fiber-reinforced resin-impregnated body. When,
Injecting the fiber reinforced resin molded article coating composition so as to have a film thickness of 20 to 600 μm between the surface of the fiber reinforced resin impregnated body and the mold surface;
A step of re-clamping at a pressure of 0.5 to 7 MPa immediately after completion of injection;
Heating the mold to a temperature at which the fiber-reinforced resin molded body coating composition is cured, and curing the fiber-reinforced resin molded body coating composition;
After the fiber reinforced resin molded body coating composition is cured, at least a step of cooling the mold part surface having an injection port for injecting the fiber reinforced resin molded body coating composition;
A step of opening the mold, and taking out from the mold a fiber reinforced resin molded body obtained by curing the fiber reinforced resin molded body coating composition on the surface of the fiber reinforced resin impregnated body. A method for producing a molded body is provided.

According to the present invention, there is also provided a mold comprising a mold part constituting the first cavity, a mold part constituting the second cavity, and a core mold part, the mold part constituting the first cavity. And the core mold part to form a first cavity, the mold part constituting the second cavity and the core mold part to form a second cavity larger than the first cavity, and the second cavity An in-mold coating can be applied in the cavity, and at least a mold part constituting the first cavity or the core mold part is provided with an injection port for injecting a matrix resin, thereby constituting the second cavity. In the mold part, using a mold provided with an injection port for injecting the fiber-reinforced resin molded body coating composition, in the method of manufacturing a fiber-reinforced resin molded body by the RTM molding method,
The mold part that constitutes the first cavity, the mold part that constitutes the second cavity, and the core mold part are preheated to a temperature at which the matrix resin and the fiber-reinforced resin molded article coating composition are cured. The fiber reinforcement is disposed in the first cavity formed by the mold, and after the mold is clamped, the matrix resin is injected into the first cavity to impregnate the fiber reinforcement. Curing the matrix resin to obtain a fiber-reinforced resin-impregnated body until the matrix resin can withstand the injection pressure and flow pressure of the fiber-reinforced resin molded article coating composition;
Replacing the mold part constituting the first cavity with the mold part constituting the second cavity while leaving the fiber reinforced resin impregnated body in the core mold part;
Injecting the fiber-reinforced resin molded article coating composition so as to have a film thickness of 20 to 600 μm between the surface of the fiber-reinforced resin impregnated body and the surface of the mold part constituting the second cavity;
A step of re-clamping at a pressure of 0.5 to 7 MPa immediately after completion of injection;
Curing the fiber-reinforced resin molded article coating composition;
After the fiber-reinforced resin molded body coating composition is cured, the mold is opened, and the fiber-reinforced resin molded body is formed by curing the fiber-reinforced resin molded body coating composition on the surface of the fiber-reinforced resin impregnated body. A method for producing a fiber-reinforced resin molded product comprising the step of removing from the product.

  Furthermore, according to the present invention, there is provided a fiber reinforced resin molded article obtained by the above-described method for producing a fiber reinforced resin molded article.

  According to the present invention, a fiber reinforced resin molded body coating composition having excellent adhesion and moisture absorption with the molded body, and the surface of the molded body can be concealed by hiding the fibers and pinholes on the surface of the molded body. It is possible to provide a fiber reinforced resin molded article having an excellent appearance and a method for producing the fiber reinforced resin molded article.

It is the schematic of the apparatus which implements in-mold coating by RTM shaping | molding. It is a partial schematic diagram of the mold structure when the film thickness of the in-mold coating is smaller than the amount of curing shrinkage in the thickness direction of the matrix resin when performing in-mold coating by RTM molding. It is a schematic diagram of the method of manufacturing using a 1st cavity and a 2nd cavity when implementing in-mold coating by RTM shaping | molding.

  Hereinafter, although the manufacturing method of the FRP molded object by the RTM molding method of this invention and the formation method of a fiber reinforced resin molded object covering molded object are demonstrated concretely, it is not limited to this.

  In FIG. 1, reference numeral 1 is a movable mold part, and 2 is a fixed mold part, which are mold members facing each other, and are molds that can be divided into at least two mold parts. The mold that can be divided into at least two mold parts is a mold having a biting structure in which one mold part is fitted into the other mold part. Sealing packing 4 is provided on the entire circumference of the fixed mold portion so as to seal the inside of the cavity. The movable mold part is configured to be moved up and down by a clamping cylinder (omitted). In the movable mold part and the fixed mold part, heating medium pipes 17 for heating the mold are respectively incorporated. A cavity 3 having a required shape is formed at a fitting portion between the movable mold part 1 and the fixed mold part 2, and a fiber reinforcing material is disposed in the cavity 3 and stored in the matrix resin tank 6. The liquid thermosetting matrix resin molding material thus prepared is injected, filled, and cured from the resin injection port 5 via the pumping pump 15. The movable mold part 1 is equipped with a reduced pressure suction part 10, a valve 13, a vacuum trap 11 and a vacuum pump 12 for the purpose of reducing the pressure inside the cavity 3.

  Further, in FIG. 1, as a means for injecting the in-mold coating composition, a fiber reinforced resin molded product coating composition injection port 7 provided with a shutoff pin (omitted), and a predetermined amount of fiber reinforced resin molded product in the injection port 7 A metering cylinder 9 for supplying the coating composition is provided.

  The method for producing an FRP molded body coated in-mold by the RTM (Resin Transfer Molding) molding method using the above apparatus has the following steps.

1. Preparatory process (1) The cavity surface temperature of the movable mold part 1 and the fixed mold part 2 is heated to a temperature at which the matrix resin and the fiber-reinforced resin molded body coating composition are cured, usually 50 to 200 ° C. In the present invention, the temperature may be such that the matrix resin is not cured and heated after the injection.
(2) The matrix resin mixed with the curing agent and the like is degassed under reduced pressure, and then charged into the matrix resin tank 6.
(3) The fiber-reinforced resin molded body coating composition mixed with the initiator or the like is degassed under reduced pressure, and then charged into the fiber-reinforced resin molded body coating composition tank 8.
(4) The reinforcing fiber material is cut into a predetermined size. If necessary, shape the product and hold the shape with an adhesive. Further, a predetermined number of sheets are stacked.

2. Reinforcing fiber material arrangement step (1) If necessary, the cut reinforcing fiber material is arranged at a predetermined position on a mold surface to which a release agent is applied. The mold part surfaces of the movable mold part 1 and the fixed mold part 2 are preferably subjected to chrome plating, nickel plating or fluororesin coating processing in consideration of releasability.

3. Vacuum suction step (1) The movable mold part 1 is operated to close the mold, and the cavity 3 is preferably degassed under reduced pressure. The mold clamping pressure at this time is a pressure that is not inferior to the injection pressure of the matrix resin, and is usually 1 to 5 MPa. Further, the vacuum suction is 20 torr or less, more preferably 10 torr or less.
(2) Close the valve 13 of the vacuum suction part.

4). Matrix resin injection impregnation step (1) The valve 14 is opened, and the matrix resin is injected into the cavity 3 via the pressure pump 15. At this time, the injection speed is preferably controlled by the degree of throttling of the valve 14.
(2) The fiber reinforcement is impregnated with a matrix resin.
(3) After the injection is completed, the valve 14 is closed.

5. Matrix resin curing step (1) The matrix resin is cured until it can withstand the injection pressure and flow pressure of the fiber-reinforced resin molded article coating composition, to obtain a fiber-reinforced resin-impregnated body.

6). Fiber Reinforced Resin Molded Body Coating Composition Injection Step (1) The movable mold part 1 is operated, and the movable mold part 1 and the fixed mold part 2 are separated by about 0.1 to 5 mm. Or it is good also as "zero" which does not apply a metal mold clamping pressure.
(2) The fiber-reinforced resin molded body coating composition, which has been weighed in a predetermined amount, is poured into the cavity 3. The injection amount of the fiber-reinforced resin molded body coating composition is set so as to have a film thickness of 20 to 600 μm. Preferably it is 50-500 micrometers. If the film thickness is less than 20 μm, an uncoated portion is likely to occur, and if the film thickness exceeds 600 μm, the weight of the fiber-reinforced resin molded body coated with the fiber-reinforced resin molded body coating composition increases and the effect of weight reduction is achieved. Get smaller.
When injecting the fiber-reinforced resin molded body coating composition into the cavity 3, it may be injected at a pressure exceeding the pressure in the cavity 3 while holding the movable mold part 1 at a position where the matrix resin is cured.
(3) Immediately after the injection of the fiber reinforced resin molded body coating composition is completed, the fiber reinforced resin molded body coating composition injection port 7 is closed, and re-clamping is performed at a pressure of 0.5 to 7 MPa, and the fiber reinforced resin molding is performed. The body coating composition is spread on the surface of the fiber reinforced resin impregnated body. A preferable re-clamping pressure is 1 to 5 MPa. If the re-clamping pressure is less than 0.5 MPa, uncovered parts and wrinkles are likely to occur due to insufficient pressure, and if the re-clamping pressure exceeds 7 MPa, the cured coating film may become uneven or pressed. Since the equipment costs for the metal mold and the like increase, the advantages of the RTM molding method are lost.

7). Fiber-reinforced resin molded body coating composition curing step (1) The fiber-reinforced resin molded body coating composition is cured by the heat of the mold. After the fiber reinforced resin molded body coating composition is cured, at least the surface of the mold part provided with an injection port for injecting the fiber reinforced resin molded body coating composition may be cooled to shorten the molding cycle.

8). Demolding step (1) The movable mold part 1 is operated to open the mold.
(2) The fiber reinforced resin molded body coated with the fiber reinforced resin molded body coating composition is taken out.

  FIG. 2 is a partial schematic view of the mold structure when the film thickness of the in-mold coating is smaller than the amount of cure shrinkage in the thickness direction of the matrix resin. In order to regulate the thickness of the molding substrate, several slide blocks 18 connected to the hydraulic cylinder 19 are provided on the outer periphery of the mold. First, after a reinforcing fiber material is arranged at a predetermined position, mold clamping is performed, the inside of the cavity is degassed under reduced pressure, and a matrix resin is injected. After the matrix resin is cured to such an extent that it can withstand the injection pressure and flow pressure of the fiber-reinforced resin molded body coating composition, the movable mold part and the fixed mold part are separated by about 0.1 to 5 mm, and then the hydraulic cylinder 19 The slide block 18 is slid from between the movable mold part and the fixed mold part. Next, a prescribed amount of the fiber-reinforced resin molded body coating composition is injected into the cavity. Similarly to the above, immediately after the completion of the injection so that the film thickness of the fiber-reinforced resin molded body coating composition is 20 to 600 μm, preferably 50 to 500 μm, the film is re-applied at a pressure of 0.5 to 7 MPa, preferably 1 to 5 MPa. Clamping is performed, and the fiber-reinforced resin molded body coating composition is spread and cured on the surface of the resin molded body. Thereby, even when thin film thickness is calculated | required, the fiber reinforced resin molded object which a coating-film defect does not produce can be obtained.

  FIG. 3 is a schematic view corresponding to the manufacturing method using the first cavity and the second cavity. In FIG. 3A, a fiber reinforced resin impregnated body is molded by a mold part and a core mold part constituting the first cavity, and the matrix resin is cured. (B) While the molded body obtained when the matrix resin is cured is fixed to the core mold part, the mold part constituting the first cavity is rotated up, and the mold part constituting the second cavity is the core. Cover the mold part and clamp the mold with a predetermined pressure. (C) Next, a fiber-reinforced resin molded body coating composition in an amount equal to or larger than the space between the second cavity and the molded body is injected. After the injection is completed, the fiber reinforced resin molded body coating composition is cured, and then the mold part constituting the second cavity is raised, and the fiber reinforced resin molded body is taken out from the mold.

  As the matrix resin, an epoxy resin, an unsaturated polyester resin, or a vinyl ester resin can be used, but an epoxy resin having a small curing shrinkage is preferable.

  As the epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, or cyclic aliphatic type epoxy resin can be used. The bisphenol A type epoxy resin is obtained by reacting bisphenol A and epichlorohydrin in the presence of an alkali. The bisphenol F type epoxy resin is obtained by reacting bisphenol F and epichlorohydrin in the presence of an alkali. A novolak-type epoxy resin can be obtained by a reaction between phenol and formaldehyde. This phenol novolac and epichlorohydrin are reacted to obtain a novolac type epoxy resin. The cycloaliphatic epoxy resin is obtained by epoxidizing a double bond of an unsaturated cycloaliphatic compound such as cyclopentadiene or cyclohexane derivative with peracetic acid.

  Among these epoxy resins, in particular, the epoxy resin itself has a low viscosity and is excellent in the impregnation property to the reinforcing fiber material, the heat resistance of the cured product, and the good physical property balance of the bisphenol A type. Epoxy resins, bisphenol F type epoxy resins and novolak type epoxy resins are preferred. The bisphenol A-type epoxy resin and bisphenol F-type epoxy resin have an epoxy equivalent of 500 g / eq. From the viewpoint of excellent fluidity at room temperature and good impregnation into a reinforcing fiber material. The following are preferable, and particularly 100 to 350 g / eq. It is preferable to be in the range.

  Examples of the curing agent for the epoxy resin include polyamines and acid anhydrides. Examples of the polyamine curing agent include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, isophoronediamine, N-aminomethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, metaxylenediamine, Examples include diaminodiphenylmethane, m-phenylenediamine, adipic acid dihydrazide, and polyamide polyamine. Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecyl succinic anhydride, pyromellitic anhydride and trimellitic anhydride. .

  The epoxy resin composition is further unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, styrene, methylstyrene, methyl (meth) acrylate for the purpose of imparting performance such as flexibility and strength to the cured product depending on the application. , Monofunctional (meth) acrylates such as glycidyl (meth) acrylate and isobornyl (meth) acrylate, 1,6 hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate, etc. These polyfunctional (meth) acrylates and radical polymerization initiators such as t-butyl hydroperoxide, t-butyl peroxybenzoate and lauroyl peroxide can be used in combination.

  The unsaturated polyester resin can be produced, for example, by reacting an organic polyol compound and an unsaturated carboxylic acid by a known method, and further reacting with a saturated polycarboxylic acid as necessary. Typical examples of the organic polyol used include ethylene glycol, propylene glycol, triethylene glycol, trimethylolpropane, glycerin, and bisphenol A. Moreover, as unsaturated polycarboxylic acid to be used, (anhydrous) maleic acid, (anhydrous) fumaric acid, (anhydrous) itaconic acid etc. can be mentioned as a typical thing, for example. An organic peroxide is mentioned as a hardening | curing agent of unsaturated polyester resin. Examples of organic peroxides include isobutyryl peroxide 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumylperoxyneodecanoate, di-3-methoxybutylperoxydicarbonate, Di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-isopropyl peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t- Typical examples are organic peroxides such as butyl peroxy 2-ethyl hexanoate, t-amyl peroxy 2-ethyl hexanoate, t-butyl peroxy isopropyl carbonate, lauroyl peroxide and benzoyl peroxide. It is done.

  The vinyl ester resin is an acid ring-opening addition reaction to a normal epoxy group in such a ratio that an epoxy compound and an unsaturated carboxylic acid have a carboxyl group equivalent of 0.5 to 1.5 per equivalent of epoxy group. Obtained by. Typical examples of the unsaturated carboxylic acid include acrylic acid and methacrylic acid. Representative examples of the epoxy compound include bisphenol A type epoxy, bisphenol F type epoxy, phenol novolac type epoxy, and the like. Examples of the curing agent for the vinyl ester resin include organic peroxides. Examples of organic peroxides include isobutyryl peroxide 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumylperoxyneodecanoate, di-3-methoxybutylperoxydicarbonate, Di-2-ethylhexyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-isopropyl peroxydicarbonate, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t- Typical examples include butyl peroxy 2-ethyl hexanoate, t-amyl peroxy 2-ethyl hexanoate, t-butyl peroxy isopropyl carbonate, lauroyl peroxide and benzoyl peroxide.

  These matrix resins have the property of easily adhering to metals, and the matrix resin has an internal mold release agent as long as it does not impair the physical properties of the fiber reinforced resin molded article and the adhesion to the fiber reinforced resin molded article coating composition. It is preferable to use in combination. Examples of the internal mold release agent include stearic acid, stearic acid such as hydroxystearic acid, zinc stearate, aluminum stearate, magnesium stearate, calcium stearate, soybean oil lecithin, silicone oil, fatty acid ester and fatty acid alcohol. Examples include basic acid esters. The compounding amount of these internal mold release agents is, for example, 0.1 to 5 parts by mass, and further 0.2 to 2 parts by mass with respect to a total of 100 parts by mass of the matrix resin and the curing agent component. preferable. Within this range, the effect of releasing from the mold is suitably exhibited.

  Examples of the fiber reinforcement include glass fiber, carbon fiber, aramid fiber, and boron fiber, and carbon fiber is particularly preferable from the viewpoint of strength and weight reduction of the molded body. In addition, as a structure of the fiber reinforcement, the surface of the obtained molded body is smoothed by laminating a sheet-like material of continuous fine count fibers such as a surfacing mat on the outermost surface of the molded body. It is preferable because of its excellent properties.

  Next, the fiber reinforced resin molded body coating composition used for in-mold coating in the present invention will be described.

The fiber-reinforced resin molded article coating composition according to the present invention is:
(A) at least one selected from the group consisting of urethane oligomers having a (meth) acryloyl group, polyester oligomers, epoxy oligomers and polyether oligomers, and unsaturated polyesters;
(B) The unsaturated monomer copolymerizable with the component (A) comprises styrene, α-methylstyrene, vinyltoluene, N-vinyl-2-pyrrolidone, benzyl (meth) acrylate, and ethoxylated phenyl (meth) acrylate. At least one selected from the group;
(C) a polymerization initiator;
Is an essential component.

(1) About (A) component (A) component used for the fiber reinforced resin molded object coating composition which concerns on this invention is a urethane oligomer which has a (meth) acryloyl group, a polyester oligomer, an epoxy oligomer, and a polyether oligomer, And at least one selected from the group consisting of unsaturated polyester resins.

(A-1) Oligomer having (meth) acryloyl group The oligomer having (meth) acryloyl group is urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and polyether (meth) acrylate.

  The mass average molecular weight of these oligomers may vary depending on the type of the oligomer, but is generally preferably about 300 to 10,000, more preferably 500 to 5,000. The oligomer having the (meth) acryloyl group suitably has at least 2 to 8, preferably 2 to 4 (meth) acryloyl groups in one molecule.

(A-1-1) Urethane (meth) acrylate oligomer The urethane (meth) acrylate oligomer as an oligomer used in the present invention includes, for example, (1) an organic diisocyanate compound, (2) an organic polyol compound, and (3 ) Hydroxyalkyl (meth) acrylate is mixed at an abundance ratio such that the NCO / OH ratio is, for example, 0.8 to 1.0, preferably 0.9 to 1.0. Can be manufactured. An oligomer having a large number of hydroxyl groups can be obtained by using excessive hydroxyl groups or using a large amount of hydroxyalkyl (meth) acrylate.

  Specifically, (1) an organic diisocyanate compound and (2) an organic polyol compound are reacted in the presence of a urethanization catalyst such as dibutyltin laurate to obtain an isocyanate-terminated polyurethane prepolymer. Next, the urethane (meth) acrylate oligomer can be produced by reacting (3) hydroxyalkyl (meth) acrylate until almost all the free isocyanate groups have reacted. In addition, the ratio of (2) organic polyol compound and (3) hydroxyalkyl (meth) acrylate is, for example, about 0.1 to 0.5 mol of the former with respect to 1 mol of the latter.

  Examples of (1) organic diisocyanate compounds used in the above reaction include 1,2-diisocyanatoethane, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, hexamethylene diisocyanate, and lysine. Diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, bis (4-isocyanatocyclohexyl) methane, methylcyclohexane-2,4-diisocyanate, methylcyclohexane-2,6-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane 1,3-bis (isocyanatoethyl) cyclohexane, 1,3-bis (isocyanatomethyl) benzene, 1,3-bis (isocyanato-1-methylethyl) benzene, and the like. These organic diisocyanate compounds can be used alone or as a mixture of two or more thereof.

  The organic polyol compound (2) used in the above reaction preferably includes, as the organic diol compound, for example, alkyl diol, polyether diol, polyester diol and the like.

Examples of the alkyl diol as the organic diol compound include ethylene glycol, 1,3-propanediol, propylene glycol, 2,3-butanediol, 1,4-butanediol, 2-ethylbutane-1,4-diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane, Typical examples include 4,8-dihydroxytricyclo [5.2.1.0 ^2,6 ] decane and 2,2-bis (4-hydroxycyclohexyl) propane.

  The polyether diol as the organic diol compound can be synthesized, for example, by polymerization of aldehyde, alkylene oxide, glycol or the like by a known method. For example, polyether diol can be obtained by addition polymerization of formaldehyde, ethylene oxide, propylene oxide, tetramethylene oxide, epichlorohydrin or the like to alkyl diol under appropriate conditions.

  Examples of the polyester diol as the organic diol compound include esterification reaction products obtained by reacting saturated or unsaturated dicarboxylic acids and / or acid anhydrides thereof with excess alkyl diols, and alkyl diols. And esterification reaction products obtained by polymerizing at least one of hydroxycarboxylic acid, a lactone that is an intramolecular ester of the hydroxycarboxylic acid, and lactide that is an intermolecular ester of the hydroxycarboxylic acid. These organic polyol compounds can be used alone or in combination of two or more thereof.

  As said (3) hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. can be mentioned. In addition, the urethane (meth) acrylate oligomer as an oligomer used in the present invention is a compound having a (meth) acryloyl group and a hydroxyl group in one molecule and an organic diisocyanate compound, and the NCO / OH ratio is, for example, 0. It can also be produced by reacting in the presence of a urethanization catalyst such as dibutyltin dilaurate at a ratio of .9 to 1.0.

  The urethane (meth) acrylate oligomer as an oligomer used in the present invention is preferably at least one of a urethane (meth) acrylate oligomer or an aliphatic urethane (meth) acrylate oligomer having an alicyclic structure, and particularly preferably a fat. A urethane (meth) acrylate oligomer having a ring structure is useful from the viewpoint of weather resistance and reactivity of the coating film.

(A-1-2) Polyester (meth) acrylate oligomer The polyester (meth) acrylate as an oligomer used in the present invention is produced, for example, by a reaction between a polyester polyol having a hydroxyl group at the terminal and an unsaturated carboxylic acid. Can do. Such a polyester polyol can be typically prepared by esterifying a saturated or unsaturated dicarboxylic acid or an acid anhydride thereof with an excess amount of an alkylene diol. Typical examples of the dicarboxylic acid used include oxalic acid, succinic acid, adipic acid, phthalic acid, and maleic acid. Examples of the alkylene diol to be used include ethylene glycol, propylene glycol, butanediol, pentanediol, and the like. Here, as unsaturated carboxylic acid, acrylic acid, methacrylic acid, etc. can be mentioned as a typical thing, for example.

(A-1-3) Epoxy (meth) acrylate oligomer The epoxy (meth) acrylate oligomer as an oligomer used in the present invention is, for example, an epoxy compound and an unsaturated carboxylic acid as described above, 1 equivalent of an epoxy group. The equivalent carboxyl group equivalent is used, for example, in a ratio of 0.5 to 1.5, and is prepared by an acid ring-opening addition reaction to an ordinary epoxy group. As an epoxy compound used here, bisphenol A type epoxy, phenolic novolak type epoxy, etc. can be mentioned suitably, for example.

(A-1-4) Polyether (meth) acrylate oligomer The polyether (meth) acrylate as an oligomer used in the present invention is, for example, a polyether polyol such as polyethylene glycol and polypropylene glycol, and the unsaturated carboxylic acid described above. It can be prepared by reaction with an acid.

(A-2) Unsaturated polyester resin On the other hand, in the present invention, the unsaturated polyester resin used as the component (A) is, for example, a reaction of an organic polyol compound and an unsaturated carboxylic acid by a known method, and further required. Accordingly, it can be produced by reacting a saturated polycarboxylic acid. Typical examples of the organic polyol used include ethylene glycol, propylene glycol, triethylene glycol, trimethylolpropane, glycerin, and bisphenol A. Further, examples of the unsaturated carboxylic acid used include (anhydrous) maleic acid, (anhydrous) fumaric acid, (anhydrous) itaconic acid, and the like.

  As these (A) components, you may use together the said (meth) acryloyl group containing oligomer and unsaturated polyester resin.

(2) Component (B) The component (B) used in the present invention is an unsaturated monomer copolymerizable with the component (A), and includes styrene, α-methylstyrene, vinyltoluene, and N-vinyl-2. -It contains at least one selected from the group consisting of pyrrolidone, benzyl (meth) acrylate and ethoxylated (meth) acrylate. By having these unsaturated monomers, adhesion to the fiber reinforcement is improved. The mass proportion of styrene, α-methylstyrene, vinyltoluene, N-vinyl-2-pyrrolidone, benzyl (meth) acrylate or ethoxylated (meth) acrylate is in the range of 5 to 70 mass% in the fiber-reinforced resin molded article coating composition. Is more preferable, and the range of 10 to 50% by mass is more preferable. If it is this range, adhesiveness with a fiber reinforcement will improve. If it exceeds 70% by mass, the cured coating film becomes brittle, which is not preferable.

  The mass ratio of the component (A) and the component (B) depends on the types of compounds used as the component (A) and the component (B), but usually (A) / (B) = 30 / It is 70-70 / 30, and 35 / 65-65 / 35 is more preferable. Within this range, a hardened coating film with good curing characteristics can be obtained, and the fluidity in the mold of the fiber-reinforced resin molded article coating composition is good, and a uniform coating can be obtained without mixing bubbles. Therefore, it is preferable.

(3) Component (C) Component (C) used in the present invention is a polymerization initiator used to generate free radicals and polymerize the components (A) and (B). An organic peroxide polymerization initiator is used.

  Examples of the organic peroxide polymerization initiator include isobutyryl peroxide 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumylperoxyneodecanoate, di-3-methoxybutylperoxy Dicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-isopropylperoxydicarbonate, t-butylperoxybenzoate, t-butylperoxyisobutyrate Organic peroxides such as t-butylperoxy 2-ethylhexanoate, t-amylperoxy 2-ethylhexanoate, t-butylperoxyisopropyl carbonate, lauroyl peroxide and benzoyl peroxide It is mentioned as a thing. These may be used alone or in combination.

  The blending amount of the organic peroxide polymerization initiator is preferably 0.5 to 5 parts by mass, more preferably 1 to 4 parts by mass with respect to 100 parts by mass in total of the {(A) + (B)} components. It is. When the blending amount of the organic peroxide polymerization initiator as the component (C) is less than 0.5 parts by mass, the reaction of the components (A) and (B) does not proceed well, resulting in poor curing and from the mold to the fiber reinforced resin. When the molded body is taken out, the coating film is peeled off and a satisfactory molded body cannot be obtained. Moreover, when it exceeds 5 mass parts, the pot life of a fiber reinforced resin molded object coating composition becomes short, and it is unpreferable practically.

(4) Component (D) As unsaturated monomers copolymerizable with component (A) other than component (B), β- (meth) acryloyloxyethyl hydrogen maleate and β- (meth) acryloyloxyethyl are used. It is preferable to further include at least one selected from the group consisting of hydrogen phthalate since adhesion with the fiber-reinforced resin impregnated body and conductivity of the coating film are improved in the presence of the conductive filler. The mass ratio of at least one of β- (meth) acryloyloxyethyl hydrogen maleate and β- (meth) acryloyloxyethyl hydrogen phthalate is 0.4 to 10% by mass in the fiber-reinforced resin molded body coating composition. If it is in the range, the performance is sufficiently exhibited, which is preferable. More preferably, it is the range of 0.5-5 mass%, and if it exists in this range, the electroconductivity of a coating film will improve in the presence of the adhesiveness with a fiber reinforced resin impregnated body, and an electroconductive filler. In addition, by including a monomer having one ethylenic double bond in one molecule and a monomer having two or more ethylenic double bonds, the hardness of the formed film is increased and scratches are less likely to occur. preferable.

  Further, examples of unsaturated monomers copolymerizable with the component (A) other than the component (B) include tripropylene glycol diacrylate (TPGDA) and 1,6-hexanediol diacrylate (1,6-HDDA). Aliphatic (meth) acrylate monomer, cyclohexyl methacrylate, and (meth) acrylate monomer having an alicyclic structure such as 1,4-cyclohexanedimethanol monoacrylate (CHDMMA), trimethylolpropane triacrylate (TMPTA), trimethylol At least one selected from the group consisting of propaneethoxytriacrylate (TMPEOTA) and β- (meth) acryloyloxyethyl hydrogen succinate, in particular, an aliphatic (meth) acrylate monomer or an alicyclic ring They comprise at least one with concrete (meth) acrylate monomers are preferred from the weather resistance and the reactivity of the surface of the coating film.

(5) About (E) component The fiber reinforced resin molded object coating composition used by this invention may contain electroconductive carbon or electroconductive metal oxide particle further as needed. Moreover, the electroconductive particle which coat | covered the electroconductive metal oxide particle on the inorganic particle surface can also be used.

  The conductive carbon black is produced by a known production method such as a furnace method, a channel method, an acetylene method, or a thermal method. From the viewpoint of conductivity, carbon black obtained by the acetylene method is preferable, but not limited thereto. A preferable powder resistance value of the conductive carbon black is 0.3 Ω · cm or less.

  Examples of the conductive metal oxide particles include tin oxide, antimony-doped tin oxide, tin-doped indium oxide, and aluminum-doped tin oxide. Furthermore, it is preferable that antimony dope tin oxide contains 0.1-5 mass% of at least 1 sort (s) of phosphorus, aluminum, and molybdenum with respect to the oxide whole quantity.

  The inorganic particles coated with the conductive metal oxide particles are preferably at least one selected from titanium dioxide, zinc oxide, alumina, silica, alkali titanate and mica. A preferable powder resistance value of the conductive metal oxide particles is 20 Ω · cm or less.

(6) Other components The fiber-reinforced resin molded article coating composition used in the present invention may further contain at least one of glass flakes and pearl pigments as necessary. Moreover, at least 1 sort (s) of the inorganic particles whose average particle diameters are 0.1 micrometer or more and 50 micrometers or less, such as calcium carbonate, talc, barium sulfate, aluminum hydroxide, clay, or mica, can be included. These inorganic particles are blended in order to disperse the shrinkage stress accompanying the film curing, prevent warping of the molded body, reduce the thermal expansion coefficient and cure shrinkage, and make the reinforcing fibers of the base material inconspicuous.

  The fiber-reinforced resin molded article coating composition used in the present invention may further contain at least one coloring pigment as long as it does not affect the polymerization reaction of the polymerization initiator, if necessary. As the color pigment, various color pigments conventionally used for plastics and paints can be used.

  In the present invention, a release agent can be optionally used in combination in order to smoothly release the fiber-reinforced resin molded body from the mold. Examples of the release agent include stearic acid, stearic acid such as hydroxystearic acid, zinc stearate, aluminum stearate, magnesium stearate and calcium stearate, soybean oil lecithin, silicone oil, fatty acid ester and fatty acid alcohol dibasic acid. Examples include esters. The compounding quantity of these mold release agents is 0.1-5 mass parts with respect to a total of 100 mass parts of said {(A) + (B)} component, Furthermore, 0.2-2 mass parts, for example. Preferably there is. Within this range, the effect of releasing from the mold is suitably exhibited.

  The fiber-reinforced resin molded body coating composition according to the present invention can be blended with a modified resin for the purpose of improving adhesion or preventing cracks in the cured coating film. Examples of the modified resin used for such a purpose include low shrinkage agents such as chlorinated polyolefin, maleic acid-modified polyolefin, saturated polyester, polyvinyl acetate, and polymethyl methacrylate.

  The fiber reinforced resin molded article coating composition used in the present invention may further include a pigment, an antistatic agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor, a curing accelerator, and a pigment as necessary. You may mix | blend various additives, such as a dispersing agent, an antifoamer, a plasticizer, and a flame retardant.

  In the present invention, various skin materials can be arranged on the outermost surface of the reinforcing fiber material. As the skin material used, for example, a printing film can be used. As such a printing film, for example, a pattern layer such as a picture, a logo, a pattern, or a character is formed on a base film by a normal forming method. As a base film, it is used as a base film of a normal insert material, and can mention plastic films, such as an acryl, a styrene, and a polycarbonate.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example and a comparative example, the scope of the present invention is not limited at all by these Examples and comparative examples.

1. Preparation of matrix resin (1) Epoxy compound 1 (EPO-1)
100 parts by weight of epoxy resin (JER828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) bisphenol A type, epoxy equivalent of 184 to 194, viscosity of 12 to 15 Pa · s, average molecular weight of about 370) previously heated to 60 ° C. In contrast, 7 parts by mass of a polymerization initiator (1- (2-cyanoethyl) -2-ethyl-4-methylimidazole), 1 part by mass of a retarder (methyl p-toluenesulfonate), and an internal mold release agent (MoldWiz INT) -1846N (trade name, manufactured by AXEL PLASTICS RESEARCH)) At a ratio of 0.5 part by mass, mixing and defoaming were performed with a planetary (rotation and revolution) mixer, and epoxy resin 1 for matrix resin (EPO-1) ) Was prepared.

(2) Epoxy acrylate compound 1 (EAC-1)
Polystyrene acetate (Sacnol SN-09T (trade name, manufactured by Denki Kagaku Kogyo)) styrene for 70 parts by mass of epoxy acrylate resin (Lipoxy R-6540 (trade name, manufactured by Showa Polymer Co., Ltd.) viscosity 300 mPa · s) 30 parts by weight of a 65% solution, 0.5 parts by weight of a curing accelerator (8% cobalt octoate), 1 part by weight of a curing agent (t-amylperoxy-2-ethylhexanoate), and an internal mold release agent (stearin 1 part by mass of zinc acid) was added, and mixing and defoaming were performed with a planetary (rotation and revolution) mixer to prepare epoxy acrylate compound 1 (EAC-1) for matrix resin.

(3) Unsaturated polyester 1 (UPE-1)
Polystyrene acetate (Sacnol SN-09T (trade name, manufactured by Denki Kagaku Kogyo Co., Ltd.)) for 65 parts by mass of unsaturated polyester resin (Sandoma PC-350-C (trade name, manufactured by DH Materials)) 35 parts by weight of a 65% solution, 0.5 parts by weight of a curing accelerator (8% cobalt octoate), 1 part by weight of a curing agent (t-amylperoxy-2-ethylhexanoate), and an internal release agent (stearin 1 part by mass of zinc acid) was added and mixed and defoamed with a planetary (rotation and revolution) mixer to prepare unsaturated polyester 1 (UPE-1) for matrix resin.

2. Fiber-reinforced resin molded article coating composition (1) Epoxy acrylate compound 2 (EAC-2)
Epoxy resin (trade name: JER828, manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type, epoxy equivalent of 184 to 194, viscosity of 12 to 15 Pa · s, average molecular weight of about 370) 1000 parts by mass, methacrylic acid 490 parts by mass, triethylamine 3 parts by mass And 0.01 mass part of hydroquinone was put in the reactor and reacted at 125 ° C. for 3 hours to obtain an epoxy acrylate compound 2 having an acid value of about 8.

(2) Epoxy acrylate compound 3 (EAC-3)
Neopol 8101 (trade name, manufactured by Nippon Iupika Co., Ltd.), bisphenol A type, viscosity 850 to 950 mPa · s, styrene 40% solution (3) Urethane acrylate compound 1 (UAC-1)
1000 parts by weight of polypropylene glycol (average molecular weight 1000), 349 parts by weight of a mixture of 2,4- and 2,6-toluene diisocyanate and 0.2 parts by weight of methylquinone were put into a reactor and reacted while stirring at 80 ° C. for 6 hours. An isocyanate group-terminated polyurethane prepolymer was obtained. Next, 233 parts by mass of hydroxyethyl acrylate and 1 part by mass of dibutyltin laurate were added and reacted at 65 ° C. for 6 hours to obtain a urethane acrylate compound having a weight average molecular weight of 2500.

(4) Urethane acrylate compound 2 (UAC-2)
EBECRYL8402 (trade name, manufactured by Daicel Cytec Co., Ltd.), bifunctional, urethane acrylate compound having a viscosity of 1250 mPa · s / 25 ° C. and a molecular weight of 1,000.

(5) Urethane acrylate compound (UAC-3)
EBECRYL8701 (trade name, manufactured by Daicel Cytec), trifunctional, viscosity 4500 mPa · s / 60 ° C., molecular weight 2000 urethane acrylate compound.

(6) Polyester acrylate compound (PES-1)
EBECRYL812 (trade name, manufactured by Daicel Cytec Co., Ltd.), a tetrafunctional polyester acrylate compound having a viscosity of 325 mPa · s / 60 ° C. and a molecular weight of 800.

(7) Polyether acrylate compound (PET-1)
EBECRYL80 (trade name, manufactured by Daicel Cytec Co., Ltd.), tetrafunctional, polyether acrylate compound having a viscosity of 3000 mPa · s / 25 ° C. and a molecular weight of 1000.

(8) Unsaturated polyester compound 2 (UPE-2)
Iupica 7685 (trade name, manufactured by Japan Iupika), acid value 10-20 mg KOH / g, styrene 55% solution.

<Examples 1 to 13 and Comparative Examples 1 to 4>
Using a mold having a cavity for obtaining a plate-shaped resin molded body having a length of 500 mm, a width of 400 mm, and a thickness of 1.4 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. The surface of the mold cavity is carefully polished with # 2000 diamond paste and then plated with chrome. The clearance of the shear edge portion was in the range of 80 to 130 μm over the entire circumference. The mold temperature was set to 140 ° C for the fixed mold part and 140 ° C for the movable mold part, and the cavity surface was preliminarily diluted with an external mold release agent Daifree MS443 (manufactured by Daikin Industries) 5 times. Had been applied. Preformed carbon reinforcing fibers (plain weave cloth, thickness 0.2 mm, 7 layers) were set on the fixed mold surface, and the movable mold part was lowered and clamped at a pressure of about 4 MPa.

  Next, the inside of the cavity was vacuumed by a vacuum pump. When the inside of the cavity reached 20 torr or less, the valve of the vacuum suction line was closed, and then the matrix resin EPO-1 was injected into the cavity from the matrix resin injection port to impregnate the carbon reinforcing fibers. When the matrix resin was filled in the cavity, the matrix resin injection was terminated. Thereafter, the matrix resin was held for 5 minutes, and the matrix resin was cured to such an extent that it could withstand the injection of the fiber reinforced resin molded body coating composition and the flow pressure, thereby obtaining a reinforced fiber resin impregnated body.

  Next, the movable mold part was raised by about 2 mm, separated from the fixed mold part, and then 32 cc (film of fiber reinforced resin molded article coating composition shown in Tables 1 and 2 from the fiber reinforced resin molded article coating composition inlet. (Equivalent to a thickness of 150 μm) was injected between the surface of the impregnated reinforcing fiber resin and the surface of the fixed mold. After completion of the injection, re-clamping was performed at a pressure of 4 MPa, and the fiber-reinforced resin molded body coating composition was cured by holding for 2 minutes. At this time, the movable mold part and the fixed mold part were slightly separated. That is, the pressure for remolding is applied to the fiber-reinforced resin molded body coating composition. Thereafter, when the fiber-reinforced resin molded article coating composition was cured, the mold temperature was kept unchanged, the movable mold part was raised, and the fiber-reinforced resin molded article was taken out of the mold. The obtained molded body was measured by the following test method. The results are shown in Tables 3 and 4.

ダイヤナールＢＲ５２（商品名、三菱レイヨン社製）、スチレン−アクリレート共重合体、重量平均分子量８５０００
サクノールＳＮ−０９Ｔ（商品名、電気化学工業社製）酢酸ビニル樹脂、重合度１０００〜１１５０

Dianal BR52 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.), styrene-acrylate copolymer, weight average molecular weight 85000
Sacnol SN-09T (trade name, manufactured by Denki Kagaku Kogyo) vinyl acetate resin, degree of polymerization 1000-1150

<Appearance of fiber reinforced resin molding>
If there is no glossiness, uneven color, wrinkles, swelling, cracking, peeling, crease, crushing, etc., by visual observation after leaving for 2 hours in the room after removal, “No abnormality in the appearance of the coating film” .

<Hardness of fiber reinforced resin molding covering>
According to JIS K 5600-5-4: scratch hardness (pencil method), the pencil hardness of the coating on the surface of the fiber-reinforced resin molded product was measured.

<Adhesiveness of coating to fiber-reinforced resin molded article>
According to JIS K 5600-5-6: Adhesion (cross-cut method), the initial coating adhesion test was carried out. Adhesion was evaluated in the following 6 grades from 0 to 5 based on the classification of the test results described in JIS K 5600-5-6.
<6-level evaluation>
0: The edges of the cut are completely smooth, and there is no peeling in any lattice eye.
1 ... Small peeling of the coating film at the intersection of cuts. It is clearly not more than 5% that the crosscut is affected.
2 The coating is peeled along the edge of the cut and / or at the intersection. The cross-cut part is clearly affected by more than 5% but not more than 15%.
3 The coating has been partially or fully peeled along the edges of the cut, and / or various parts of the eye have been partially or completely peeled off. The cross-cut portion is clearly affected by more than 15% but not more than 35%.
4 ... The covering is partially or completely peeled along the edge of the cut, and / or some eyes are partially or completely peeled off. The cross-cut portion is clearly affected by more than 35% but not more than 65%.
5: When the degree of peeling exceeds Category 4.

<Swell of fiber-reinforced resin molding>
The swell size was measured according to JIS B 0601: arithmetic mean swell Wa.

<Moisture resistance>
According to JIS K 5600-7-2: Moisture resistance (continuous condensation method), a long-term durability test (test conditions were 50 ± 1 ° C., relative humidity 95% or more, test time 240 hours) was performed. Evaluation was made immediately after taking out and after standing for 2 hours in the room, and no wrinkles, blisters, cracks, rust, peeling, etc. were observed on the coating film, and clouding, whitening, discoloration, etc. were observed after standing for 2 hours. If there is no error, “No abnormality” is assumed.

<Surface resistance value of fiber-reinforced resin-coated molded product>
The surface resistance value of the fiber-reinforced resin-coated molded body was measured using a Hiresta UP MCP-HT450 type measuring instrument (manufactured by Mitsubishi Chemical Corporation) after being left in a room of 23 ± 2 ° C. and 50 ± 5% RH for 24 hours. did.

<Pot life>
JIS K 5600-2-6: The pot life of the fiber-reinforced resin molded article coating composition at 23 ± 2 ° C. was measured according to the pot life.

(Examples 14 to 20 and Comparative Example 5)
Using a mold having a cavity for obtaining a plate-shaped resin molded body having a length of 500 mm, a width of 400 mm, and a thickness of 1.4 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. The surface of the mold cavity is carefully polished with # 2000 diamond paste and then plated with chrome. The clearance of the shear edge portion was in the range of 80 to 130 μm over the entire circumference. The mold temperature was set to 140 ° C for the fixed mold part and 140 ° C for the movable mold part, and the cavity surface was preliminarily diluted with an external mold release agent Daifree MS443 (manufactured by Daikin Industries) 5 times. Had been applied. Preformed carbon reinforcing fibers (plain weave cloth, thickness 0.2 mm, 7 layers) were set on the fixed mold surface, and the movable mold part was lowered and clamped at a pressure of about 4 MPa.

  Next, the inside of the cavity was vacuumed by a vacuum pump. When the inside of the cavity reached 20 torr or less, the valve of the vacuum suction line was closed, and then the matrix resin EPO-1 was injected into the cavity from the matrix resin injection port to impregnate the carbon reinforcing fibers. When the matrix resin was filled in the cavity, the matrix resin injection was terminated. Thereafter, the matrix resin was held for 5 minutes, and the matrix resin was cured to such an extent that it could withstand the injection of the fiber reinforced resin molded body coating composition and the flow pressure, thereby obtaining a reinforced fiber resin impregnated body.

  Next, the movable mold part was raised by about 1 mm, separated from the fixed mold part, and then 32 cc of the fiber reinforced resin molded article coating composition shown in Table 5 (film thickness 150 μm) from the fiber reinforced resin molded article coating composition inlet. The amount of the resin was impregnated between the surface of the impregnated reinforcing fiber resin and the surface of the fixed mold. After completion of the injection, re-clamping was performed at a pressure of 4 MPa, and the fiber-reinforced resin molded body coating composition was cured by holding for 2 minutes. At this time, the movable mold part and the fixed mold part were slightly separated. That is, the pressure for remolding is applied to the fiber-reinforced resin molded body coating composition. Thereafter, when the fiber-reinforced resin molded article coating composition was cured, the mold temperature was kept unchanged, the movable mold part was raised, and the fiber-reinforced resin molded article was taken out of the mold. The obtained molded body was measured by the test method. The results are shown in Table 6.

Ｚｅｌｅｃ ＵＮ（商品名、Ｓｔｅｐａｎ Ｃｏｍｐａｎｙ製）、非中和性アルコールホスヘート

Zelec UN (trade name, manufactured by Stepan Company), non-neutralizing alcohol phosphate

(Examples 21 to 24)
Using a mold having a cavity for obtaining a plate-shaped resin molded body having a length of 500 mm, a width of 400 mm, and a thickness of 1.4 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. The surface of the mold cavity is carefully polished with # 2000 diamond paste and then plated with chrome. The clearance of the shear edge portion was in the range of 80 to 130 μm over the entire circumference. The mold temperature was set to 140 ° C for the fixed mold part and 140 ° C for the movable mold part, and the cavity surface was preliminarily diluted with an external mold release agent Daifree MS443 (manufactured by Daikin Industries) 5 times. Had been applied. Preformed carbon reinforcing fibers (plain weave cloth, thickness 0.2 mm, 7 layers) were set on the fixed mold surface, and the movable mold part was lowered and clamped at a pressure of about 4 MPa.

  Next, the inside of the cavity was vacuumed by a vacuum pump. When the inside of the cavity reached 20 torr or less, the valve of the vacuum suction line was closed, and then the matrix resin EPO-1 was injected into the cavity from the matrix resin injection port to impregnate the carbon reinforcing fibers. When the matrix resin was filled in the cavity, the matrix resin injection was terminated. Thereafter, the matrix resin was held for 5 minutes, and the matrix resin was cured to such an extent that it could withstand the injection of the fiber reinforced resin molded body coating composition and the flow pressure, thereby obtaining a reinforced fiber resin impregnated body.

  Next, the movable mold part was raised by about 2 mm, separated from the fixed mold part, and then 32 cc of the fiber reinforced resin molded article coating composition shown in Table 7 (film thickness 150 μm) from the fiber reinforced resin molded article coating composition inlet. The amount of the resin was impregnated between the surface of the impregnated reinforcing fiber resin and the surface of the fixed mold. After completion of the injection, re-clamping was performed at a pressure of 4 MPa, and the fiber-reinforced resin molded body coating composition was cured by holding for 2 minutes. At this time, the movable mold part and the fixed mold part were slightly separated. That is, the pressure for remolding is applied to the fiber-reinforced resin molded body coating composition. Thereafter, when the fiber-reinforced resin molded article coating composition was cured, the mold temperature was kept unchanged, the movable mold part was raised, and the fiber-reinforced resin molded article was taken out of the mold. The obtained molded body was measured by the test method. The results are shown in Table 8.

(Examples 25-26)
Using a mold having a cavity for obtaining a plate-shaped resin molded body having a length of 500 mm, a width of 400 mm, and a thickness of 1.4 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. The surface of the mold cavity is carefully polished with # 2000 diamond paste and then plated with chrome. The clearance of the shear edge portion was in the range of 80 to 130 μm over the entire circumference. The mold temperature was set to 140 ° C for the fixed mold part and 140 ° C for the movable mold part, and the cavity surface was preliminarily diluted with an external mold release agent Daifree MS443 (manufactured by Daikin Industries) 5 times. Had been applied. Preformed carbon reinforcing fibers (plain weave cloth, thickness 0.2 mm, 7 layers) were set on the fixed mold surface, and the movable mold part was lowered and clamped at a pressure of about 4 MPa.

  Next, the inside of the cavity was vacuumed by a vacuum pump. When the inside of the cavity reached 20 torr or less, the valve of the vacuum suction line was closed, and then the matrix resin EAC-1 was injected into the cavity from the matrix resin injection port and impregnated with carbon reinforcing fibers. When the matrix resin was filled in the cavity, the matrix resin injection was terminated. Thereafter, the matrix resin was held for 5 minutes, and the matrix resin was cured to such an extent that it could withstand the injection and flow pressure of the fiber reinforced resin molded body coating composition, thereby obtaining a reinforced fiber resin impregnated body.

  Next, the movable mold part was raised by about 2 mm, separated from the fixed mold, and then 43 cc of the fiber reinforced resin molded body coating composition shown in Table 9 (with a film thickness of 200 μm) from the fiber reinforced resin molded body coating composition inlet. Equivalent amount) was injected between the surface of the impregnated reinforcing fiber resin and the surface of the stationary mold. After completion of the injection, re-clamping was performed at a pressure of 4 MPa, and the fiber-reinforced resin molded body coating composition was cured by holding for 2 minutes. At this time, the movable mold part and the fixed mold part were slightly separated. That is, the pressure for remolding is applied to the fiber-reinforced resin molded body coating composition. Thereafter, when the fiber-reinforced resin molded article coating composition was cured, the mold temperature was kept unchanged, the movable mold part was raised, and the fiber-reinforced resin molded article was taken out of the mold. The obtained molded body was measured by the test method. The results are shown in Table 10.

(Examples 27 to 28)
Using a mold having a cavity for obtaining a plate-shaped resin molded body having a length of 500 mm, a width of 400 mm, and a thickness of 1.4 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. The surface of the mold cavity is carefully polished with # 2000 diamond paste and then plated with chrome. The clearance of the shear edge portion was in the range of 80 to 130 μm over the entire circumference. The mold temperature was set to 140 ° C. for the fixed mold part and 140 ° C. for the movable mold part. Preformed carbon reinforcing fibers (plain weave cloth, thickness 0.2 mm, 7 layers) were set on the fixed mold surface, and the movable mold part was lowered and clamped at a pressure of about 4 MPa.

  Next, the inside of the cavity was vacuumed by a vacuum pump. When the inside of the cavity reached 20 torr or less, the valve of the vacuum suction line was closed, and then the matrix resin UPE-1 was injected into the cavity from the matrix resin injection port to impregnate the carbon reinforcing fibers. When the matrix resin was filled in the cavity, the matrix resin injection was terminated. Thereafter, the matrix resin was held for 5 minutes, and the matrix resin was cured to such an extent that it could withstand the injection of the fiber-reinforced resin molding coating composition and the flow pressure, thereby obtaining a reinforcing fiber resin-impregnated body.

  Next, the movable mold part was raised by about 2 mm, separated from the fixed mold, and then 43 cc (film) of the fiber reinforced resin molded body coating composition used in Examples 25 and 26 from the fiber reinforced resin molded body coating composition inlet. (Equivalent to a thickness of 200 μm) was injected between the surface of the impregnated reinforcing fiber resin and the surface of the fixed mold. After completion of the injection, re-clamping was performed at a pressure of 4 MPa, and the fiber-reinforced resin molded body coating composition was cured by holding for 2 minutes. At this time, the movable mold part and the fixed mold part were slightly separated. That is, the pressure for remolding is applied to the fiber-reinforced resin molded body coating composition. Thereafter, when the fiber-reinforced resin molded article coating composition was cured, the mold temperature was kept unchanged, the movable mold part was raised, and the fiber-reinforced resin molded article was taken out of the mold. The obtained molded body was measured by the test method. The results are shown in Table 11.

(Examples 29 to 30)
Using a mold having a cavity for obtaining a plate-shaped resin molded body having a length of 500 mm, a width of 400 mm, and a thickness of 2.0 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. The surface of the mold cavity is carefully polished with # 2000 diamond paste and then plated with chrome. The clearance of the shear edge portion was in the range of 80 to 130 μm over the entire circumference. The mold temperature was set to 140 ° C for the fixed mold part and 140 ° C for the movable mold part, and the cavity surface was preliminarily diluted with an external mold release agent Daifree MS443 (manufactured by Daikin Industries) 5 times. Had been applied. Glass preformed fibers (first layer surfacing mat, second layer and beyond, plain weave structure cloth, thickness 0.4 mm, five layers) are set on the fixed mold surface, and the movable mold part is lowered. Clamping was performed at a pressure of about 4 MPa.

  Next, the inside of the cavity was vacuumed by a vacuum pump. When the inside of the cavity reached 20 torr or less, the valve of the vacuum suction line was closed, and then the matrix resin EPO-1 was injected into the cavity from the matrix resin injection port to impregnate the glass reinforcing fibers. When the matrix resin was filled in the cavity, the matrix resin injection was terminated. Thereafter, the matrix resin was held for 5 minutes, and the matrix resin was cured to such an extent that it could withstand the injection of the fiber reinforced resin molded body coating composition and the flow pressure, thereby obtaining a reinforced fiber resin impregnated body.

  Next, the movable mold part was raised by about 2 mm, separated from the fixed mold, and then 32 cc of the fiber reinforced resin molded article coating composition used in Examples 25 and 26 (film) from the fiber reinforced resin molded article coating composition inlet. (Equivalent to a thickness of 150 μm) was injected between the surface of the impregnated reinforcing fiber resin and the surface of the fixed mold. After completion of the injection, re-clamping was performed at a pressure of 4 MPa, and the fiber-reinforced resin molded body coating composition was cured by holding for 2 minutes. At this time, the movable mold part and the fixed mold part were slightly separated. That is, the pressure for remolding is applied to the fiber-reinforced resin molded body coating composition. Thereafter, when the fiber-reinforced resin molded article coating composition was cured, the mold temperature was kept unchanged, the movable mold part was raised, and the fiber-reinforced resin molded article was taken out of the mold. The obtained molded body was measured by the test method. The results are shown in Table 12.

(Examples 31-32)
Using a mold having a cavity for obtaining a plate-shaped resin molded body having a length of 500 mm, a width of 400 mm, and a thickness of 1.4 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. The surface of the mold cavity is carefully polished with # 2000 diamond paste and then plated with chrome. The clearance of the shear edge portion was in the range of 80 to 130 μm over the entire circumference. The mold temperature was set to 140 ° C for the fixed mold part and 140 ° C for the movable mold part, and the cavity surface was preliminarily diluted with an external mold release agent Daifree MS443 (manufactured by Daikin Industries) 5 times. Had been applied. Preformed carbon reinforcing fibers (plain weave cloth, thickness 0.2 mm, 7 layers) were set on the fixed mold surface, and the movable mold part was lowered and clamped at a pressure of about 2 MPa.

  Next, the inside of the cavity was vacuumed by a vacuum pump. When the inside of the cavity reached 20 torr or less, the valve of the vacuum suction line was closed, and then the matrix resin EPO-1 was injected into the cavity from the matrix resin injection port to impregnate the carbon reinforcing fiber body. When the matrix resin was filled in the cavity, the matrix resin injection was terminated. Thereafter, the matrix resin was held for 5 minutes, and the matrix resin was cured to such an extent that it could withstand the injection of the fiber reinforced resin molded body coating composition and the flow pressure, thereby obtaining a reinforced fiber resin impregnated body.

  Next, the movable mold part was raised by about 2 mm, separated from the fixed mold, and then 32 cc of the fiber reinforced resin molded article coating composition used in Examples 25 and 26 (film) from the fiber reinforced resin molded article coating composition inlet. (Equivalent to a thickness of 150 μm) was injected between the surface of the impregnated reinforcing fiber resin and the surface of the fixed mold. After completion of the injection, the mold was clamped again at a pressure of 4 MPa and held for 5 seconds, and then the mold clamping pressure was reduced to 1.5 MPa over 1 second. Thereafter, the fiber-reinforced resin molded body coating composition was cured by holding for 2 minutes. At this time, the movable mold part and the fixed mold part were slightly separated. That is, the pressure for remolding is applied to the fiber-reinforced resin molded body coating composition. Thereafter, when the fiber-reinforced resin molded article coating composition was cured, the mold temperature was kept unchanged, the movable mold part was raised, and the fiber-reinforced resin molded article was taken out of the mold. The obtained molded body was measured by the test method. The results are shown in Table 13.

(Examples 33 to 34)
Using a mold having a cavity for obtaining a plate-shaped resin molded body having a length of 500 mm, a width of 400 mm, and a thickness of 1.4 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. The surface of the mold cavity is carefully polished with # 2000 diamond paste and then plated with chrome. The clearance of the shear edge portion was in the range of 80 to 130 μm over the entire circumference. The mold temperature was set to 140 ° C for the fixed mold part and 140 ° C for the movable mold part, and the cavity surface was preliminarily diluted with an external mold release agent Daifree MS443 (manufactured by Daikin Industries) 5 times. Had been applied. Preformed carbon reinforcing fibers (plain weave cloth, thickness 0.2 mm, 7 layers) were set on the fixed mold surface, and the movable mold part was lowered and clamped at a pressure of about 2 MPa.

  Next, the inside of the cavity was vacuumed by a vacuum pump. When the inside of the cavity reached 20 torr or less, the valve of the vacuum suction line was closed, and then the matrix resin EPO-1 was injected into the cavity from the matrix resin injection port to impregnate the carbon reinforcing fibers. When the matrix resin was filled in the cavity, the matrix resin injection was terminated. Thereafter, the matrix resin was held for 5 minutes, and the matrix resin was cured to such an extent that it could withstand the injection of the fiber reinforced resin molded body coating composition and the flow pressure, thereby obtaining a reinforced fiber resin impregnated body.

  Next, after setting to “zero” so as not to apply the mold clamping pressure, 32 cc of the fiber reinforced resin molded body coating composition used in Examples 25 and 26 from the fiber reinforced resin molded body coating composition injection port (with a film thickness of 150 μm). Equivalent amount) was injected between the surface of the impregnated reinforcing fiber resin and the surface of the stationary mold. After completion of the injection, re-clamping was performed at a pressure of 2 MPa, and the fiber-reinforced resin molded body coating composition was cured by holding for 2 minutes. At this time, the movable mold part and the fixed mold part were slightly separated. That is, the pressure for remolding is applied to the fiber-reinforced resin molded body coating composition. Thereafter, when the fiber-reinforced resin molded article coating composition was cured, the mold temperature was kept unchanged, the movable mold part was raised, and the fiber-reinforced resin molded article was taken out of the mold. The obtained molded body was measured by the test method. The results are shown in Table 14.

(Examples 35-37 and Comparative Examples 6-7)
Using a mold having a cavity for obtaining a plate-shaped resin molded body having a length of 500 mm, a width of 400 mm, and a thickness of 1.4 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIGS. The surface of the mold cavity is carefully polished with # 2000 diamond paste and then plated with chrome. The clearance of the shear edge portion was in the range of 80 to 130 μm over the entire circumference. The mold temperature was set to 140 ° C for the fixed mold part and 140 ° C for the movable mold part, and the cavity surface was preliminarily diluted with an external mold release agent Daifree MS443 (manufactured by Daikin Industries) 5 times. Had been applied. In Examples 35-37, the mold structure shown in FIG. 2 was used, and in Comparative Examples 6-7, the mold structure shown in FIG. 1 was used. Carbon reinforcing fibers preformed on the fixed mold surface (plain weave structure) The cross, thickness of 0.2 mm, 7 sheets stacked) was set, the movable mold part was lowered, and the mold was clamped at a pressure of about 4 MPa.

  Next, the inside of the cavity was vacuumed by a vacuum pump. When the inside of the cavity reached 20 torr or less, the valve of the vacuum suction line was closed, and then the matrix resin EPO-1 was injected into the cavity from the matrix resin injection port to impregnate the carbon reinforcing fibers. When the matrix resin was filled in the cavity, the matrix resin injection was terminated. Thereafter, the matrix resin was held for 5 minutes, and the matrix resin was cured to such an extent that it could withstand the injection of the fiber reinforced resin molded body coating composition and the flow pressure, thereby obtaining a reinforced fiber resin impregnated body.

  Next, after raising the movable mold part by about 1 mm and separating from the fixed mold part, in Examples 35 to 37, after pulling out the slide block, in Example 18 from the fiber reinforced resin molded article coating composition injection port The used fiber reinforced resin molded body coating composition was injected between the surface of the reinforced fiber resin impregnated body and the surface of the fixed mold in an amount to give a predetermined film thickness. After completion of the injection, re-clamping was performed at a pressure of 4 MPa, and the fiber-reinforced resin molded body coating composition was cured by holding for 2 minutes. At this time, the movable mold part and the fixed mold part were slightly separated. That is, the pressure for remolding is applied to the fiber-reinforced resin molded body coating composition. Thereafter, when the fiber-reinforced resin molded article coating composition was cured, the mold temperature was kept unchanged, the movable mold part was raised, and the fiber-reinforced resin molded article was taken out of the mold.

  On the other hand, in Comparative Examples 6 to 7, the movable mold part was raised by about 1 mm, separated from the fixed mold, and then the fiber reinforced resin molding used in Example 18 from the fiber reinforced resin molded article coating composition inlet. An amount of the body coating composition having a predetermined film thickness was injected between the molded body and the surface of the fixed mold. After completion of the injection, the mold was re-clamped at a pressure of 4 MPa, and held for 2 minutes to cure the fiber-reinforced resin molded body coating composition. At this time, when the film thickness was 15 μm with a small injection amount, there was no gap between the movable mold part and the fixed mold part.

  The obtained fiber reinforced resin molded product was measured by the test method. The results are shown in Table 15.

(Examples 38 to 39 and Comparative Examples 8 to 9)
Using a mold having a cavity for obtaining a plate-shaped resin molded body having a length of 500 mm, a width of 400 mm, and a thickness of 1.4 mm, in-mold coating was performed on the molded body according to the embodiment shown in FIG. The surface of the mold cavity is carefully polished with # 2000 diamond paste and then plated with chrome. The clearance of the shear edge portion was in the range of 80 to 130 μm over the entire circumference. The mold temperature was set to 140 ° C for the fixed mold part and 140 ° C for the movable mold part, and the cavity surface was preliminarily diluted with an external mold release agent Daifree MS443 (manufactured by Daikin Industries) 5 times. Had been applied. Preformed carbon reinforcing fibers (plain weave cloth, thickness 0.2 mm, 7 layers) were set on the fixed mold surface, and the movable mold part was lowered and clamped at a pressure of about 2 MPa.

  Next, the inside of the cavity was vacuumed by a vacuum pump. When the inside of the cavity reached 20 torr or less, the valve of the vacuum suction line was closed, and then the matrix resin EPO-1 was injected into the cavity from the matrix resin injection port to impregnate the carbon reinforcing fibers. When the matrix resin was filled in the cavity, the matrix resin injection was terminated. Thereafter, the matrix resin was held for 5 minutes, and the matrix resin was cured to such an extent that it could withstand the injection of the fiber reinforced resin molded body coating composition and the flow pressure, thereby obtaining a reinforced fiber resin impregnated body.

  Next, the movable mold part was raised by about 2 mm, separated from the fixed mold part, and then 21 cc (film thickness) of the fiber reinforced resin molded article coating composition used in Example 25 from the fiber reinforced resin molded article coating composition inlet. (Equivalent to 100 μm) was injected between the surface of the reinforced fiber resin impregnated body and the surface of the fixed mold. After completion of the injection, the mold was re-clamped at a predetermined pressure, and held for 2 minutes to cure the fiber-reinforced resin molded body coating composition. Thereafter, when the fiber-reinforced resin molded article coating composition was cured, the mold temperature was kept unchanged, the movable mold part was raised, and the fiber-reinforced resin molded article was taken out of the mold. The obtained molded body was measured by the test method. The results are shown in Table 16.

(Examples 40 to 41)
A mold having a cavity for obtaining a plate-shaped resin molded body having a length of 500 mm, a width of 400 mm, and a thickness of 1.4 mm, and having a rapid heating and cooling mechanism, is applied to the molded body according to the embodiment shown in FIG. In-mold coating was performed. The surface of the mold cavity is carefully polished with # 2000 diamond paste and then plated with chrome. The clearance of the shear edge portion was in the range of 80 to 130 μm over the entire circumference. The mold temperature part was set to 140 ° C. for the fixed mold part and 140 ° C. for the movable mold part, and external release agent die-free MS443 (manufactured by Daikin Industries) was diluted 5 times in advance on the cavity surface. Things have been applied. Preformed carbon reinforcing fibers (plain weave cloth, thickness 0.2 mm, 7 layers) were set on the fixed mold surface, and the movable mold part was lowered and clamped at a pressure of about 4 MPa.

  Next, the inside of the cavity was vacuumed by a vacuum pump. When the inside of the cavity reached 20 torr or less, the valve of the vacuum suction line was closed, and then the matrix resin EPO-1 was injected into the cavity from the matrix resin injection port to impregnate the carbon reinforcing fibers. The matrix resin injection was terminated when the matrix resin was filled in the cavity. Thereafter, the matrix resin was held for 5 minutes, and the matrix resin was cured to such an extent that it could withstand the injection of the fiber reinforced resin molded body coating composition and the flow pressure, thereby obtaining a reinforced fiber resin impregnated body.

  Next, the movable mold part was raised by about 1 mm, separated from the fixed mold part, and then 32 cc of the fiber reinforced resin molded body coating composition used in Examples 25 and 26 from the fiber reinforced resin molded body coating composition inlet. An amount equivalent to a film thickness of 150 μm was injected between the surface of the impregnated reinforcing fiber resin and the surface of the fixed mold. After completion of the injection, re-clamping was performed at a pressure of 4 MPa, and the fiber-reinforced resin molded body coating composition was cured by holding for 2 minutes. At this time, the movable mold part and the fixed mold part were slightly separated. That is, the pressure for remolding is applied to the fiber-reinforced resin molded body coating composition.

  Subsequently, the movable mold part and the fixed mold part were rapidly cooled to 40 ° C., and then the movable mold part was raised, and the fiber-reinforced resin molded body was taken out from the mold. The obtained molded body was measured by the test method. The results are shown in Table 17.

(Examples 42 to 43)
A first cavity for obtaining a box-shaped resin molded body having a length of 500 mm, a width of 400 mm, a height of 100 mm, a drawing angle of 2 ° in the height direction, and a plate thickness of 1.4 mm, and a mold larger than the first cavity A mold having a second cavity for applying an inner coating and a core mold portion, and an injection port for injecting a matrix resin into the first cavity or the core mold portion, and an inner coating for the mold. An FRP molded body is manufactured by an RTM molding method (Resin Transfer Molding) using a mold provided with an injection port for injecting a fiber-reinforced resin molded body coating composition into a mold portion having a second cavity to be applied. In the method, the first cavity, the second cavity and the core mold part are set to 140 ° C., and the first cavity surface and the core mold part surface are preliminarily provided with an external release agent die-free MS. A solution obtained by diluting 443 (manufactured by Daikin Industries, Ltd.) five times was applied. Preformed carbon reinforcing fibers (plain weave structure cloth, thickness 0.2 mm, 7 layers) were set on the core mold surface, the first cavity was lowered, and the mold was clamped at a pressure of about 4 MPa.

  Next, the inside of the cavity was vacuumed by a vacuum pump. When the inside of the cavity reached 20 torr or less, the valve of the vacuum suction line was closed, and then the matrix resin EPO-1 was injected into the cavity from the matrix resin injection port to impregnate the carbon reinforcing fibers. When the matrix resin was filled in the cavity, the matrix resin injection was terminated. Thereafter, the matrix resin was held for 5 minutes, and the matrix resin was cured to such an extent that it could withstand the injection of the fiber reinforced resin molded body coating composition and the flow pressure, thereby obtaining a reinforced fiber resin impregnated body.

  Next, with the obtained reinforced fiber resin impregnated body fixed to the core mold part, the first mold was rotated up and the second cavity was placed on the core mold part, and the mold was clamped at a pressure of 2 MPa. Next, 83 cc of the fiber-reinforced resin molded body coating composition used in Examples 25 and 26 was injected between the surface of the reinforcing fiber resin-impregnated body and the surface of the fixed mold from the fiber-reinforced resin molded body coating composition injection port. . After completion of the injection, the fiber-reinforced resin molded body coating composition was cured for 2 minutes. Then, the 2nd cavity was raised and the fiber reinforced resin molding was taken out from the type | mold. According to this method, it is possible to give a film thickness even to a molded product shape with a small punch angle, and the film thickness of the obtained molded body was about 200 μm on the entire surface. The obtained molded body was measured by the test method. The results are shown in Table 18.

DESCRIPTION OF SYMBOLS 1 Movable mold part 2 Fixed mold part 3 Cavity 4 Sealing packing 5 Matrix resin injection port 6 Matrix resin tank 7 Fiber reinforced resin molded article coating composition injection port 8 Fiber reinforced resin molded article coating composition tank 9 Weighing Cylinder 10 Decompression suction part 11 Vacuum trap 12 Vacuum pump 13 Valve 14 Valve 15 Pressure feed pump 16 Share edge 17 Heat medium piping 18 Slide block 19 Hydraulic cylinder

Claims (16)

(A) at least one selected from the group consisting of a urethane oligomer having a (meth) acryloyl group, an epoxy oligomer, a polyester oligomer and a polyether oligomer, and an unsaturated polyester;
(B) an unsaturated monomer copolymerizable with the component (A), which is styrene, α-methylstyrene, vinyltoluene, N-vinyl-2-pyrrolidone, benzyl (meth) acrylate, and ethoxylated phenyl (meth) acrylate At least one unsaturated monomer selected from the group consisting of:
(C) A fiber-reinforced resin molded article coating composition comprising a polymerization initiator.   (D) Unsaturated monomer copolymerizable with component (A) other than component (B), β- (meth) acryloyloxyethyl hydrogen maleate and β- (meth) acryloyloxyethyl hydrogen The fiber-reinforced resin molded article coating composition according to claim 1, further comprising at least one unsaturated monomer selected from phthalates.   The fiber-reinforced resin molded article coating composition according to claim 1 or 2, further comprising (E) conductive particles obtained by coating conductive carbon black or conductive metal oxide particles on the surface of inorganic particles. RTM (Resin Transfer Molding) using a mold that can be divided into at least two mold parts, provided with a heating means and provided with an injection port for injecting a matrix resin and an injection port for injecting a fiber-reinforced resin molded body coating composition ) In a method for producing a fiber-reinforced resin molded body by a molding method,
The mold is preheated to a temperature at which the matrix resin and the fiber-reinforced resin molded body coating composition according to any one of claims 1 to 3 are cured, and a fiber reinforcing material is formed in a cavity formed by the mold. After the mold is clamped, the matrix resin is injected into the cavity and impregnated in the fiber reinforcement, and the matrix resin is injected into the fiber-reinforced resin molded article coating composition and flows. Curing the matrix resin until it can withstand pressure to obtain a fiber reinforced resin impregnated body;
Injecting the fiber reinforced resin molded article coating composition between the fiber reinforced resin impregnated body surface and the mold surface so as to have a film thickness of 20 to 600 μm;
A step of re-clamping at a pressure of 0.5 to 7 MPa immediately after completion of injection;
Curing the fiber-reinforced resin molded article coating composition;
After the fiber reinforced resin molded body coating composition is cured, the mold is opened, and the fiber reinforced resin molded body formed by curing the fiber reinforced resin molded body coating composition on the surface of the fiber reinforced resin impregnated body And a step of taking out from the mold. RTM molding using a mold that can be divided into at least two mold parts, provided with a heating means and a cooling means, and provided with an injection port for injecting a matrix resin and an injection port for injecting a fiber-reinforced resin molded article coating composition In a method for producing a fiber-reinforced resin molded body by the method,
The mold is preheated to a temperature at which the matrix resin and the fiber-reinforced resin molded body coating composition according to any one of claims 1 to 3 are cured, and a fiber reinforcing material is formed in a cavity formed by the mold. After the mold is clamped, the matrix resin is injected into the cavity and impregnated in the fiber reinforcement, and the matrix resin is injected into the fiber-reinforced resin molded article coating composition and flows. Curing the matrix resin until it can withstand pressure to obtain a fiber reinforced resin impregnated body;
Injecting the fiber reinforced resin molded article coating composition between the fiber reinforced resin impregnated body surface and the mold surface so as to have a film thickness of 20 to 600 μm;
A step of re-clamping at a pressure of 0.5 to 7 MPa immediately after completion of injection;
Curing the fiber-reinforced resin molded article coating composition;
A step of cooling the surface of the mold part provided with an injection port for injecting at least the fiber-reinforced resin molded body coating composition after curing the fiber-reinforced resin molded body coating composition;
And a step of opening the mold and taking out the fiber reinforced resin molded body obtained by curing the fiber reinforced resin molded body coating composition on the surface of the fiber reinforced resin impregnated body from the mold. Manufacturing method of resin molding. RTM molding using a mold that can be divided into at least two mold parts, provided with a heating means and a cooling means, and provided with an injection port for injecting a matrix resin and an injection port for injecting a fiber-reinforced resin molded article coating composition In a method for producing a fiber-reinforced resin molded body by the method,
The mold is adjusted in advance to a temperature at which the matrix resin does not cure, a fiber reinforcing material is disposed in the cavity formed by the mold, the mold is clamped, and the matrix is then placed in the cavity. Injecting resin to impregnate the fiber reinforcement;
The mold is heated to a temperature at which the matrix resin can withstand the injection pressure and flow pressure of the fiber-reinforced resin molded article coating composition, and the matrix resin is cured to obtain a fiber-reinforced resin-impregnated body. When,
Injecting the fiber-reinforced resin molded body coating composition according to any one of claims 1 to 3 so as to have a film thickness of 20 to 600 μm between the surface of the fiber-reinforced resin impregnated body and the mold surface; ,
A step of re-clamping at a pressure of 0.5 to 7 MPa immediately after completion of injection;
Heating the mold to a temperature at which the fiber-reinforced resin molded body coating composition is cured, and curing the fiber-reinforced resin molded body coating composition;
After the fiber reinforced resin molded body coating composition is cured, at least a step of cooling the mold part surface having an injection port for injecting the fiber reinforced resin molded body coating composition;
A step of opening the mold, and taking out from the mold a fiber reinforced resin molded body obtained by curing the fiber reinforced resin molded body coating composition on the surface of the fiber reinforced resin impregnated body. Manufacturing method of a molded object.   The mold having a biting structure in which one mold part is fitted in the other mold part is used as the mold that can be divided into the at least two mold parts. The manufacturing method of the fiber reinforced resin molding as described in any one of.   Immediately before injecting the matrix resin into the cavity, the mold that can be divided into the at least two mold parts is provided with packing so that the cavity can be sealed, and means for depressurizing the cavity formed by the mold. The method for producing a fiber-reinforced resin molded article according to any one of claims 4 to 7, wherein the inside of the cavity is degassed under reduced pressure.   When injecting the fiber reinforced resin molded body coating composition between the surface of the fiber reinforced resin impregnated body and the surface of the mold, the mold clamping pressure is applied after injection without applying the mold clamping pressure. The manufacturing method of the fiber reinforced resin molding in any one of Claims 4-8.   When injecting the fiber-reinforced resin molded body coating composition between the surface of the fiber-reinforced resin impregnated body and the surface of the mold, the at least two mold parts are separated by 0.1 to 5 mm and re-clamped after the injection. The method for producing a fiber-reinforced resin molded article according to any one of claims 4 to 9, wherein: A mold comprising a mold part constituting a first cavity, a mold part constituting a second cavity, and a core mold part, wherein the mold part constituting the first cavity and the core mold part A first cavity is formed, and a second cavity larger than the first cavity is formed by a mold part that constitutes the second cavity and the core mold part, and in-mold coating is formed in the second cavity. The mold part constituting the first cavity or the core mold part is provided with an injection port for injecting a matrix resin, and the mold part constituting the second cavity includes a fiber. In a method for producing a fiber-reinforced resin molded body by an RTM molding method using a mold provided with an injection port for injecting a reinforced resin molded body coating composition,
The mold part that constitutes the first cavity, the mold part that constitutes the second cavity, and the core mold part are made of a matrix resin and the fiber-reinforced resin molded body coating composition according to any one of claims 1 to 3. Is heated in advance to a temperature at which the mold is cured, a fiber reinforcing material is disposed in the first cavity formed by the mold, the mold is clamped, and then the matrix resin is injected into the first cavity. The fiber reinforced material is impregnated, and the matrix resin is cured until the matrix resin can withstand the injection pressure and flow pressure of the fiber reinforced resin molding coating composition, and the fiber reinforced resin is impregnated. Obtaining a body;
Replacing the mold part constituting the first cavity with the mold part constituting the second cavity while leaving the fiber reinforced resin impregnated body in the core mold part;
Injecting the fiber-reinforced resin molded article coating composition so as to have a film thickness of 20 to 600 μm between the surface of the fiber-reinforced resin impregnated body and the surface of the mold part constituting the second cavity;
A step of re-clamping at a pressure of 0.5 to 7 MPa immediately after completion of injection;
Curing the fiber-reinforced resin molded article coating composition;
After the fiber-reinforced resin molded body coating composition is cured, the mold is opened, and the fiber-reinforced resin molded body is formed by curing the fiber-reinforced resin molded body coating composition on the surface of the fiber-reinforced resin impregnated body. A method for producing a fiber-reinforced resin molded product, comprising the step of:   12. The method according to claim 11, further comprising the step of cooling at least the surface of the mold part forming the second cavity after the fiber-reinforced resin molded body coating composition is cured and before the mold is opened. The manufacturing method of the fiber reinforced resin molding as described in any one of.   The method for producing a fiber-reinforced resin molded article according to any one of claims 4 to 12, wherein the matrix resin is selected from the group consisting of an epoxy resin, an unsaturated polyester resin, and a vinyl ester resin.   The said matrix resin is used in combination with an internal mold release agent, The manufacturing method of the fiber reinforced resin molding of Claim 13 characterized by the above-mentioned.   The method for producing a fiber-reinforced resin molded article according to any one of claims 4 to 14, wherein the fiber reinforcing material is at least one selected from glass fibers and carbon fibers.   A fiber-reinforced resin molded article obtained by the method for producing a fiber-reinforced resin molded article according to any one of claims 4 to 15.

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