JP2012166490A - Painted molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a painted molded article excellent in surface hardness and antifouling properties.SOLUTION: The painted molded article includes: a fiber-reinforced molding obtained by use of a fiber-reinforced molding material constituted by combining a thermosetting resin and a fibrous base material; a primer layer provided on the molding; a coating material layer provided on the primer layer; and an ultraviolet cured layer composed of an ultraviolet curable resin composition and provided on the coating material layer. The ultraviolet curable resin composition contains an oligomer of a urethane polyfunctional (meth)acrylate or a mixture of the oligomer and a monomer thereof, and a resin and/or compound containing fluorine and silicon.

Description

  The present invention relates to a coated molded body obtained by applying a hard coat to a molded body obtained by molding and curing a fiber-reinforced molding material.

  Conventionally, a molded body obtained by molding using a fiber reinforced molding material called FRP (Fiber Reinforced Plastics) has excellent mechanical strength and durability, as is well known. For example, in addition to housing-related parts such as bathtubs, water storage tanks, septic tanks, exterior / interior panels, etc., they have been widely used as vehicle-related parts, advertising boards, leisure boats, bobbins and the like.

  In order to obtain such FRP, the thermosetting resin composition is impregnated or coated (hereinafter simply referred to as “impregnation”) on a fibrous base material that is a reinforcing fiber, and is necessary. In addition to the sheet molding compound (SMC), bulk molding compound (BMC), prepreg, and premix methods that heat-press the composite material that has been semi-cured by aging treatment depending on It is used without being cut and is impregnated with a thermosetting resin, wound around a mold called a mandrel, molded to a predetermined thickness, heated and cured, and a glass mat impregnated with resin is used by human hands. There is a hand lay-up method in which layers are formed and molded by heating and cured by heating.

  Moreover, the molded object obtained by those shaping | molding methods is utilized as raw materials, such as a housing-related part and a vehicle-related part, utilizing the characteristic which the thermosetting molding material reinforced with the fiber has. In particular, when used as a vehicle-related part, the appearance is important, so that the molded product may be given a predetermined coating for the purpose of improving the design.

  By the way, when a molded body with such a coating is used as a railway vehicle interior material, when it is touched by a large number of passengers, the surface hardness is low, so there is a problem that scratches etc. are likely to occur, and dirt caused by hand. There is a problem that it is easy to get dirty due to low contamination resistance against the adhesion.

  Therefore, in order to solve such a problem, Patent Document 1 discloses a thermosetting resin molding in which an acrylic paint that can be cross-linked with an electron beam or ultraviolet rays is applied in order to improve the scratch resistance and water repellency of a molded product. A method for surface modification of articles is disclosed. However, only acrylic paints that can be cross-linked with electron beams or ultraviolet rays have a problem that it is difficult to remove stains such as oil-based ink and dust adhering to the surface.

Patent Document 2 clearly shows that a hard coat sheet having excellent antifouling properties and water repellency (oil resistance) can be obtained by blending a radiation curable silicone resin with a radiation curable resin (acrylic). Has been. However, in a blend of a radiation curable resin (acrylic) and a radiation curable silicone resin, the improvement in scratch resistance (abrasion) could not be sufficiently realized.

JP 60-90224 A JP-A-11-29720

  Here, the present invention has been made in the background of such circumstances, and the problem to be solved is to provide a coated molded article excellent in surface hardness and antifouling property. is there.

  And as a result of intensive studies to solve the above problems by the present inventors, fiber reinforced molding obtained by using a fiber reinforced molding material configured by combining a thermosetting resin and a fibrous base material In a coated molded body in which a primer layer is provided on a body, a coating layer is provided thereon, and an ultraviolet curable layer made of an ultraviolet curable resin composition is further provided thereon, urethane is used as the ultraviolet curable resin composition. By using an ultraviolet curable resin composition comprising a polyfunctional acrylate or urethane polyfunctional methacrylate oligomer or a mixture of an oligomer and a monomer and a resin and / or compound containing fluorine and silicon, surface hardness and antifouling properties are achieved. The inventors have found that an excellent coated molded body can be obtained, and have completed the present invention.

  That is, in the present invention, a primer layer and a paint layer are sequentially formed on the surface of a molded body obtained by using a fiber reinforced molding material comprising at least a thermosetting resin and a fibrous base material. On top of that, an ultraviolet curable resin composition is formed with a UV curable layer, and the UV curable resin composition is an urethane polyfunctional acrylate or urethane polyfunctional methacrylate oligomer or oligomer. The gist of the present invention is a coated molded body comprising a mixture with a monomer and a resin and / or compound containing fluorine and silicon.

  In addition, according to one of the preferable aspects of the coating molded object according to this invention, the said thermosetting resin is a thermosetting phenol resin.

  Moreover, according to another one of the preferable aspects of the coating molded object according to this invention, the said coating layer is formed using an acrylic silicone resin coating material.

  Thus, in the coated molded body according to the present invention, the ultraviolet curable resin composition comprises a urethane polyfunctional acrylate or urethane polyfunctional methacrylate oligomer or a mixture of oligomer and monomer, a resin containing fluorine and silicon, and / or Or a compound molded body having an ultraviolet-cured layer excellent in friction resistance and antifouling property, and thereby the coated molded body is, for example, a bathtub, a water tank, a septic tank, an exterior It can be advantageously used as housing-related parts such as interior panels, vehicle-related parts, advertising boards, leisure boats, bobbins and the like.

  Furthermore, in the present invention, by using a thermosetting phenol resin as the thermosetting resin, a coating molded body having excellent flame retardancy can be obtained, and in particular, vehicle-related parts and houses where flame retardancy is important. It can be advantageously used as related parts. Further, when an acrylic silicon resin paint is used as the paint, the adhesion with the ultraviolet curable resin composition can be further improved, and the paint having sufficient adhesion, antifouling property and surface hardness as a vehicle interior material. It becomes a phenol resin molding.

  Hereinafter, in accordance with the present invention, on a fiber reinforced molded article comprising a thermosetting resin and a fibrous base material, a primer layer is provided, and a paint layer is provided thereon, and further UV-cured thereon. The coated molded body having an ultraviolet curable layer made of a resin composition will be described in detail.

  First, the fiber-reinforced molded body material that gives the molded body used in the present invention is intended to include at least a thermosetting resin and a fibrous base material.

  Therefore, as the thermosetting resin, a thermosetting phenol resin or an unsaturated polyester resin is generally used, but at least one of other thermosetting resins such as an epoxy resin, a melamine resin, and a guanamine resin. It is also possible to use seeds alone, or to use these resins in combination within a quantitative range that does not impair the curability of the thermosetting phenol resin or unsaturated polyester resin. Among these, the thermosetting phenol resin is particularly suitable because it is advantageous in terms of flame retardancy. Examples of such thermosetting phenol resins include resol type phenol resins, benzyl ether type phenol resins, novolac type phenol resins, modified or modified phenol resins thereof, and mixtures thereof. Can do. Among such thermosetting phenol resins, in particular, a resol type phenol resin can be suitably employed from the viewpoint of coatability and curing characteristics.

  And, such a thermosetting resin will be used for the production of a fiber reinforced molding material as a thermosetting resin composition containing it, and as a content in such a thermosetting resin composition, In general, it is contained at a rate of 35 to 70% by mass, and preferably 40 to 60% by mass from the viewpoint of flame retardancy.

  In addition, an inorganic filler is mix | blended with this thermosetting resin composition as needed. Examples of the inorganic filler include aluminum hydroxide, calcium carbonate, talc, clay, kaolin clay, microballoon, silica sand, calcium silicate, aluminum silicate, etc., one or two of these More than one species can be blended as needed.

  Moreover, when it contains the inorganic filler as mentioned above, in the thermosetting resin composition, it is desirable to contain generally in the ratio of 30-65 mass% and 40-60 mass%.

  Further, if necessary, the thermosetting resin composition may include various kinds of conventional accelerators (thickening agents), mold release agents, silane coupling agents, and the like in addition to the inorganic filler. Additives can be formulated. Here, examples of the curing accelerator include hydroxides and oxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and magnesium oxide. Examples of the mold release agent include zinc stearate and calcium stearate. Examples of the stearic acid-based metal salt are as follows.

  And when preparing the thermosetting resin composition used for this invention like this, the method similar to the past can be employ | adopted. For example, using a known mixing device such as MTI / universal mixer manufactured by Tsukishima Kikai Co., Ltd., in addition to the thermosetting resin which is an essential component, a desired inorganic filler, and further if necessary By adding other various additives simultaneously or in any order, and stirring and mixing, the intended paste-like thermosetting resin composition is prepared. In preparing such a thermosetting resin composition, it is also possible to add a solvent such as water, alcohol, or acetone as necessary.

  The thermosetting resin composition thus obtained is advantageously used for the production of a fiber-reinforced molding material as a binder for a fibrous base material. Hereinafter, such a thermosetting resin composition and a fiber are used. The fiber-reinforced molding material according to the present invention that is configured to include a porous substrate will be specifically described. In the following, a sheet molding compound (SMC) having a sheet form will be taken up as a representative example of the fiber reinforced molding material and will be described in detail.

  First, the fiber reinforced molding material according to the present invention contains at least a paste-like thermosetting resin composition (hereinafter referred to as a paste) as described above and a fibrous base material as essential components.

  On the other hand, the fibrous base material is not particularly limited as long as it has a reinforcing function mainly composed of fibrous materials, depending on the characteristics required for the fiber reinforced molding material and the application field thereof. Thus, an arbitrary shape and material are appropriately selected and used. Examples of the shape of the fibrous base material include various fibers having shapes such as filament, roving, strand, chopped strand, paper, mat, and cloth. The material of the fibrous base material is, for example, glass fiber, carbon fiber, aramid fiber, phenol fiber, polyamide fiber, polyester fiber, alumina fiber, metal fiber, whisker, milled fiber, linter pulp, hemp fiber, Examples include wood chops. These fibrous base materials may be used independently and may use 2 or more types together. Among these, in SMC, glass fiber is preferably used from the viewpoints of cost, strength, availability, and the like.

  In addition, when using the said glass fiber as a fiber base material, it is desirable to use a silane coupling agent together, and this improves the affinity of the thermosetting resin contained in the paste and the glass fiber. As a result, the adhesiveness between the thermosetting resin and the glass fiber can be effectively improved. Examples of such silane coupling agents include aminosilanes such as N-β (aminoethyl) -γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane, and epoxy silanes such as γ-glycidoxypropyltrimethoxysilane. Are preferably used. Moreover, although this silane coupling agent will generally be used in the ratio which becomes the range of 0.01-5 mass parts with respect to 100 mass parts of glass fiber, the effect by addition of a silane coupling agent From the standpoint of the development of the product, cost, etc., it is preferably used in a proportion of 0.05 to 3.0 parts by mass, and is usually added and mixed in advance in the paste as described above. The

  And the fiber reinforced molding material according to this invention can be produced by impregnating the said fiber base material with the said paste by the method similar to the past. At this time, the mixing ratio of the fibrous base material in the fiber reinforced molding material (SMC) is particularly a ratio of 3 to 60% by mass, preferably 5 to 40% by mass, and more preferably 8 to 35% by mass. It will be made to contain in the ratio. This is because if the blending ratio is less than 3% by mass, the reinforcing effect by the fibrous base material cannot be sufficiently exerted and there is a possibility of causing insufficient strength, and conversely, exceeding 60% by mass. This is because it tends to be difficult to impregnate the fibrous base material with the paste.

  More specifically, the fiber-reinforced molding material according to the present invention can be typically produced as follows. That is, a known SMC apparatus is used, and the above-mentioned paste is applied at a predetermined thickness on one surface of a carrier film made of polyethylene, polypropylene, or the like disposed above and below. Next, the fibrous base material is spread on the paste applied to the lower carrier film, and the upper carrier film is further superimposed thereon, so that the fibrous base material is sandwiched between the upper and lower pastes. . The fiber is impregnated with the carrier film and the paste in the vertical direction at the same time that the fibrous base material is impregnated with the paste by pressurizing it by passing it between a plurality of rolls. A sheet having a three-layer structure in which a base material and a carrier film are sequentially laminated is prepared, and then semi-cured by being subjected to aging treatment (thickening treatment) as necessary, and the fiber-reinforced molding material according to the present invention As a result, the SMC is manufactured. Here, when the aging treatment is performed, the conditions can be appropriately set in consideration of the moldability of SMC. For example, the heat treatment is performed at a temperature of 50 to 70 ° C. for several hours to several days. Applied.

  Moreover, when manufacturing the target SMC molded body using the SMC according to the present invention as described above, it is possible to adopt the same method as the conventional one. For example, first, the target molded body shape is determined. Prepare a mold that can be separated into upper and lower parts, put a required amount of SMC from which the carrier film has been peeled into this mold, heat and pressurize, and then open the mold and open the desired molded body. A desired molded article can be obtained by a normal press molding method of taking out. In addition, as a pressure employ | adopted there, it can set suitably by the magnitude | size, shape, etc. of the target molded object, for example, when producing the panel for building materials as a SMC molded object, generally 1 Mpa or more, A molding pressure of 80 MPa or less and a molding temperature of 30 ° C. or higher and 240 ° C. or lower can be employed.

  Unlike the above, when obtaining the desired molded body by the hand lay-up method, the fiber reinforced molding material used for it is a thermosetting resin from the viewpoint of impregnation and strength into the fibrous base material. It is desirable that the composition does not contain an inorganic filler. As the fibrous base material, carbon fiber is preferably used from the viewpoint of strength and specific gravity. Thus, in the molded body obtained by using the fiber reinforced molding material, in other words, in the fiber reinforced molded body (FRP), first, the primer layer is formed on the surface in the same manner as in the past. It will be formed.

Here, as a primer for forming such a primer layer, a known primer such as a urethane resin, an epoxy resin, or an acrylic resin, which is a general primer, can be used, and in particular, a thermosetting resin. In consideration of adhesion to a fiber reinforced molded body using a phenol resin as an epoxy resin primer, it is preferably used. Examples of the epoxy resin primer used here include Esco and Epomarine GX manufactured by Kansai Paint Co., Ltd., Eponics manufactured by Dainippon Paint Co., Ltd., Stark E manufactured by Natco Co., Ltd. and the like.
Next, on the primer layer thus formed, a coating layer for protecting the surface of the molded body and imparting design properties is formed using a predetermined coating material in accordance with a conventional coating method. Is done.

  In addition, as a paint for forming such a paint layer, acrylic resin, urethane resin, acrylic silicon resin, silicon resin, fluororesin, or inorganic paint, which are general paints, can be used. Considering the adhesiveness with the composition and the adhesiveness with the primer, an acrylic silicone resin paint is preferably used. Examples of the acrylic silicon resin paint include Ares Silicon and Cera Silicon manufactured by Kansai Paint Co., Ltd., Arco SP manufactured by Natco Co., Ltd., and Silica Cox S manufactured by Rock Paint Co., Ltd. Further, on the coating layer, an ultraviolet curable layer is formed with a predetermined thickness from the ultraviolet curable resin composition according to the present invention.

  Here, in order to form such an ultraviolet curable layer, the ultraviolet curable resin composition contains an oligomer of urethane polyfunctional acrylate or urethane polyfunctional methacrylate or a mixture of oligomer and monomer as a main component, As an antifouling agent component, a resin and / or compound containing fluorine and silicon is contained. And, when the film thickness of the ultraviolet curable layer (coating film) formed with such an ultraviolet curable resin composition is less than 1 μm, desirable friction resistance is not exhibited, and when it exceeds 10 μm, cracks occur. Therefore, the thickness is preferably 1 μm or more and 10 μm or less, and more preferably 2 μm or more and 8 μm or less. Further, such an ultraviolet curable layer preferably has a water contact angle of 90 ° or more, and more preferably 95 ° or more, from the viewpoint of stain resistance.

Here, as the urethane polyfunctional acrylate or urethane polyfunctional methacrylate oligomer or oligomer and monomer mixture contained in the UV curable resin composition, the polyfunctional acrylate and methacrylate having a urethane bond in the skeleton are mainly used. The acrylates and methacrylates can be monomers or prepolymers. Other polyfunctional acrylates or methacrylates or resins having an unsaturated group with a low functional group number may be used in combination. Examples of the isocyanate constituting urethane include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, 1,3-xylylene diisocyanate, 1, Examples include 4-xylylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-hexaethylene diisocyanate, 4-diphenylpropane diisocyanate, norbornane diisocyanate, lysine diisocyanate, and isophorone diisocyanate. Examples of polyols include ethylene glycol, diethylene glycol, Ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, Examples include butylene glycol, neopentyl glycol, polyether polyol, polyester polyol, and polycaprolactone polyol. As the isocyanate, 1,4-hexaethylene diisocyanate is preferable, and as the polyol, neopentyl glycol is preferable. Urethane polyfunctional acrylate or urethane polyfunctional methacrylate oligomer or a mixture of oligomer and monomer preferably has a molecular weight of 1000 to 50000, and if it is less than 1000, the cured coating tends to become brittle, such as cracks. There is a problem that problems are likely to occur, and those having a value larger than 50000 tend to have difficulty in achieving the desired hardness. Further, the viscosity at 60 ° C. is preferably 500 to 10,000 mPa · s. When the viscosity is less than 500 and more than 10,000, it is difficult to control the film thickness.
Further, the content of urethane polyfunctional acrylate or urethane polyfunctional methacrylate oligomer or mixture of oligomer and monomer in the ultraviolet curable resin composition is preferably 5 to 90% by mass with respect to the mass of the ultraviolet curable resin composition, 20-70 mass% is more preferable. In addition, when the content is less than 5% by mass, the adhesion tends to decrease. When the content is higher than 90% by mass, the surface hardness of the ultraviolet curable resin composition is hardly expressed.

  In addition, in the resin and / or compound containing fluorine and silicon contained in the ultraviolet curable resin composition together with the urethane polyfunctional acrylate or the oligomer of the urethane polyfunctional methacrylate as described above or a mixture of the oligomer and the monomer, ultraviolet irradiation is performed. Examples of such groups include radical polymerizable double bonds such as acrylic groups and cationic polymerizable groups such as epoxy groups. Examples of the resin and / or compound containing fluorine and silicon include a reaction product of perfluoropolyether and a silicon compound and a fluorine-siloxane graft polymer. From the viewpoint of cost and productivity, a reaction product of perfluoropolyether and a silicon compound is preferable.

  The content of the resin and / or compound containing fluorine and silicon contained in the ultraviolet curable resin composition described above is good with respect to the mass of the ultraviolet curable resin composition when the content is less than 1% by mass. Contamination is not expressed, and if the content exceeds 20% by mass, there is no change in the antifouling performance compared to the content of 10-15% by mass, which may cause adverse effects on the appearance, In order to impair productivity, the proper content is preferably 1 to 20% by mass, more preferably 5 to 15% by mass, based on the mass of the ultraviolet curable resin.

  Further, the ultraviolet curable resin composition used in the present invention may include other acrylates such as 1,4-butanediol acrylate, 1,6-hexanediol diacrylate, polyethylene glycol diacrylate, neodymium hydroxypivalate as required. Pentyl glycol diacrylate, neopentyl glycol diacrylate, dicyclopentanyl diacrylate, ethylene oxide modified phosphate diacrylate, allylated cyclohexyl diacrylate, trimethylol propane triacrylate, dipentaerythritol triacrylate, propionic acid modified dipentaerythritol tri Acrylate, caprolactone acid modified dicyclopentanyl diacrylate, pentaerythritol triacrylate, propylene oxide modified Methylolpropane triacrylate, dipentaerythritol pentaacrylate, propionic acid modified dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, other methacrylates such as ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, neopentyl glycol dimethacrylate, glycerin dimethacrylate, dimethylol tricyclo Decanedimethacrylate, trimethylolpropane trimethacrylate, Toxylated trimethylolpropane trimethacrylate, urethane, silicon, fluorine, oxetane, styrene, melamine, and other resins and barium hydroxide, magnesium hydroxide, aluminum hydroxide, silicon oxide, titanium oxide, calcium sulfate , Barium sulfate, calcium carbonate, basic zinc carbonate, basic carbonate, silica sand, clay, talc, silica compounds, inorganic fillers such as titanium dioxide, coupling agents such as silanes and titanates, disinfectants, preservatives , Plasticizers, flow regulators, antistatic agents, thickeners, pH regulators, surfactants, leveling regulators, antioxidants, antifoaming agents, UV absorbers, colored pigments, antirust pigments, etc. May be added.

  Furthermore, the curable resin composition of the present invention is not limited to the ultraviolet curable resin composition described above, but is a thermosetting resin such as an epoxy resin, a melamine resin, a polyurethane resin, a silicon resin, or a fluorine resin. The composition can be used in combination, and is not particularly limited.

  And there is no restriction | limiting in particular regarding the method of apply | coating with respect to the fiber reinforced molded object in order to form the ultraviolet curing layer according to this invention in order to form the ultraviolet curing resin composition mentioned above, spray coating, dipping, roll coating, gravure Known coating methods such as coat, air knife coat, air doctor coat, blade coat, spin coat, die coat, reverse coat, and bar coater can be used. By using and curing, the target cured layer can be formed.

  The details of the hard coat (hard coating film) in the present invention will be described by the following examples, but the present invention is not limited to the following examples. In addition, the evaluation method of the adhesiveness, antifouling property (adhesion property, wiping off property, durability), and surface hardness which were obtained by the present Example and the comparative example is as follows.

(1) Adhesion According to the adhesion (cross cut method) of JIS K5600-5-6 (1999 version), 100 1 mm grids (10 × 10) are made on the coating surface of the test substrate, and After cellophane tape (made by Nichiban) is completely attached on the grid, the tape is peeled off immediately by keeping the tape at one end of the tape at an angle of about 60 °. I checked the number of grids left without.

(2) Antifouling (A) Adhesion Draw a line with an oil-based magic marker (Zebra's Himacky (black) thick), and check whether the coating surface repels magic ink. Evaluated.
○ = The drawn line was repelled.
X = The drawn line was not repelled.
(I) Wipeability Draw a line with an oil-based magic marker (Zebra's Himacky (black) thick), and after 1 minute, wipe it back and forth with cotton (KURAFLEX, Kuraray Laflex), and use the following criteria. Evaluated.
○ = It was wiped off.
X = It was not wiped off.
(C) Durability Evaluation of the wiping property was repeatedly performed at the same location, and the following criteria were evaluated until wiping could not be performed.
◎ = Wipe off 3 times or more.
○ = 1 to 2 times.
X = Wipe could not be removed.

(3) Surface hardness In the Taber abrasion test, the test point was worn by wear wheel CS10F, 1 kg load, 100 rotations, and the difference in glossiness before and after the abrasion was measured using the specular gloss meter described in JIS K5600-4-7. And evaluated according to the following criteria. In this evaluation, the smaller the amount of change, the higher the hardness.
◎ = Change 0 to less than 20% ○ = Change 20 to less than 40% × = Change 40% or more

Example 1
First, 40 parts by mass of a resol-type phenolic resin (trade name: AKP-012, manufactured by Asahi Organic Materials Co., Ltd.), 35 parts by mass of kaolin clay having a densely packed bulk density of 0.81 g / cm, and curing acceleration 0.6 parts by weight of calcium hydroxide as a thickener (thickening agent), 1 part by weight of zinc stearate as a release agent, and 0 of 3-glycidoxypropyltrimethoxysilane as a silane coupling agent 1 part by mass was stirred and mixed with a hand mixer for 10 minutes to prepare a paste for SMC as a thermosetting resin composition.

  Next, using the SMC manufacturing apparatus, the SMC paste obtained above was applied to a polypropylene carrier film having a thickness of 40 μm, and the roving was cut into a length of about 2.54 cm (about 1 inch). The glass fiber is spread, and the carrier film coated with the paste is overlapped, so that the glass fiber is sandwiched between the pastes to form a sheet with a three-layer structure, and a plurality of rollers provided above and below. In between, the glass fiber was impregnated with the paste and the thickness of the sheet was adjusted. At this time, the glass fiber was used at a ratio of 25 parts by mass with respect to about 75 parts by mass of the paste. Thereafter, the obtained sheet was subjected to aging treatment at a temperature of 50 ° C. for 70 hours to obtain SMC having an average thickness of about 2 mm.

  Then, about 220 g of the obtained SMC was cut out, and this was cut into a cavity of a molding die with a chrome plating surface finish mounted on a pressure press machine preheated to 150 ° C. (length: 270 mm, width: 210 mm, depth) Then, the mold was immediately set and subjected to heat and pressure molding at a molding pressure of 5.88 MPa for 5 minutes to produce a fiber reinforced molded body having a thickness of 2.2 mm.

  Furthermore, on the fiber reinforced molded body thus obtained, an epoxy resin (manufactured by Kansai Paint Co., Ltd., product name Esco, solid content 71%) is used as a primer layer forming material, and a diluent (manufactured by Kansai Paint Co., Ltd., product name). After diluting to a solid content of 40% using Tect EP thinner, paint with spray coating to give a film thickness of 15-30 μm (Dry) and leave at 30 ° C. for 2 hours. To form a primer layer. After that, after using acrylic silicon resin (product name: Ares Silicone, manufactured by Kansai Paint Co., Ltd.) as a paint, it is diluted to a concentration of 35% with a diluent (product name: Ares Silicone Thinner, product of Kansai Paint Co., Ltd.) Then, coating was performed by spray coating so that a film thickness (Dry) of 40 to 60 μm was obtained, and thereafter, heating was performed in a circulating dryer at 80 ° C. for 90 minutes to form a hard coating film serving as a coating layer.

Thereafter, an ultraviolet curable layer was formed on the hard film as follows. That is, 100 parts by mass of UV-7600B (manufactured by Nippon Synthetic Industry Co., Ltd., solid content: 100%) which is an oligomer of urethane polyfunctional acrylate, and fluorine-siloxane graft polymer (Kanto Denka Kogyo Co., Ltd.) which is a resin containing fluorine and silicon. 5 parts by weight of a product manufactured by Co., Ltd., trade name F Clear KD3500UV, solid content 20%), and a hydroxyalkylphenone photopolymerization initiator (trade name, Irgacure-184, manufactured by Ciba Geigy Co.) as a polymerization initiator. Use it at a ratio of 3% by mass with respect to the total amount (105 parts by mass), add it to a mixed solvent of methyl ethyl ketone, propylene glycol monomethyl ether and isopropyl alcohol as a diluent solvent, and stir and mix uniformly. To obtain an ultraviolet curable resin composition having a solid content of 30% After coating with a bar coater, this was heated in a circulating dryer at 60 ° C. for 10 minutes, and the coated surface was irradiated with ultraviolet rays using a high-pressure mercury lamp so that the integrated light amount was 500 mJ / cm ^2. Then, a hard cured film (ultraviolet cured layer) having a film thickness of 4 μm was formed.

-Example 2-
A hard cured coating was formed on the fiber-reinforced molded body in the same manner as in Example 1 except that the blending amount of the fluorine-siloxane graft polymer described in Example 1 was changed from 5% by mass to 10% by mass. Formed.

Example 3
Except that the acrylic silicone resin described in Example 1 was changed to an acrylic urethane resin (trade name Hilock DX, manufactured by Rock Paint Co., Ltd.), coating was performed on the fiber-reinforced molded body in the same manner as in Example 1. gave.

Example 4
The fluorine-siloxane graft polymer described in Example 1 was changed to a reaction product of a perfluoropolyether having a group that is polymerized by ultraviolet irradiation and a silicon compound (trade name: OPTOOL DAC-HP, manufactured by Daikin Industries, Ltd.). Except for this, a hard film was formed on the fiber-reinforced molded body in the same manner as in Example 1.

-Comparative Example 1-
When preparing the ultraviolet curable resin composition described in Example 1, Example 1 was used except that polyester acrylate (trade name Aronix M-8030, manufactured by Toa Gosei Co., Ltd.) was used instead of UV-7600B. Similarly, a hard cured film was formed on the fiber-reinforced molded body.

-Comparative Example 2-
When preparing the ultraviolet curable resin composition described in Example 1, Example 1 was used except that epoxy acrylate (manufactured by Showa Denko Co., Ltd., trade name Lipoxy SP-1509) was used instead of UV-7600B. Similarly, a hard cured film was formed on the fiber-reinforced molded body.

-Comparative Example 3-
When preparing the ultraviolet curable resin composition described in Example 1, the same procedure as in Example 1 was used except that a siloxane graft polymer (trade name Reseda GS-1015 manufactured by Toa Gosei Co., Ltd.) was used as an antifouling agent. Thus, a hard cured film was formed on the fiber-reinforced molded body.

-Comparative Example 4-
When preparing the ultraviolet curable resin composition described in Example 4, the same procedure as in Example 1 was used except that alkyl fluoroacrylate (trade name Biscoat 17F, manufactured by Osaka Organic Chemical Co., Ltd.) was used as an antifouling agent. A hard cured film was formed on the fiber-reinforced molded body.

-Comparative Example 5-
When preparing the ultraviolet curable resin composition described in Example 1, the antifouling agent was changed to no addition, and the addition amount of the initiator associated therewith was adjusted. A hard cured film was formed on the reinforced molded body.

  Tables 1 and 2 show the evaluation results of the physical properties of the cured films formed in the above Examples and Comparative Examples.

As is clear from the results of Tables 1 and 2, in the comparison between Example 1 and Comparative Examples 1 and 2, the ultraviolet curable resin composition composed of urethane acrylate had high surface hardness and High adhesion. Further, from the comparison between Example 1 and Comparative Examples 3 and 4, the ultraviolet curable resin composition containing a resin containing fluorine and silicon has a sufficiently high antifouling durability and further has a surface hardness. It has improved. Moreover, it turns out that what used especially the resin containing a fluorine and a silicon | silicone as an ultraviolet curable resin composition can acquire high adhesiveness with respect to an acrylic silicone resin coating material.

Claims (3)

A primer layer and a paint layer are sequentially formed on the surface of a molded body obtained by using a fiber reinforced molding material composed of at least a thermosetting resin and a fibrous base material, and further UV-cured thereon. It is a coating molded body in which an ultraviolet curable layer is formed with a functional resin composition,
The ultraviolet curable resin composition comprises urethane polyfunctional acrylate or urethane polyfunctional methacrylate oligomer or a mixture of oligomer and monomer, and a resin and / or compound containing fluorine and silicon. body.   The said thermosetting resin is a thermosetting phenol resin, The coating molded object of Claim 1 characterized by the above-mentioned. The paint molded body according to claim 1, wherein the paint layer is formed using an acrylic silicon paint.