JP4274538B2 - In-mold coated transparent molded body - Google Patents

Description

  The present invention relates to an in-mold coated transparent molded body, and more specifically, a thermoplastic transparent resin material is molded in a mold by an injection molding method, an injection compression molding method, an injection press molding method, or the like. An in-mold coating composition is injected between the surface of the obtained molded body and the mold cavity surface, and the in-mold coating composition is cured in the mold to cover the surface of the resin molded body in the mold. The present invention relates to an in-mold coated transparent molded body obtained by a so-called in-mold coating molding method (in-mold coating method or IMC method) for producing an integrally molded product in which the composition is in close contact.

  For the purpose of improving the scratch resistance (abrasion resistance) of the surface of transparent resin moldings used in automobiles, home appliances, building materials, etc., or improving the weather resistance and extending the product life. It has been widely practiced to paint the surface. As such a coating film forming method, a method of curing the coating film by irradiating energy rays such as ultraviolet rays after spray coating is used. As such a coating composition, for example, a photopolymerizable polyfunctional urethane compound (for example, see Patent Document 1) or a crosslinked polymerizable compound having a (meth) acryloyloxy group is applied to a polycarbonate molded body. And ultraviolet curing (for example, see Patent Document 2), and those using urethane acrylate oligomers (for example, see Patent Documents 3 and 4). However, in recent years, there has been a strong interest in environmental issues, and the release of harmful organic substances from paint factories to the atmosphere tends to be severely restricted. Problems such as adhesion and pinholes have occurred, and there is an urgent need to develop technologies that can replace these methods.

  In such a situation, after injecting the paint between the surface of the resin molded body molded in the mold and the cavity surface of the mold, the paint is cured in the mold and the coating film is formed on the surface of the resin molded body. An in-mold coating forming method for producing an intimate integrated molded body is attracting attention.

  In-mold coating molding method (IMC method) forms a film (coating film) in the mold, so that the coating composition is solvent-free and becomes a 100% film, so the burden on the environment is small. Since the formation of the film is also cured by a radical reaction, it is an excellent coating method with less energy consumption for forming the film compared to the reaction by heat or ultraviolet irradiation.

  The coating material used for in-mold coating of thermoplastic resin has a coating appearance, transparency, adhesion, and scratch resistance because it is required to have a property of curing at a lower temperature than a coating for thermosetting resin. In general, it is difficult to develop paints that have good properties, and those already developed as paints used in in-mold coating molding methods are for thermosetting molding resins and some thermoplastics such as ABS resins and nylons. It is limited to the enamel paint for resin (for example, refer patent documents 5-8).

Polycarbonate resins are used in automotive headlamps and synthetic resin lenses because they are excellent in transparency and impact resistance. However, the surface of the polycarbonate resin is easily damaged, and it has been proposed to apply various hard coat paints.
JP 58-101121 A JP-A-1-308416 JP 7-247383 A Japanese Patent Laid-Open No. 11-343460 JP-A-60-212467 JP 60-47011 A JP-A-8-258080 Japanese Patent Laid-Open No. 11-240042

  Therefore, the object of the present invention is to have excellent adhesion to thermoplastic transparent resin base materials such as polycarbonate resin, and to cover with a film excellent in high transparency, weather resistance, durability, scratch resistance, etc. Another object of the present invention is to provide a molded thermoplastic transparent resin product.

  As a result of intensive studies to solve the above problems, the inventors of the present invention are able to copolymerize a specific urethane oligomer and the oligomer in a thermoplastic transparent resin molded body produced by an in-mold coating molding method. By using an in-mold coating composition obtained by blending a specific proportion of an organic peroxide polymerization initiator into a vehicle component composed of a specific ethylenically unsaturated monomer, the problem can be solved. As a result, the present invention has been completed.

That is, according to the present invention, in an injection molding method, an injection compression molding method or an injection press molding method, a step of clamping a mold composed of a fixed mold portion and a movable mold portion, and injection of a thermoplastic transparent resin into the cavity Molding, cooling the thermoplastic transparent resin, reducing the clamping force or slightly opening the mold, injecting the in-mold coating composition into the cavity, and clamping again A step of curing the injected in-mold coating composition; and an in-mold coating transparent molded body produced by removing the molded body from the mold after the in-mold coating composition is cured. (A) urethane oligomer having 2 to 8 (meth) acryloyl groups in at least one molecule,
(B) at least one monomer having two ethylenic double bonds in one molecule;
(C) at least one monomer having three or more ethylenic double bonds in one molecule;
(D) comprising an organic peroxide polymerization initiator,
The mass ratio of the urethane oligomer (a) to the monomer (b) and the monomer (c)
(A) / {(b) + (c)} = 10/90 to 70/30,
The mass ratio of the monomer (b) and the monomer (c) is
(B) / (c) = 5/95 to 95/5,
The mass ratio of the organic peroxide polymerization initiator (d) is
(D) / {(a) + (b) + (c)} = 0.1 / 100 to 5/100 An in-mold coated transparent molded product is provided.

  According to the present invention, there is provided an in-mold coated transparent molded body which is integrated as a film having good adhesion by curing a coating composition in a mold on the surface of a molded body of a thermoplastic transparent resin. Can do.

  The in-mold coated transparent molded body of the present invention can be used for transparent resin parts for automobiles such as headlamp covers and sunroofs, resin lenses, and home appliance parts.

  Hereinafter, embodiments of the present invention will be specifically described.

  The thermoplastic transparent resin molded article according to the present invention comprises a molded article made of a thermoplastic transparent resin composition and a coating of an in-mold coating composition formed on the surface thereof.

  As the thermoplastic transparent resin, thermoplastic transparent resins used for various conventionally known molding materials can be used. For example, polycarbonate resin, polystyrene resin, polyethylene terephthalate resin, polymethyl methacrylate resin, polychlorinated resin. A vinyl resin, a polyethylene resin, a polypropylene resin, etc. are mentioned.

  Such a thermoplastic transparent resin molding material contains, for example, an ultraviolet absorber, an antioxidant, a release agent, an antistatic agent, a flame retardant, a plasticizer, and the like so as to satisfy characteristics according to the application. Can do.

  Next, the in-mold coating composition used in the present invention will be described.

  The in-mold coating composition used in the present invention comprises (a) a urethane oligomer having 2 to 8 (meth) acryloyl groups in at least one molecule, and (b) two ethylenic diesters in one molecule. At least one monomer having a heavy bond, (c) at least one monomer having three or more ethylenic double bonds in one molecule, and (d) an organic peroxide polymerization initiator are essential components, Furthermore, optional components such as oligomers such as polyester (meth) acrylate oligomers and silicon (meth) acrylate oligomers, mold release agents, antioxidants, ultraviolet absorbers, curing accelerators, polymerization inhibitors, and antifoaming agents, as necessary. Is included.

  As the urethane oligomer having 2 to 8 (meth) acryloyl groups in at least one molecule of (a) used in the present invention, specifically, the weight average molecular weight (Mw) of the oligomer is Although it may vary depending on the type, it is generally 500 to 50,000, preferably 1,000 to 30,000.

  The urethane oligomer used in the present invention includes, for example, a molar ratio NCO / OH of a functional group containing (i) an organic diisocyanate compound, (ii) an organic polyol compound, and (iii) a hydroxyalkyl (meth) acrylate. However, it can be produced by a usual method by mixing at an abundance ratio of 0.8 to 1.0, preferably 0.9 to 1.0.

  Specifically, (i) an organic diisocyanate compound and (ii) an organic polyol compound are reacted in the presence of a urethanization catalyst such as dibutyltin dilaurate to obtain an isocyanate-terminated polyurethane prepolymer. Next, the urethane oligomer can be produced by reacting (iii) hydroxyalkyl (meth) acrylate until most of the free isocyanate groups have reacted.

  The ratio of (ii) the organic polyol compound and (iii) hydroxyalkyl (meth) acrylate is, for example, about 0.2 to 0.5 mol for the former with respect to 1 mol of the latter.

  Examples of (i) 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, or the like can be used. These organic diisocyanate compounds can be used alone or as a mixture of two or more thereof.

  The organic polyol compound (ii) used in the above reaction is preferably an organic diol compound, and examples thereof include alkyl diols, polyether diols, and polyester diols.

  Examples of the alkyl diol include ethylene glycol, 1,3-propanediol, propylene glycol, 2,3-butanediol, 1,4-butanediol, 2-ethylbutane-1,4-diol, and 1,5-pentanediol. 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,4-cyclohexanediol, 1,4-dimethylolcyclohexane and 2,2-bis ( 4-Hydroxycyclohexyl) propane and the like can be mentioned as typical examples.

  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.

  Polyester diols as organic diol compounds include, for example, esterification reaction products obtained by reacting saturated or unsaturated dicarboxylic acids and / or their anhydrides with excess alkyl diols, and hydroxy diols with alkyl diols. An esterification reaction product obtained by polymerizing a lactone which is a carboxylic acid and / or an intramolecular ester thereof and / or a lactide which is an intermolecular ester can be used.

  The above (ii) organic polyol compounds may be used alone or in combination of two or more thereof.

  As the above (iii) hydroxyalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol Examples thereof include tri (meth) acrylate and 2-hydroxy-3-acryloyloxypropyl (meth) acrylate.

  In addition, the urethane oligomer used in the present invention has a molar ratio NCO / OH of a functional group containing a compound having 2 to 4 (meth) acrylate groups and a hydroxyl group in one molecule and an organic diisocyanate. It can also be produced by reacting at a ratio of 0.9 to 1.0 in the presence of a urethanization catalyst such as dibutyltin dilaurate.

  The component (b) used in the present invention is a monomer having two ethylenic double bonds in one molecule that can be copolymerized with the above (a) urethane oligomer.

  Examples of such a monomer (b) having two ethylenic double bonds in one molecule include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonane Representative examples include diol di (meth) acrylate, glycerin di (meth) acrylate, neopentyl glycol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, and the like.

  The component (b) may be used alone or as a mixture of two or more thereof.

  The component (c) used in the present invention is a monomer having three or more ethylenic double bonds in one molecule that can be copolymerized with the above (a) urethane oligomer.

  Examples of the monomer (c) having three or more ethylenic double bonds in one molecule include, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth). Representative examples include acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, and the like. The component (c) may be used alone or as a mixture of two or more thereof.

  The mass ratio of the urethane oligomer (a) to the monomer (b) and the monomer (c) depends on the type of the compound used as the component (a) and the components (b) and (c). (A) / {(b) + (c)} = 10/90 to 70/30, preferably 20/80 to 60/40, and the mass ratio of the monomer (b) to the monomer (c) is (B) / (c) = 5/95 to 95/5, preferably 10/90 to 90/10.

  If the mass proportion of each component is within this range, it has an appropriate viscosity characteristic and excellent adhesion to a thermoplastic base material, and also has high transparency, weather resistance, durability, scratch resistance, etc. An in-mold coated molded body having a coating performance is obtained.

  In particular, {(b) + (c)}, which is the total amount of monomer components, is suitably used in an amount of 43 to 900 parts by weight, preferably 67 to 400 parts by weight, per 100 parts by weight of component (a). is there. If the amount of the {(b) + (c)} component is 43 parts by mass or more with respect to 100 parts by mass of the component (a), the viscosity of the coating composition becomes too high, and the fluidity in the mold. Is preferable because a uniform coating can be obtained without inferiority.

  On the other hand, if the amount of {(b) + (c)} component is 900 parts by mass or less with respect to 100 parts by mass of component (a), the viscosity of the coating composition becomes too low, or the flow in the mold This is preferable because a uniform coating can be obtained without air bubbles being taken into the coating composition.

  The component (c) is used in an amount of 5.3 to 1,900 parts by weight, preferably 11 to 900 parts by weight, based on 100 parts by weight of the component (b). If the amount of the component (c) is 5.3 parts by mass or more, it has excellent adhesion to the thermoplastic base material, and if it is 1,900 parts by mass or less, the cured coating film has cracks and the like. This is preferable because a robust cured coating film can be obtained without causing the above problems.

  In the in-mold coating composition used in the present invention, a monomer having one ethylenic double bond in one molecule can be used. However, if it is added in a large amount, the scratch resistance of the coating is inferior. If available, it can be used.

  The component (d) organic peroxide polymerization initiator used in the present invention is a compound that generates free radicals. That is, the coating composition covers the surface of the molded body in the mold, and the organic peroxide polymerization initiator is thermally decomposed by the heat of the mold surface or the molded body to generate radicals, which are contained in the coating composition. Suitably, the radical polymerization reaction of the heavy bond is initiated to cure the coating composition.

  Examples of such organic peroxide polymerization initiators include bis (4-t-butylcyclohexyl) peroxydicarbonate, t-amylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, Milperoxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-octyl peroxy octoate, t-amyl peroxy octoate, t-butyl peroxy octoate, t-octyl peroxy benzoate 1,1-di-t-butylperoxycyclohexane, t-butylperoxy-3,5,5-trimethylhexanoate, 2,2-di-t-butylperoxybutane, t-butylperoxyisopropyl Carbonate and t-amyl peroxybe Zoeto can be preferably used.

  The blending amount of the organic peroxide polymerization initiator (d) used in the present invention is such that the mass ratio of each component is (d) / {(a) + (b) + (c)} = 0.1 / 100. It is appropriate that it is ˜5 / 100, preferably 0.2 / 100 to 4/100. It takes a long time if the blending amount of the organic peroxide polymerization initiator (d) is 0.1 parts by mass or more with respect to 100 parts by mass of the {(a) + (b) + (c)} component. This is practical because a sufficient curing reaction can be performed in a short time. On the other hand, when the blending amount of the organic peroxide polymerization initiator (d) is 5 parts by mass or less, it is possible to achieve good adhesion with the molded body without initiating a rapid reaction in the mold. .

  At least one of the monomer (b) and / or monomer (c) used in the present invention swells or dissolves the thermoplastic transparent resin, whereby the interface between the in-mold coating composition and the thermoplastic transparent resin. Is particularly preferable since a fusion layer of both components is formed and both components exhibit strong adhesion.

  The in-mold coating composition used in the present invention may be blended with an oligomer such as a polyester (meth) acrylate oligomer or a silicon (meth) acrylate oligomer, or a release agent, if necessary.

  The polyester (meth) acrylate oligomer can be produced, for example, by a reaction between a polyester polyol having a hydroxyl group at the terminal and an unsaturated carboxylic acid.

  The silicon (meth) acrylate oligomer is produced, for example, by an ester reaction between a hydroxyl group of an alcoholic siloxane compound and (meth) acrylic acid. The in-mold coating composition using the silicon (meth) acrylate oligomer is particularly excellent in light stability or weather resistance, and is effective when the in-mold coated transparent molded body is used outdoors for a long period of time.

  In the present invention, in order to smoothly release the coating film obtained by curing the in-mold coating composition in the mold from the mold, a release agent can be optionally used in combination. For example, a release agent having a melting point of 125 ° C. or lower is particularly suitable. If the melting point of the release agent is, for example, 125 ° C. or less, a desired release effect can be sufficiently obtained. This is because, even if the temperature of the mold is about 40 to 110 ° C., considering that the molten thermoplastic resin having a high temperature of 200 to 240 ° C. is cooled and solidified in the mold, the in-mold coating composition This is because it is considered that the surface temperature of the molded body at the time when is injected is sufficiently higher than the melting point of 125 ° C. of the release agent. Examples of such release agents include stearic acid, stearates such as zinc stearate, aluminum stearate, magnesium stearate, calcium stearate, soybean oil lecithin, silicone oil, fatty acid ester, and fatty acid alcohol dibasic acid. Mention may be made of esters.

  If the compounding quantity of a mold release agent is 0.1-5 mass parts with respect to a total of 100 mass parts of said (a), (b) and (c) component, a mold release effect will be exhibited suitably. The

  If necessary, the in-mold coating composition used in the present invention may contain various additives such as an antioxidant, an ultraviolet absorber, a curing accelerator, a polymerization inhibitor, an antifoaming agent, and a slip agent. May be.

  The viscosity of the in-mold coating composition to be injected into the cavity is preferably in the range of 70 to 10,000 mPa · s at 20 ° C.

  If the viscosity of the in-mold coating composition is 70 mPa · s or more at 20 ° C., when the in-mold coating composition flows in the cavity, air entrainment is suppressed and leakage from the mold is prevented, and the mold is uniform. Fluidity is obtained. Moreover, when the viscosity is 10,000 mPa · s or less, excessive high-pressure injection is not required when injecting the in-mold coating composition into the cavity, which is preferable.

  Further, the relationship between the maximum flow distance x (cm) in the cavity of the coating composition in the mold and the gelation time y (sec) at the temperature in the mold cavity satisfies the following formula (1). Is preferred.

0.1x + 10 ≧ y ≧ 0.02x + 0.5 (1)
Note that 0.1 and 0.02, which are constant terms of the maximum flow distance x in the equation (1), have units of [sec / cm].

  When the gelation time y (sec) is 0.1x + 10 or less, the mold coating composition is excellent in productivity without requiring a long time for curing in the cavity, and y is 0.02x + 0.5 or more. If so, even a large resin molded body having a long flow distance can be applied without gelation in the middle of the flow, and the adhesion to the thermoplastic transparent resin is also excellent. It is preferable. Here, the gelation time y is defined as the time required for the in-mold coating composition to stop flowing, and the gelation time referred to here is an ICAM-1000 deelectrometer (Micromet Instruments, Inc.). It is the gel inflation time (sec) measured by (manufactured).

  The thermoplastic transparent resin is preferably a polycarbonate resin.

  Furthermore, when the refractive index of the thermoplastic transparent resin is n, the refractive index of the in-mold coating composition is preferably in the range of 0.9n to 1.1n. If the refractive index of the in-mold coating composition is within this range, a product having excellent transparency of the in-mold coating can be obtained.

  The injection molding method described in the present invention is a so-called general injection molding method in which a mold is not opened by a filling pressure of a thermoplastic transparent resin at the time of injection filling.

  The injection compression molding method means a molding method in which the space between the fixed mold and the movable mold is slightly expanded by the filling pressure of the resin at the time of injection filling of the resin. The molding method means a molding method in which the space between the fixed mold and the movable mold is slightly widened at the start of injection filling of the resin.

  The molding method for producing the in-mold coated transparent molded body of the present invention is preferably an injection molding method, an injection compression molding method or an injection press molding method, but is not limited to these methods.

  Hereinafter, the manufacturing method of the in-mold coated transparent molded body of the present invention will be described with reference to FIG.

  FIG. 1 is an explanatory diagram showing the overall configuration of an in-mold coating molding apparatus (hereinafter referred to as “IMC apparatus”) used in the production of an in-mold coating transparent molded body according to the present invention.

  The IMC device 100 uses a toggle type injection molding machine, and roughly comprises a mold clamping device 10, an injection device 20, a control device 30, and a mold device 50.

  The mold clamping device 10 includes a fixed platen 11 and a movable platen 12 to which the mold device 50 is attached, guided by a tie rod 14, and a hydraulic cylinder for mold clamping drive (hereinafter referred to as "clamping cylinder"). The mold plate 50 is configured to open and close when the movable plate 12 moved forward and backward by 13 moves forward and backward with respect to the fixed plate 11.

  In order to carry out this in-mold coating molding apparatus, an injection molding machine having a toggle type clamping mechanism is effective as described in JP-A-2001-38783. The reason is that when the movable mold 52 and the fixed mold 51 are opened widely, a large stroke amount can be obtained while the mold clamping cylinder 13 is driven at a relatively low hydraulic pressure. Because of the toggle boost characteristic that the mold moves slightly even with a large stroke of the clamping cylinder, the mold can be operated quickly and the mold can be opened delicately with high precision. This is because both are compatible.

  In the toggle type mold clamping mechanism, the actuator for opening and closing the mold and the actuator for generating the mold clamping force are the same mold clamping cylinder 13, so that the transition from the mold open state to the predetermined mold clamping state can be performed quickly. This quick operation is effective for re-clamping after in-mold coating composition is injected.

  The injection device 20 is provided with a screw 21 having a spiral flight, which is rotationally driven by a hydraulic motor 23 along the inner peripheral surface of a cylindrical barrel 22 and can freely move forward and backward. Yes. As the screw 21 rotates, the resin pellets supplied into the hopper 25 are sent to the front of the screw 21 and are heated by the heater attached to the outer peripheral surface of the barrel 22 during this time. The resin pellets are melted by receiving the kneading operation.

  When the amount of molten resin sent to the front of the screw 21 reaches a preset amount, the rotary motion of the hydraulic motor 23 is stopped and the injection cylinder 24 is driven to advance the screw 21. The molten resin stored in front of the screw 21 is injected into the mold cavity 53 of the mold apparatus 50 via the nozzle 26.

  The mold apparatus 50 includes a fixed mold 51 attached to the fixed platen 11 and a movable mold 52 attached to the movable platen 12. The movable mold 52 contains a coating composition in the mold cavity 53. A coating composition injection machine 55 for injection is provided.

  Next, the configuration of the control device 30 will be described. As shown in FIG. 1, the control device 30 links the operation of the mold clamping device 10 and the operation of the injection device 20 to control the overall system of the control device 30, and the injection device. And an injection control unit 38 for controlling the operation of 20. These control units 31 and 38 have the same control performance as the control unit in a normal injection molding machine.

  On the other hand, as a control unit having a control function unique to the IMC device 100, the operation of the coating composition injection machine 55 in response to a molding condition data signal (referring to a change pattern of molding conditions; the same applies hereinafter) from the mold clamping condition setting unit 32. For mold clamping while receiving the molding condition data signal transmitted from the injection machine control unit 35 for controlling the mold, the mold clamping condition setting unit 32 and the change pattern storage unit 34 described later, and feeding back the measurement signal of the stroke sensor 16 The mold clamping control unit 33 that controls the servo valve 15, the mold opening amounts of the molds 51 and 52 (hereinafter referred to as “mold opening amount”) sent from the mold clamping condition setting unit 32, and the molds 51 and 52. A change pattern storage unit 34 is provided which converts the mold clamping force (hereinafter referred to as “clamping force”) into a molding condition data signal and sends it to the mold clamping control unit 33.

  Here, in the mold clamping condition setting unit 32, each of the opening / closing speed of the mold clamping device 10, the operation timing, the mold opening amount, the mold clamping force, the injection amount of the coating composition injection machine 55, the injection speed, the injection timing, and the injection pressure. Molding conditions are set. Then, the mold clamping condition setting unit 32 transmits the molding condition data signal to the injector control unit 35 regarding the molding conditions regarding the injection amount, the injection speed, the injection timing, and the injection pressure of the coating composition injector 55, and the mold clamping is performed. The molding condition data signal is transmitted to the mold clamping control unit 33 for the molding conditions related to the opening / closing speed and the operation timing of the apparatus 10, and the molding condition data signal is transmitted to the mold clamping control unit 33 as the change pattern storage unit. 34.

  Prior to control, the change pattern storage unit 34 stores a correlation between the stroke of the clamping cylinder 13 and the mold opening amount, and a correlation between the stroke of the clamping cylinder 13 and the clamping force. . The change pattern storage unit 34 converts the molding condition data signal transmitted from the mold clamping condition setting unit 32 into a stroke of the mold clamping cylinder 13 based on the stored correlation, and the mold clamping control unit 33. Send to.

  For this reason, after the mold apparatus 50 is attached to the fixed platen 11 and the movable platen 12, the die height adjustment and mold clamping according to the mold thickness (die height) of the mold apparatus 50 are performed by the same procedure as that of normal injection molding. In the state where the force adjustment is completed, the change pattern storage unit 34 continuously receives detection signals of the stroke sensor 16, the mold opening amount sensor 17, and the mold clamping force sensor 18 while opening and closing the mold apparatus 50. Thus, the correlation between the stroke of the mold clamping cylinder 13 and the mold opening amount and the correlation between the stroke of the mold clamping cylinder 13 and the mold clamping force are calculated and stored.

  Next, the operation of the IMC device 100 when performing in-mold coating using the IMC device 100 having the control device 30 configured as described above will be described.

  First, the 1st manufacturing method of the in-mold coating transparent molded object which concerns on this invention is demonstrated using FIG.

  In accordance with a control signal transmitted from the mold clamping control unit 33 and feedback control by the mold clamping servo valve 15, the mold clamping cylinder 13 moves the movable mold according to the mold closing speed pattern set in the mold clamping condition setting unit 32. The mold 52 is moved forward from the mold opening limit position and brought into contact with the fixed mold 51. Subsequently, while performing feedback control by the control signal transmitted from the mold clamping control unit 33 and the servo valve 15 for mold clamping, the molding condition data signal (the mold clamping force of the mold clamping force) set in the mold clamping condition setting unit 32. In accordance with the change pattern), the movable mold 52 is further advanced by the mold clamping cylinder 13 to extend the tie rod 14 and apply a predetermined mold clamping force to the mold apparatus 50. At this time, the movable mold 52 and the fixed mold 51 are below the melting point (or glass transition temperature Tg) of the thermoplastic transparent resin, and after the in-mold coating composition is injected, the coating composition is in the mold. It is kept at an appropriate temperature so as to be cured. Note that the mold apparatus capable of producing the in-mold coated transparent molded body of the present invention leaks the coating composition from the split surface even when the mold is slightly opened during the coating composition injection described later. It is necessary to have a structure that does not come out. The mold apparatus 50 described here has a structure in which the coating composition does not leak from the split surface even if the mold is slightly opened by making the split surface a shear edge structure.

  When the screw 21 is advanced by the injection cylinder 24 while controlling the opening of the injection servo valve 27 by a control signal transmitted from the injection control unit at a predetermined timing during the operation of the mold clamping device 10, the screw The molten thermoplastic transparent resin stored in front of 21 is injected into the mold cavity 53 via the nozzle 26 and formed as a resin molded body. The operation timing signals are exchanged by the molding device control unit 31 so that the operation of the mold clamping device 10 and the operation of the injection device 20 are linked.

  The molten resin injected into the mold is subjected to pressure (holding pressure) for a certain period of time as in general injection molding, and a solidified and shrunk amount of resin is added and injected during that time. Then, after the pressure holding is completed, the molten resin is solidified while maintaining the clamping force.

  When the resin in the mold is solidified to some extent and the surface can withstand the injection pressure of the coating composition, the movable mold 52 is then moved backward by the mold clamping cylinder 13 and transmitted from the mold clamping control unit 33. A mold opening amount set in the mold clamping condition setting unit 32 is given by a control signal and the mold clamping servo valve 15 while feedback control is performed, and a gap is formed between the surface of the transparent resin molded body and the mold cavity 53 surface. After being provided, the coating composition is injected by a control signal transmitted from the injector control unit 35 in accordance with the injection amount, injection speed, injection timing, and injection pressure of the coating composition injector 55 set in the mold clamping condition setting unit 32. The machine 55 is driven to inject the coating composition into the mold cavity 53.

  Subsequently, while the feedback control is performed by the control signal transmitted from the mold clamping control unit 33 and the servo valve 15 for mold clamping, the movable mold 52 is advanced again by the mold clamping cylinder 13 and is set in the mold clamping condition setting unit 32. The mold clamping force is generated according to the molding condition data of the mold clamping force. In this way, it is possible to spread the injected coating composition over the entire surface of the transparent resin molded body and to provide optimum pressure conditions for the appearance and adhesion strength of the coating film.

  Since the mold temperature is maintained at a temperature at which the coating composition is cured, the coating composition is cured while being held with a set clamping force to form a film.

  At this time, since the coating composition is cured while being pressed against the surface of the mold, the surface state (unevenness or the like) of the mold is accurately transferred to the coating surface of the coating composition.

  Thereafter, the mold clamping cylinder 13 is controlled according to the operation timing and the mold opening speed pattern set in the mold clamping condition setting unit 32 while performing feedback control by the control signal transmitted from the mold clamping control unit 33 and the servo valve 15 for mold clamping. Thus, the movable mold 52 is retracted to a predetermined mold opening position, and the molded body coated with the coating composition is taken out from the mold apparatus 50. In this way, one cycle is completed.

  The mold temperature at the time of molding is set within a range in which the thermoplastic transparent resin can be cooled to an extent that can withstand the flow of the coating composition in the mold and the coating composition can be cured. It is preferable that the temperature is not higher than the melting point of the thermoplastic transparent resin, preferably not higher than 10 ° C. and not lower than the curing temperature of the coating composition, preferably not lower than 10 ° C.

  Next, the 2nd manufacturing method of the in-mold coating transparent molded object of this invention is demonstrated using FIG.

  In accordance with a control signal transmitted from the mold clamping control unit 33 and feedback control by the mold clamping servo valve 15, the mold clamping cylinder 13 moves the movable mold according to the mold closing speed pattern set in the mold clamping condition setting unit 32. The mold 52 is advanced from the mold opening limit position, and is stopped at a position where a predetermined distance is provided between the mold 52 and the fixed mold 51. At this time, the movable mold 52 and the fixed mold 51 are kept at an appropriate temperature so that the coating composition is cured in the mold at a temperature equal to or lower than the melting point (or glass transition temperature Tg) of the thermoplastic transparent resin. I'm leaning. Note that the mold apparatus 50 described here has a sheared edge structure on the split surface, so that the coating composition leaks from the split surface even when the mold is slightly opened at the time of resin filling and coating composition injection. No structure.

  During operation of the mold clamping device 10, when the screw 21 is advanced by the injection cylinder 24 while controlling the opening degree of the injection servo valve 27 by a control signal transmitted from the injection control unit at a predetermined operation timing, The molten thermoplastic transparent resin stored in front of the screw 21 is injected into the mold cavity 53 via the nozzle 26. The operation timing signals are exchanged by the molding device control unit 31 so that the operation of the mold clamping device 10 and the operation of the injection device 20 are linked.

  In the second manufacturing method using the injection press molding method, the molded mold resin melted in a state where the fixed mold 51 and the movable mold 52 are not subjected to clamping force and are kept at a predetermined interval. Is ejected. Then, while the molten resin is being injected into the mold cavity, or after the molten resin is completely injected, feedback control is performed by the control signal transmitted from the mold clamping control unit 33 and the servo valve 15 for mold clamping. , The movable mold 52 is further advanced by the mold clamping cylinder 13 in accordance with the molding condition data (mold clamping force change pattern) of the mold clamping force set in the mold clamping condition setting unit 32, and a predetermined mold clamping force. Raise to.

  The advantage of using the injection press molding method is that the molten resin for the molded body is injected while the mold is opened in a predetermined amount, so that the resin flow pressure is greatly reduced and the residual stress remaining in the molded body is normal injection. Since it is much less than the molding method, it is preferable for molding a transparent resin molding. Then, by applying a predetermined clamping force during injection or after completion of injection, the pressure of the resin generated at the end of the molded body can be made higher than that of a normal injection molding method. For these reasons, the thickness of the molded body can be made more uniform than in the case of a normal injection molding method. After a predetermined clamping force is applied, the molten resin is solidified while maintaining the clamping force.

  When the thermoplastic transparent resin in the mold is solidified to some extent and the surface can withstand the injection pressure of the coating composition, the movable mold 52 is then moved backward by the mold clamping cylinder 13, and the mold clamping control unit 33 The mold opening amount set in the mold clamping condition setting unit 32 is given by the control signal to be transmitted and the servo valve 15 for mold clamping while performing feedback control, so that the space between the surface of the transparent resin molding and the mold cavity 53 surface is given. After the gap is provided, the coating composition is coated by a control signal transmitted from the injector controller 35 in accordance with the injection amount, injection speed, injection timing, and injection pressure of the coating composition injector 55 set in the mold clamping condition setting unit 32. The composition injector 55 is driven to inject the coating composition into the mold cavity 53.

  Next, while the feedback control is performed by the control signal transmitted from the mold clamping control unit 33 and the servo valve 15 for mold clamping, the movable mold 52 is advanced again by the mold clamping cylinder 13 and is set in the mold clamping condition setting unit 32. The mold clamping force is generated according to the molding condition data of the mold clamping force. In this way, it is possible to spread the injected coating composition over the entire surface of the transparent resin molded body and to provide optimum pressure conditions for the appearance and adhesion strength of the coating film.

  Since the mold temperature is maintained at a temperature at which the coating composition is cured, the coating composition is cured while being held with a set clamping force to form a film.

  At this time, since the coating composition is cured while being pressed against the surface of the mold, the surface state (unevenness or the like) of the mold is accurately transferred to the coating surface of the coating composition.

  Thereafter, the mold clamping cylinder 13 is controlled according to the operation timing and the mold opening speed pattern set in the mold clamping condition setting unit 32 while performing feedback control by the control signal transmitted from the mold clamping control unit 33 and the servo valve 15 for mold clamping. Thus, the movable mold 52 is retracted to a predetermined mold opening position, and the molded body coated with the coating composition is taken out from the mold apparatus 50. In this way, one cycle is completed.

  As described above, the second manufacturing method using the injection press molding method can reduce the residual stress remaining in the molded body, and can form the thickness of the molded body more uniformly than the normal injection molding method. It has an excellent effect of being able to.

  Therefore, the in-mold coated transparent molded body produced by the second production method is good in that the thickness of the coating can be reduced because the distortion is less and the thickness of the coating is more uniform than before. In-mold coated transparent molded product.

  The in-mold coated transparent molded body of the present invention can be used for transparent resin parts for automobiles such as headlamp covers and sunroofs, resin lenses, and home appliance parts.

  Hereinafter, the present invention will be described in more detail with reference to examples.

  In the examples, “parts” and “%” are based on mass.

(A) Preparation of urethane oligomer <UAC-1>
1000 parts by weight of polycaprolactone diol (molecular weight 500), 840 parts by weight of isophorone diisocyanate, 1.0 part by weight of hydroquinone monomethyl ether and 1.8 parts by weight of dibutyltin laurate are charged in a reaction vessel and reacted at 75 ° C. for 3 hours with stirring. Then, 228 parts by mass of 2-hydroxyethyl acrylate and 0.5 part by mass of hydroquinone monomethyl ether were added and reacted at 75 ° C. for 4 hours to obtain a weight average molecular weight (Mw) of 2800 having two acrylate groups in one molecule. A urethane oligomer (UAC-1) was prepared.

<UAC-2>
An ethylene oxide adduct of 2,2-bis (4-hydroxyhexyl) propane was charged in a reaction vessel with 524 parts by mass of bis (4-isocyanatocyclohexyl) methane and 0.36 parts by mass of dibutyltin dilaurate and stirred at 40 ° C. (Molecular weight 1000) After dropping 1000 parts by mass and reacting for 3 hours, 273 parts by mass of 2-hydroxyethyl methacrylate in which 1.8 parts by mass of hydroquinone was dissolved was added dropwise and reacted at 75 ° C. for 4 hours. A urethane oligomer (UAC-2) of Mw3200 having two acrylate groups in one molecule was prepared.

<UAC-3>
An ethylene oxide adduct of 2,2-bis (4-hydroxyhexyl) propane was charged in a reaction vessel with 524 parts by mass of bis (4-isocyanatocyclohexyl) methane and 0.36 parts by mass of dibutyltin dilaurate and stirred at 40 ° C. (Molecular weight 1000) After dropping 1000 parts by mass and reacting for 3 hours, 467 parts by mass of glycerin dimethacrylate and 0.5 parts by mass of hydroquinone monomethyl ether were then added and reacted at 75 ° C. for 4 hours. An Mw3300 urethane oligomer (UAC-3) having 4 acrylate groups was prepared.

<UAC-4>
1000 parts by weight of polycaprolactone diol (molecular weight 500), 840 parts by weight of isophorone diisocyanate, 1.0 part by weight of hydroquinone monomethyl ether and 1.8 parts by weight of dibutyltin laurate are charged in a reaction vessel and reacted at 75 ° C. for 3 hours with stirring. Then, 607 parts by mass of pentaerythritol triacrylate and 0.5 parts by mass of hydroquinone monomethyl ether were added and reacted at 75 ° C. for 4 hours to give a urethane oligomer of Mw 3400 having 6 acrylate groups in one molecule (UAC-4) Was prepared.

Preparation of In-mold Coating Composition The in-mold coating compositions of Examples 1 to 8 and Comparative Examples 1 to 3 were blended and prepared as shown in Table 1. First, the components (a) UAC-2 to UAC-4, 1,6HDDA, PETE, TMP (EO) T, PETeA, ST, Tinuvin 1130, Zelec-NE and HQMMA of the urethane oligomer are charged into a stainless steel tank. And uniformly dispersed by a stirrer. This is called the main agent for convenience.

  On the other hand, BBCHPDC and DBP components were mixed in advance, and the paste-like material was added to the main agent, mixed uniformly, degassed while decompressing, and entrained bubbles were removed.

(Examples 1-8 and Comparative Examples 1-3)
A shear-edge structure with which a box-shaped product having a length of 450 mm, a width of 650 mm, a depth of 10 mm, and a thickness of 3 mm can be obtained on a toggle injection molding machine for in-mold coating molding having a mold clamping capacity of 850 tf with a coating composition injection device. First, a polycarbonate resin (Iupilon ML300, manufactured by Mitsubishi Engineering Plastics) melted at 280 ° C. with a mold clamping force of 750 tf was injection molded. The mold temperature at this time was 95 ° C., and the cooling time was 30 seconds.

  Thereafter, the mold was separated by 1.0 mm, and 9.5 cc of each of Examples 1 to 8 and Comparative Examples 1 to 3 of the in-mold coating compositions shown in Table 1 were injected. The time required for injection of the coating composition was 1.1 seconds. The maximum flow distance x in the cavity of the coating composition was 55 cm. Re-clamping was started 0.1 seconds after the completion of the injection of the coating composition, the mold was clamped to 10 tf over 1 second, and after holding for 90 seconds, the mold was opened and the in-mold coated molded body was taken out. A cured film having a thickness of about 30 μm was formed on the entire surface of the molded body.

  Each of the obtained in-mold coatings was evaluated for the presence / absence of coating failure, transparency, coating adhesion, scratch resistance, etc. as follows. The results are shown in Table 2.

<Test and evaluation method>
(1) Coatability: The coating state of the coating composition on the surface of the molded body was visually determined.
[Evaluation] ○… Full coat × × Uncoated part

(2) Curability of film: According to JIS K 5600-5-4 (scratch hardness) test, the surface of the film was scratched with an HB pencil, and the state of the film was visually determined.
[Evaluation] ○… No traces left △… Streaks on the film ×… The film is torn

  (3) Transparency: The haze value was measured using a haze meter.

(4) Presence or absence of cracks; The presence or absence of cracks on the surface of the coating was visually determined.
[Evaluation] ○… No cracks △… Sometimes ×… Many

(5) Adhesiveness: The initial coating film adhesiveness test was carried out according to the adhesiveness (cross-cut method) of JIS K 5600-5-6. The evaluation of adhesion was evaluated based on the following 6 grades from 0 to 5 based on the classification of test results described in JIS K 5600-5-6.
[Evaluation of adhesion]
0: The edge of the cut part is completely smooth, and there is no peeling in the eyes of any lattice.
1: Small peeling of the coating at the intersection of cuts (cross cut). 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 portion 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 portions of the grid's eyes have been partially or completely peeled off. The cross-cut part is clearly affected by more than 15% but not more than 35%.
4: The coating is partially or completely peeled along the edge of the cut, and / or some lattice eyes are partially or completely peeled off. It is clearly not more than 35% that the cross-cut is affected.
5: Any of the peeling degrees that cannot be classified even with classification 4.

  (6) Warm water resistance: According to the liquid resistance (water immersion method) of JIS K 5600-6-2, the test piece prepared as described above was immersed in warm water of 40 ± 1 ° C. for 240 hours. After completion of the prescribed test period, the test piece is taken out and allowed to stand at room temperature for 24 hours. evaluated.

  (7) Cooling and cycling characteristics: A test piece prepared as described above was allowed to stand in a 110 ° C. thermostatic bath for 1 hour, and immediately in a −30 ° C. thermostatic bath for 1 hour, and a 100 cycle test. Went. After the end of the 100 cycle test period, the test piece was taken out and placed at room temperature for 24 hours, and the adhesion of the film was evaluated in 6 stages from 0 to 5 in the same manner as described above.

  (8) Scratch resistance: Using a test piece prepared as described above, a wearer CS-10F, a load of 500 g, a wear frequency of 100 times with a Taber type abrasion tester described in JIS K 5600-5-9. Under these conditions, the wear wheel placed on the coating was rotated, and the haze value of the coating surface after the test was measured using a haze meter. The evaluation of scratch resistance was expressed by (cloudiness value after test) − (cloudiness value before test).

・１，６ＨＤＤＡ（１，６−ヘキサンジオールジアクリレート）（ｂ）成分に対応。１分子内に２個の二重結合を持つモノマー。ポリカーボネート樹脂を溶解する。
・ＰＥＴＡ（ペンタエリスリトールトリアクリレート）（ｃ）成分に対応。１分子内に３個の二重結合を持つモノマー。ポリカーボネート樹脂を膨潤も溶解もしない。
・ＴＭＰ（ＥＯ）Ｔ（エトキシ化トリメチロールプロパントリアクリレート）（ｃ）成分に対応。１分子内に３個の二重結合を持つモノマー。ポリカーボネート樹脂を膨潤も溶解もしない。
・ＰＥＴｅＡ（ペンタエリスリトールテトラアクリレート）（ｃ）成分に対応。１分子内に４個の二重結合を持つモノマー。ポリカーボネート樹脂を膨潤も溶解もしない。
・ＳＴ（スチレン）１分子内に１個の二重結合を持つモノマー。
・Ｔｉｎｕｖｉｎ１１３０：紫外線吸収剤（チバガイギー社製商品名）
・ＺＥＬＥＣ−ＮＥ：内部離型剤（デュポン社製商品名）
・ＨＱＭＭＥ（ヒドロキノンモノメチルエーテル）重合禁止剤
・ＢＢＣＨＰＤＣ（ビス（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート）有機過酸化物重合開始剤
・ＤＢＰ（ジブチルフタレート）可塑剤

-Corresponds to 1,6HDDA (1,6-hexanediol diacrylate) (b) component. A monomer having two double bonds in one molecule. Dissolve the polycarbonate resin.
-Corresponds to PETA (pentaerythritol triacrylate) (c) component. A monomer having three double bonds in one molecule. Does not swell or dissolve the polycarbonate resin.
-TMP (EO) T (ethoxylated trimethylolpropane triacrylate) (c) Corresponds to the component. A monomer having three double bonds in one molecule. Does not swell or dissolve the polycarbonate resin.
-Corresponds to PETeA (pentaerythritol tetraacrylate) (c) component. A monomer having four double bonds in one molecule. Does not swell or dissolve the polycarbonate resin.
ST (styrene) A monomer having one double bond in one molecule.
Tinuvin 1130: UV absorber (trade name, manufactured by Ciba Geigy)
・ ZELEC-NE: Internal mold release agent (trade name, manufactured by DuPont)
・ HQMME (hydroquinone monomethyl ether) polymerization inhibitor ・ BBCHPDC (bis (4-t-butylcyclohexyl) peroxydicarbonate) organic peroxide polymerization initiator ・ DBP (dibutyl phthalate) plasticizer

(Examples 9 and 10 and Comparative Examples 4 and 5)
A toggle-type injection molding machine for in-mold coating molding with a mold clamping capacity of 850 tf with a coating composition injection device having a shear edge structure that can obtain a flat product having a length of 1500 mm, a width of 50 mm, a depth of 5 mm, and a thickness of 3 mm. First, a polycarbonate resin (Iupilon ML300, manufactured by Mitsubishi Engineering Plastics) melted at 280 ° C. with a mold clamping force of 750 tf was injection molded. The mold temperature at this time was 95 ° C., and the cooling time was 30 seconds.

  Thereafter, the mold was opened 1 mm, and 4 cc of each of Examples 9 and 10 and Comparative Examples 4 and 5 of the in-mold coating compositions prepared with the respective formulations shown in Table 3 were injected. The time required for injection of the coating composition was 0.5 seconds. The maximum flow distance x in the cavity of the coating composition was 150 cm. Re-clamping was started 0.1 seconds after the completion of the coating composition injection, the mold was clamped to 10 tf over 1 second, held for 60 seconds, the mold was opened, and the in-mold coated molded body was taken out. A cured film having a thickness of about 50 μm was formed on the entire surface of the molded body.

  With respect to the obtained in-mold coated molded article, the cured state of the film, the presence or absence of poor coating properties, the adhesion of the film, and the like were evaluated by the methods described above. The results are shown in Table 4.

(Example 11 and Example 12)
A shear-edge structure with which a box-shaped product having a length of 450 mm, a width of 650 mm, a depth of 10 mm, and a thickness of 3 mm can be obtained on a toggle injection molding machine for in-mold coating molding having a mold clamping capacity of 850 tf with a coating composition injection device. Attach the mold, and first inject the polycarbonate resin (Iupilon ML300, manufactured by Mitsubishi Engineering Plastics) melted at 280 ° C into the mold cavity with the 5mm mold opened as the initial opening amount. The mold was closed and the clamping force was further increased to 500 tf. The mold temperature at this time was 95 ° C.

  The polycarbonate resin filled in the cavity was held for 30 seconds in a state where a clamping force was applied, and solidified to such an extent that the surface could withstand the flow of the coating composition.

  Next, the mold was opened by 1 mm, and 9.5 cc of each of Examples 11 and 12 of the in-mold coating composition prepared with each formulation shown in Table 5 was injected. The time required for injection of the coating composition was 1.0 second. The maximum flow distance x in the cavity of the coating composition was 55 cm. Re-clamping was started 0.1 seconds after the completion of the coating composition injection, the mold was clamped to 10 tf over 1 second, held for 60 seconds, the mold was opened, and the in-mold coated molded body was taken out. A cured coating film having a thickness of about 30 μm was formed on the entire surface of the molded body.

  With respect to the obtained in-mold coated molded article, the cured state of the film, the presence or absence of poor coating properties, the adhesion of the film, and the like were evaluated by the methods described above. The results are shown in Table 6.

・ＴＰＧＤＡ（トリプロピレングリコールジアクリレート）（ｂ）成分に対応。ポリカーボネート樹脂を膨潤も溶解もしないモノマー。

・ Compatible with TPGDA (tripropylene glycol diacrylate) (b) component. Monomer that does not swell or dissolve polycarbonate resin.

1 is an overall configuration diagram of an in-mold coating forming apparatus according to an embodiment of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Clamping device 11 Fixed platen 12 Movable platen 13 Clamping cylinder 14 Tie rod 15 Clamping servo valve 16 Stroke sensor 17 Mold opening sensor 18 Clamping force sensor 20 Injection device 21 Screw 22 Barrel 23 Hydraulic motor 24 Injection cylinder 25 Hopper 26 Nozzle 27 Injection Servo Valve 30 Control Device 31 Molding Device Control Unit 32 Mold Clamping Condition Setting Unit 33 Mold Clamping Control Unit 34 Change Pattern Storage Unit 35 Injection Machine Control Unit 38 Injection Control Unit 50 Mold Device 51 Fixed Mold 52 Movable Mold 53 Mold cavity 54 Coating composition pressure sensor 55 Coating composition (paint) injection machine 100 In-mold coating molding apparatus

Claims (3)

In the injection molding method, the injection compression molding method or the injection press molding method, a step of clamping a mold composed of a fixed mold portion and a movable mold portion, and a step of injecting a thermoplastic transparent resin into the cavity and molding , Cooling the thermoplastic transparent resin, reducing the clamping force or slightly opening the mold, injecting the in-mold coating composition into the cavity, re-clamping, and the injected mold A step of curing the inner coating composition; and an in-mold coating transparent molded body produced by removing the molded body from the mold after the in-mold coating composition is cured, wherein the inner coating composition comprises (a) at least Urethane oligomer having 2 to 8 (meth) acryloyl groups in one molecule,
(B) at least one monomer having two ethylenic double bonds in one molecule;
(C) at least one monomer having three or more ethylenic double bonds in one molecule;
(D) comprising an organic peroxide polymerization initiator,
The mass ratio of the urethane oligomer (a) to the monomer (b) and the monomer (c)
(A) / {(b) + (c)} = 10/90 to 70/30,
The mass ratio of the monomer (b) and the monomer (c) is
(B) / (c) = 5/95 to 95/5,
The mass ratio of the organic peroxide polymerization initiator (d) is
(D) / {(a) + (b) + (c)} = 0.1 / 100 to 5/100
An in-mold coated transparent molded body characterized in that:   The in-mold coated transparent molded article according to claim 1, wherein at least one of the monomer (b) and the monomer (c) swells or dissolves the thermoplastic transparent resin. Mold coating a transparent molded article according to claim 1 or 2, wherein the thermoplastic transparent resin is a polycarbonate resin.

Images