JP2013226839A - Method of manufacturing molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a molded article, which has excellent antifouling properties and decontamination properties against dirt derived from oil-based ink or the like, and also has high design performance even when casting and molding a mold material formed of a resin composition having a polysiloxane structure under a sealed condition, and which maintains such effects over a long period of time.SOLUTION: A layer formed of a compound (A) which is urethane (meth)acrylate having a structure derived from polysiloxane (a1) having a polyalkylene oxide chain in a side chain and polymerizable unsaturated double bond, and a radical polymerizable resin composition (B) containing a curing agent is formed on a surface of a base material (C). A mold (II) subjected to mold releasing processing by a silicon mold release agent (I) is mounted on a surface of the layer which is uncured or semi-cured, and the radical polymerizable resin composition (B) is cured.

Description

  The present invention relates to a method for producing a molded article that achieves both excellent antifouling and decontamination properties and high design properties.

  Building materials such as bathtubs, wall materials, floor materials, etc. are required to have a high-class design, and in recent years, the surface has irregularities such as grain, stone, cloth, and grain. Members with an abstract pattern, members with a matte treatment that gives minute irregularities to the surface, and members with a smooth surface that can give a mirror finish have been commercialized. .

  As a method of imparting the unevenness and excellent smoothness to the surface of the building member or the like, a press molding method using a molding die is generally applied. Specifically, the molding material is applied or placed on one surface of the mold, and then the other mold having an uneven shape or a smooth surface is laminated and pressed for a predetermined time, This is a method of curing a molding material. At this time, the surface of the molded product to which the concavo-convex pattern or smooth shape is applied is generally in a sealed state in which the molding die is in close contact with each other, and is thus shielded from air.

  On the other hand, in recent years, excellent antifouling properties and decontamination properties have been demanded for molded articles as described above, in addition to the above-described high design properties. Here, the antifouling property and the decontamination property are, for example, that oily ink or the like is hardly adhered to the surface of the molded product, and even if temporarily adhered, it can be easily removed by lightly rubbing with a cloth or the like. The characteristic is shown. Such characteristics are particularly required for, for example, wall materials and floor materials.

  As what can form the hardened | cured material which has the said outstanding antifouling property etc., photocurable (meth) acrylate type resin, photocurable polysiloxane type urethane (meth) acrylate resin, photocurable silicon block ( A photocurable (meth) acrylate resin composition containing a (meth) acrylate resin and a photopolymerization initiator is known (see Patent Document 1).

  Also obtained by copolymerizing a specific hydrophilic vinyl monomer, hydroxyl group-containing vinyl monomer and carboxyl group-containing vinyl monomer in the presence of a polymer having a reactive double bond via an ether bond in the side chain of silicon. It is known that the antifouling coating composition containing the graft copolymer is excellent in antifouling properties including repaintability and storage stability (see Patent Document 2).

  The active energy ray-curable resin composition containing a polyfunctional urethane acrylate resin composed of a polysiloxane skeleton and organic isocyanurate and an unsaturated monomer has a high surface hardness and forms a film with excellent scratch resistance. It is known that it can be performed (see Patent Document 3).

  However, when the resin compositions disclosed in Patent Documents 1 to 3 are molded by the press molding method as described above, a molded product having a pattern with desired irregularities on the surface can be obtained. Since the surface of the surface was formed in a sealed state that was shielded from air, the antifouling property and decontamination property of the surface were not sufficient in practice. Further, although the antifouling property and the like are required to be sustainable for as long as possible due to its characteristics, the composition may not be able to be maintained for a practically sufficient long time.

  As described above, even when molded under sealed conditions, it has been extremely difficult to produce a molded product having a surface that achieves both high designability and excellent antifouling and decontamination properties. It was difficult.

JP 2003-192751 A Japanese Patent Laid-Open No. 7-278467 Japanese Patent Laid-Open No. 6-1819

  The problem of the present invention is that even when a molding material comprising a resin composition having a polysiloxane structure is cast and molded under a sealed condition, for example, excellent antifouling properties against stains derived from oil-based inks and the like An object of the present invention is to provide a method for producing a molded article which has a decontamination property, can achieve both high designability and can maintain such an effect over a long period of time.

  The inventors have a polysiloxane structure in a molding material that can contribute to improvement of antifouling property, etc., because the surface of a molded product provided with a concavo-convex pattern by the mold does not have excellent antifouling property etc. However, it was considered that the cause was that it was not localized on the surface of the molded product.

  Therefore, the present inventors examined a method for localizing the polysiloxane structure on the surface of the molded product, and performed various studies such as adjusting the molding temperature and pressure. As a result of examining the method of forming by applying a silicone mold release agent to the surface of the mold that contacts the surface of the molded product in the above investigation, it is excellent in prevention even when molded under sealed conditions. We have found that it is possible to produce molded articles having soiling properties.

  That is, the present invention is a urethane (meth) acrylate having a structure derived from polysiloxane (a1) having a polyalkylene oxide chain in the side chain and a polymerizable unsaturated double bond on the surface of the substrate (C). After forming a layer composed of the radically polymerizable resin composition (B) containing the compound (A) and a curing agent, a mold release treatment is performed on the surface of the uncured or semi-cured layer with the silicon-based mold release agent (I). The mold (II) subjected to is placed, and then the radical polymerizable resin composition (B) is cured, which relates to a method for producing a molded product.

  According to the method for producing a molded product of the present invention, a molded product having excellent antifouling properties and contamination removal properties can be produced by a closed molding method. The manufactured molded product is required to have both antifouling property, decontamination property and high design property, for example, outdoor use such as a roof of a building, an outer wall, a waterproof layer; furniture, kitchen counter, kitchen sink, wash bowl It can be used for housing components such as wash counters, wash cabinet cabinet doors, bathtubs, bathroom walls and floors, toilet toilets, etc .;

First, the manufacturing method of the 1st molded product of this invention is demonstrated.
The present invention relates to a compound (A) having a structure derived from polysiloxane (a) and a polymerizable unsaturated double bond on the surface of a mold (II) that has been subjected to a mold release treatment with a silicon-based mold release agent (I). ) Containing a radical polymerizable resin composition (B), and then curing the radical polymerizable resin composition (B).

  In the present invention, it is important to use a combination of the mold (II) subjected to the mold release treatment with the silicon mold release agent (I) and the radical polymerizable resin composition (B) as a molding material. is there. Here, when any of the mold (II) and the radical polymerizable resin composition (B) is lacking, it is excellent in antifouling property and decontamination property (hereinafter sometimes abbreviated as antifouling property etc.). It is difficult to obtain a molded product having a surface having an uneven pattern. For example, when a fluorine-based mold release agent is used instead of the silicon-based mold release agent (I), it is difficult to obtain a high-design molded product excellent in antifouling property.

  Thus, by using the silicon-based mold release agent (I) as a mold release agent and the radical polymerizable resin composition (B) as a molding material in combination, the radical polymerizable resin composition ( Even when B) is molded under hermetically sealed conditions, the polysiloxane structure derived from polysiloxane (a) is localized on the surface of the molded product, and a molded product having excellent antifouling properties can be obtained. it can.

  Specifically, the first method for producing a molded product includes the step (i) of obtaining a mold (II) in which the inner surface of the mold is subjected to a mold release treatment using the silicon mold release agent (I), the mold release A step (ii) of forming a layer comprising the radical polymerizable resin composition (B) on the surface of the treated mold (II), and a step of molding and curing the radical polymerizable resin composition (B); (Iii).

  In the step (i), for example, a silicon release agent (I) is applied to the inner surface of the mold, and the silicon release agent (I) or a cured product thereof is applied to the inner surface of the mold. It can carry out by the method of forming the thin film layer which becomes.

  Examples of the coating method include a roll coating method such as a gravure coating method and a reverse coating method; a bar coating method such as a Mayer bar; a spray coating method; an air knife coating method; a brush coating method; a cloth coating method; Known methods such as the method can be mentioned.

  Curing of the silicon release agent (I) after the application can be performed by a method corresponding to the type of the silicon release agent (I) to be used, such as heat treatment, ultraviolet irradiation, and electron beam irradiation.

  The thin film layer formed in the step (i) preferably has a thickness of approximately 0.02 to 10 μm on the inner surface of the mold.

  As the mold (II) subjected to the mold release treatment, a mold obtained by previously kneading, molding and curing the material constituting the mold and the silicon-based mold release agent (I) is used. You can also. However, even in such a mold, from the viewpoint of promoting the localization of the polysiloxane structure in the radical polymerizable resin composition (B) on the surface of the molded product, the silicon-based separation is further provided on the inner surface of the mold. It is preferable to form a thin film layer using the mold agent (I).

  Examples of the silicon release agent (I) used in the step (i) include those capable of forming a film by addition polymerization with a platinum catalyst, those capable of forming a film by condensation polymerization with an organic tin catalyst, Moisture-curing type that can form a film by reacting with water (humidity), UV-crosslinking type or electron beam-crosslinking type that can form a film by radical polymerization or cationic polymerization with a photopolymerization initiator be able to. As the silicon release agent (I), various commercially available silicon release agents can be used.

  The silicon-based release agent is usually used by appropriately diluting with a solvent (water in the case of an aqueous type) such as toluene, hexane, heptane, methyl ethyl ketone (MEK), and ethyl acetate.

  As the mold used for the production of the mold (II), any mold can be used as long as it is usually used in the field. For example, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polyvinyl alcohol Known plastics such as FRP made of hard vinyl chloride, soft vinyl chloride, ABS resin, unsaturated polyester resin, vinyl ester resin, epoxy resin, etc .; wood; metal; glass and the like can be used. The mold (II) may be a film or a sheet.

  As the mold (II) subjected to the mold release treatment, it is preferable to use a mold having a concavo-convex pattern or a planar shape from the viewpoint of imparting desired designability to the surface of the molded product. Examples of such concavo-convex patterns include those obtained by copying natural concavo-convex shapes such as wood grain, stone grain, cloth grain, and grain grain, character symbols, lines, and various abstract patterns. In addition, the planar shape includes a smooth shape used for glossy mirror surface treatment with almost no unevenness.

  Next, the step (ii) of forming a layer composed of the radical polymerizable resin composition (B) on the surface of the mold (II) subjected to the mold release treatment will be described.

  The radical polymerizable resin composition (B) is, for example, a roll coating method such as a gravure coating method or a reverse coating method; a bar coating method such as a Mayer bar; a spray coating method; an air knife coating method; a flow coater method; Method: Can be applied by an injection method or the like. Thereby, the uncured or semi-cured layer made of the radical polymerizable resin composition (B) can be formed on the inner surface of the mold (II).

  The thickness of the layer made of the radical polymerizable resin composition (B) can be appropriately adjusted according to the molded product to be produced.

  Next, the step (iii) of molding and curing the radical polymerizable resin composition (B) will be described.

  Examples of a method for forming the radical polymerizable resin composition (B) and imparting a pattern due to the mold (II) on the surface thereof include a cast molding method, a film molding method, a hand lay-up molding method, and a spray. Examples thereof include an up molding method, an RTM (resin transfer molding) molding method, a continuous molding method, and a press molding method.

  Curing of the radical polymerizable resin composition (B) can proceed by a method of irradiating active energy rays, and when a peroxide or a reducing agent is used in combination in the composition (B), It can be allowed to proceed by leaving it under heat treatment or at room temperature. For example, when the mold is a film or sheet made of a transparent plastic, the curing can be advanced by a method of irradiating the surface of the mold with ultraviolet rays or the like.

  The manufacturing method of the 1st molded article of the present invention as mentioned above is suitable for manufacture of a decorative film, a decorative board, etc., for example.

Next, the manufacturing method of the 2nd molded product of this invention is demonstrated.
According to the second method for producing a molded article of the present invention, the structure derived from the polysiloxane (a) and the polymerizable unsaturation are formed on the surface of the mold (II) subjected to the mold release treatment with the silicon mold release agent (I). After forming the layer made of the radical polymerizable resin composition (B) containing the compound (A) having a double bond, the substrate (C) is placed on the uncured or semi-cured layer surface, Next, the method for producing a molded product is characterized in that the radical polymerizable resin composition (B) is cured.

  Specifically, the method for producing the second molded product includes a step (iv) of obtaining a mold (II) subjected to a mold release treatment on the inner surface of the mold using the silicon-based mold release agent (I), the mold release A step (v) of forming a layer comprising the radical polymerizable resin composition (B) on the surface of the treated mold (II); an uncured or semi-cured material comprising the radical polymerizable resin composition (B); A step (vi) of placing the substrate (C) on the layer surface, and a step (vii) of molding and curing the radical polymerizable resin composition (B).

  Said process (iv) and (v) in the manufacturing method of a 2nd molded article can be performed by the method similar to said process (i) and (ii) demonstrated by the manufacturing method of said 1st molded article. .

  In the step (vi), the base material (C) integrated with the molded product made of the radical polymerizable resin composition (B) is converted into an uncured or semi-cured material made of the radical polymerizable resin composition (B). This is a step of placing and laminating on the layer surface.

  Examples of the substrate (C) include polyethylene terephthalate, polycarbonate, polymethyl methacrylate, triacetyl cellulose, polyvinyl alcohol, hard vinyl chloride, soft vinyl chloride, ABS resin, unsaturated polyester resin, vinyl ester resin, and epoxy resin. Known plastics such as FRP, wood, metal, concrete, asphalt, glass, paper, and the like can be used.

  The substrate (C) is preferably placed directly on the surface of the layer made of the radical polymerizable resin composition (B) while the surface of the layer is uncured or semi-cured. Thereby, the molded product which the hardened | cured material of the radical polymerizable resin composition (B) and the base material (C) integrated can be obtained, without using an adhesive agent etc. separately. Further, the molded product obtained by almost completely curing the radical polymerizable resin composition (B) and the substrate (C) may be bonded together using an adhesive or the like.

  Said process (vii) can be performed by the method similar to the said process (iii) demonstrated by the manufacturing method of said 1st molded article.

  The manufacturing method of the 2nd molded product of this invention as mentioned above is suitable for manufacture of a decorative board, a door, a kitchen panel, a flooring etc., for example.

Next, the manufacturing method of the 3rd molded article of this invention is demonstrated.
The third method for producing a molded article of the present invention is a radical polymerization containing a compound (A) having a structure derived from polysiloxane (a) and a polymerizable unsaturated double bond on the surface of a substrate (C). After forming the layer made of the conductive resin composition (B), the mold (II) subjected to the release treatment with the silicon-based release agent (I) is placed on the uncured or semi-cured layer surface. Then, the radically polymerizable resin composition (B) is cured, which is a method for producing a molded product.

  In the third method for producing a molded article, first, a layer made of the radical polymerizable resin composition (B) is formed on the surface of the substrate (C), and then the surface of the uncured or semi-cured layer is formed. The method can be performed in the same manner as the method for producing the second molded article of the present invention except that the mold (II) is placed on the mold.

  The manufacturing method of the 3rd molded article of the present invention as mentioned above is suitable for manufacture of a decorative board, a door, a kitchen panel, a flooring, etc., for example.

Next, the manufacturing method of the 4th molded product of this invention is demonstrated.
According to the fourth method for producing a molded article of the present invention, the structure derived from the polysiloxane (a) and the polymerizable unsaturation are formed on the surface of the mold (II) which has been subjected to the mold release treatment with the silicon mold release agent (I). After forming a layer made of the radical polymerizable resin composition (B) containing the compound (A) having a double bond, the radical polymerizable resin composition (B) is cured or semi-cured to form a gel coat layer. And forming a back layer obtained by curing the resin composition on the surface of the gel coat layer.

  A fourth method for producing a molded article includes a step (viii) of forming a gel coat layer made of the radical polymerizable resin composition (B) on the surface of the mold (II), and a resin composition on the surface of the gel coat layer. A step (ix) of forming a back layer formed by curing the product.

  Said process (viii) can be performed by the method similar to the case of the manufacturing method of said 1st molded article. That is, it is possible to employ a method in which the layer (B) made of the radical polymerizable resin composition is formed on the surface of the mold (II), which is molded and cured. The mold (II) and its mold release processing method and the like may be the same as those in the first method for manufacturing a molded product.

  The step (ix) is a step of forming a back layer of a molded product by forming a layer made of a resin composition on the surface of the gel coat layer obtained in the step (viii) and curing the layer. is there.

  The layer made of the resin composition is formed on the gel coat layer formed on the surface of the mold (II), for example, resin transfer molding molding method (RTM molding method), SMC molding method, BMC molding method, hand layup molding. It can be formed by laminating the resin composition by a method, a casting molding method or the like.

  Examples of the resin composition that can be used for forming the back layer include those conventionally used as an artificial marble forming resin composition and a fiber reinforced resin composition.

  Examples of the artificial marble forming resin composition that can be used include unsaturated polyester resins, vinyl ester resins, thermosetting acrylic resins, epoxy resins, and the like including fillers and pattern materials.

  As said fiber reinforced resin composition, unsaturated polyester resin etc. which contain glass fiber, a polyester fiber, etc. can be used, for example.

  By the above manufacturing method, it is possible to obtain a molded article having a gel coat layer having excellent antifouling properties and high design properties on the surface of an artificial marble or fiber reinforced resin molded article.

  The method for producing the fourth molded article of the present invention as described above is, for example, the production of bathtubs, unit baths, washstands, kitchenware, corrugated sheets, boats, tanks, panels, vehicle members, housing materials, automobile members, etc. It is suitable for.

Next, the radical polymerizable resin composition (B) used in the method for producing a molded product of the present invention will be described.
The radical polymerizable resin composition (B) contains a compound (A) having a structure derived from polysiloxane (a) and a polymerizable unsaturated double bond, and other additives as required. is there.

  The compound (A) essentially comprises a polymerizable unsaturated double bond that contributes to curing and a structure derived from polysiloxane (a) that contributes to imparting excellent antifouling properties and the like. Here, in the radical polymerizable resin composition using the compound having no structure derived from the polysiloxane (a) instead of the compound (A), a molded product is manufactured using the mold (II). Even so, it is difficult to obtain a molded product having good antifouling properties. Moreover, if it is a radical polymerizable resin composition using the compound which does not have a polymerizable unsaturated double bond instead of the said compound (A), by using the said type | mold (II), high design property Although a molded product having good antifouling properties and the like can be obtained, there is a problem that the effect is remarkably reduced in a short period of time.

  By using the compound (A) having a structure derived from the polysiloxane (a) and a polymerizable unsaturated double bond as in the present invention, a molded article having excellent antifouling property and the like that can be sustained over a long period of time. It can be manufactured.

  Specifically, the compound (A) having a structure derived from polysiloxane (a) and a polymerizable unsaturated double bond has urethane (meth) acrylate (A1) having a polysiloxane structure and a polysiloxane structure. An ester (meth) acrylate (A2), an epoxy (meth) acrylate (A3) having a polysiloxane structure, or the like can be used. In the present invention, these may be used alone or in combination of two or more. However, since they are particularly excellent in the curability of the radical polymerizable resin composition (B) and the antifouling property of the molded product, It is preferable to use urethane (meth) acrylate (A1) having a siloxane structure.

  The urethane (meth) acrylate (A1) that can be used as the compound (A) includes a polysiloxane (a) having an active hydrogen atom-containing group, an active hydrogen atom-containing group, and at least one polymerizable unsaturated disilane. What the polymerizable monomer (d) which has a heavy bond couple | bonded through the isocyanate group containing compound (b) is preferable.

  Moreover, as the urethane (meth) acrylate (A1), it is necessary to use one having at least one (meth) acryloyl group. It is preferable to use what has more than this, and it is more preferable to use what has 2-5 pieces.

The urethane (meth) acrylate (A1) is obtained by reacting, for example, a polysiloxane (a) having an active hydrogen atom-containing group with an isocyanate group-containing compound (b) to obtain a structure derived from the polysiloxane (a). It can manufacture by obtaining the compound (c) which has an isocyanate group, and making this compound (c) and the said polymerizable monomer (d) react.
The active hydrogen atom-containing group is preferably a hydroxyl group.

  The polysiloxane (a) having an active hydrogen atom-containing group is, for example, a block type in which an active hydrogen atom-containing group such as a hydroxyalkyl group or an amino group is bonded to the end of a polysiloxane chain as a main chain. The number of active hydrogen atoms is preferably 1 or 2, and the graft type of the active hydrogen atom-containing group is bonded to the side chain of the polysiloxane chain, and the number of active hydrogen atoms is 1 or more. Things.

  The polysiloxane (a) is selected from the group consisting of an alkyl group and a phenyl group because it gives particularly excellent antifouling properties and the urethane (meth) acrylate (A1) can be produced particularly stably. Those composed of two or more bonded silicon atoms are preferred. Here, the alkyl group is preferably linear or branched, and more preferably linear. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 5, and particularly preferably a methyl group or an ethyl group. Specific examples include polydimethylsiloxane, polydiethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polyethylphenylsiloxane, polydiphenylsiloxane, and the like.

  As said polysiloxane (a), it is preferable to use what has a hydroxyl equivalent of 300-10000, and it is more preferable to use what is 700-5000. By using the polysiloxane (a) having a hydroxyl group equivalent within this range, a radical polymerizable composition capable of forming a cured product particularly excellent in compatibility as a molding material and antifouling property can be obtained. .

  As a commercial item of the said polysiloxane (a), although Shin-Etsu Chemical Co., Ltd. X-22-160AS, KF-6001, KF-6002, etc. are mentioned, it is not limited to these.

  As the polysiloxane (a), a polysiloxane (a1) having a polyalkylene oxide chain in the side chain is used because the transparency of the obtained molded product can be maintained and the antifouling property is particularly excellent. Is preferred.

  As the polysiloxane (a1), it is preferable to use a polysiloxane chain as a main chain in which a polyalkylene oxide chain is grafted as a side chain in a pendant form. The polyalkylene oxide chain is an alkylene oxide opened. Those consisting of ring reactants are preferred.

  By using the urethane (meth) acrylate (A1-1) obtained by using the polysiloxane (a1), it is possible to produce a high-hardness molded product excellent in antifouling property against oil and dust. it can.

  As said polyalkylene oxide chain | strand, polyalkylene oxides, such as a polyethylene oxide, a polypropylene oxide, a polybutylene oxide, are preferable, for example, and a polyethylene oxide is more preferable. As said polyalkylene oxide, the 2-15 mol addition product of alkylene oxide is preferable.

  The polysiloxane (a1) has an active hydrogen atom-containing group together with the polyalkylene oxide chain. Such an active hydrogen atom-containing group is preferably a hydroxyl group.

  Specific examples of the polysiloxane (a1) include those represented by the following general formula (1).

In the general formula (1), R ¹ represents an alkylene group having 1 to 6 carbon atoms, R ² and R ³ each independently represents an alkylene group having 2 to 4 carbon atoms, and R ⁴ represents Each independently represents an alkyl group having 1 to 8 carbon atoms or a phenyl group. In general formula (1), a and b are each independently an integer of 1 to 8, and m and n are each independently an integer of 1 to 10.

  Examples of the commercially available polysiloxane (a1) include FZ-2191 and SH-3771 manufactured by Toray Dow Corning Co., Ltd., and KF353A manufactured by Shin-Etsu Chemical Co., Ltd., but are not limited thereto. is not.

  As said polysiloxane (a1), it is preferable to use what has a hydroxyl equivalent of 300-8000, and it is more preferable to use what is 700-3000. By using the polysiloxane (a1) having a hydroxyl group equivalent within this range, a molded product having particularly excellent decontamination property can be produced.

  As said polysiloxane (a1), it is preferable to use what the mass ratio of the said polyalkylene oxide chain part and a polysiloxane chain part is 1 / 0.05 to 1/110, 1/2 to 1 / It is more preferable to use 50, and it is particularly preferable to use what is 1/2 to 1/5. By using the polysiloxane (a1) having a mass ratio in the above range, a molded product particularly excellent in antifouling property and the like can be produced.

  The polysiloxane (a1) may have other molecular chains in addition to the polyalkylene oxide chain part and the polysiloxane chain part, for example, the polyalkylene oxide chain part and the polysiloxane chain part. However, it may be bonded through other molecular chains or chemical bonds.

  The isocyanate group-containing compound (b) used in the production of the urethane (meth) acrylate (A1) has two or more isocyanate groups in the molecule. For example, hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4 -Cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, 2,4-tolylene diisocyanate, its isomer or a mixture of these isomers, 4,4-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), xylylene diisocyanate, norbornene diisocyanate Or an adduct of the diisocyanate and a trihydric or higher aliphatic polyhydric alcohol such as trimethylolpropane, an isocyanurate structure which is a trimer of diisocyanate, Biuret by reaction with isocyanate and water, or polymeric MDI and the like can be used.

  From the viewpoint of preventing discoloration of the cured product of the radical polymerizable resin composition (B), the isocyanate group-containing compound (b) is an aliphatic or alicyclic isocyanate group-containing compound having two or more isocyanate groups. Is preferably used.

  Examples of the polymerizable monomer (d) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, or ethylene oxide adducts thereof, propylene Oxide adduct, butylene oxide adduct, tetrahydrofuran adduct, ε-caprolactan adduct or ε-caprolactam adduct, or trimethylolpropane di (meth) acrylate, trimethylolpropane acrylate methacrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Penta (meth) acrylate etc. can be used individually or can use 2 or more types together. Among these, it is preferable to use pentaerythritol tri (meth) acrylate because it is excellent in the reactivity of the radical curing reaction of the molding material and improves the hardness of the surface of the molded product.

  Moreover, when producing the urethane (meth) acrylate (A1), in addition to the polymerizable monomer (d), for the purpose of preventing the curing inhibition of the radical polymerizable resin composition (B) by air, A hydroxyl group-containing allyl ether compound may be used.

  Examples of the hydroxyl group-containing allyl ether compound include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, and tripropylene. Glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane diallyl ether Glyceryl diallyl ether, pentaerythritol triallyl ether, etc. Can be used allyl ether compounds such valence alcohols, it is preferred to use the allyl ether compound having inter alia one hydroxyl group.

  The urethane (meth) acrylate (A1) can be produced, for example, by the following two-stage reaction process.

  In the first stage reaction step, the compound (c) having a structure derived from the polysiloxane (a) and an isocyanate group is obtained by reacting the polysiloxane (a) with the isocyanate group-containing compound (b). It is a process to obtain. At this time, the equivalent ratio of the isocyanate group (—NCO) of the isocyanate group-containing compound (b) to the active hydrogen atom-containing group such as a hydroxyl group of the polysiloxane (a) (NCO / active hydrogen atom-containing group). Is preferably 1.5 to 2.5.

  The first stage reaction step is preferably performed in a temperature range of room temperature to about 100 ° C. Moreover, although the reaction process of the 1st step | paragraph can also be performed under a non-solvent, the polymerizable unsaturated monomer as a crosslinking component mentioned later can also be used as a solvent as needed.

  In the first reaction step, a catalyst may be used as necessary.

  Examples of the catalyst include organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate; organic tin compounds such as tin octylate, dibutyltin oxide, and sibutyltin dilaurate; stannous chloride, stannous bromide A known catalyst such as acid or alkali such as stannous iodide can be used. It is preferable that the addition amount of these catalysts is 10-10000 ppm with respect to the whole preparation amount.

  The second reaction step is a step of reacting the isocyanate group of the compound (c) obtained in the first reaction step with the hydroxyl group of the polymerizable monomer (d). .

  The polymerizable monomer (d) is preferably used so that the hydroxyl group it has is in the range of 1 to 2 equivalents relative to 1 equivalent of the isocyanate group of the compound (c).

  The second stage reaction step is preferably performed in a temperature range of room temperature to about 90 ° C. Moreover, although the reaction process of the 2nd stage can also be performed under a non-solvent, the polymerizable unsaturated monomer as a crosslinking component mentioned later can also be used as a solvent as needed.

  In the second stage reaction step, if necessary, the same catalyst as that exemplified as being usable in the first stage reaction step may be used.

  Moreover, in order to suppress the radical polymerization of the polymerizable unsaturated double bond of the polymerizable monomer (d), a radical polymerization inhibitor can be used as necessary.

  As the radical polymerization inhibitor, for example, hydroquinone monomethyl ether, di-tert-butyl hydroquinone, p-tert-butylcatechol, phenothiazine and the like can be used. The addition amount of the radical polymerization inhibitor is preferably about 10 to 10,000 ppm with respect to the total charged amount.

  Examples of the ester (meth) acrylate (A2) having a polysiloxane structure that can be used as the compound (A) include a reaction between the polysiloxane (a) having the active hydrogen atom-containing group and an unsaturated monobasic acid. A reaction product of a polysiloxane having a carboxyl group and a monomer having at least one polymerizable unsaturated double bond and an active hydrogen atom-containing group. Specifically, if it is a commercial product, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X-22-174DX, X- manufactured by Shin-Etsu Chemical Co., Ltd. 22-2426, X-22-2475, etc. can be used.

  Examples of the polysiloxane (a) having an active hydrogen atom-containing group include X-22-160AS, KF-6001, KF-6002, and KF-6003 manufactured by Shin-Etsu Chemical Co., Ltd. Can do. Moreover, as the polysiloxane (a) having the active hydrogen atom-containing group, polysiloxane (a1) having a polyalkylene oxide chain in the side chain can also be used.

  Examples of the polysiloxane having a carboxyl group include commercially available products such as X-22-162C and X-22-3710 manufactured by Shin-Etsu Chemical Co., Ltd.

  Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid, monomethylmalate, monopropylmalate, monobutylmalate, and mono (2-ethylhexyl) malate. These can be used, and these can be used alone or in combination of two or more.

  Reaction of polysiloxane (a) having active hydrogen atom-containing group with unsaturated monobasic acid, polysiloxane having carboxyl group, at least one polymerizable unsaturated double bond and active hydrogen atom-containing group For example, the reaction with the monomer having an ester can be carried out in the presence of an esterification catalyst or, if necessary, a radical polymerization inhibitor.

  As the esterification catalyst, for example, tertiary amines such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane, and diethylamine hydrochloride can be used. The amount of the esterification catalyst used is preferably about 100 to 300,000 ppm with respect to the total amount charged.

  Examples of the epoxy (meth) acrylate (A3) having a polysiloxane structure that can be used as the compound (A) include, for example, a polysiloxane having an epoxy group and (meth) acrylic acid or a derivative thereof as an esterification catalyst. And an esterification catalyst that is obtained by reacting in the presence of a radical polymerization inhibitor, if necessary, a polysiloxane having a carboxyl group, and a compound having a (meth) acryl group and an epoxy group. And the like obtained by reacting in the presence of a radical polymerization inhibitor.

Examples of the polysiloxane having an epoxy group include KF-105, X-22-163A, X-22-163B, X-22-169AS, and X-22-169B manufactured by Shin-Etsu Chemical Co., Ltd. be able to.
Moreover, as the polysiloxane having a carboxyl group, the same ones as described above can be used.
Moreover, glycidyl methacrylate etc. can be used as a compound which has the said (meth) acryl group and an epoxy group.

  The production of the epoxy (meth) acrylate (A3) is preferably performed using an esterification catalyst in a temperature range of 60 to 140 ° C, more preferably 80 to 120 ° C.

  As the obtained epoxy (meth) acrylate (A3), those having an epoxy equivalent of 200 to 2500 are preferable.

In addition to the essential components, the radical polymerizable resin composition (B) may be, if necessary, urethane (meth) acrylate or epoxy (meth) acrylate having no structure derived from the polysiloxane (a). Other commonly known unsaturated polyester resins, polyurethane resins, acrylic resins, alkyd resins, urea resins, melamine resins, polyvinyl acetate, vinyl acetate copolymers, polydiene elastomers, saturated polyester resins, Saturated polyethers, celluloses and derivatives thereof, fats and oils, and other conventional natural and synthetic polymer compounds may be contained within a range not impairing the effects of the present invention.
For example, when the urethane (meth) acrylate (A1) is used as the compound (A), the urethane (meth) acrylate (D) or unsaturated polyester having no structure derived from the polysiloxane (a). Resin (E) is preferably used in combination, and particularly urethane (meth) acrylate (D) having no structure derived from polysiloxane (a) is preferably used in combination.

The urethane (meth) acrylate (A1) and the urethane (meth) acrylate (D) having no structure derived from the polysiloxane (a) have a mass ratio [(A1) / (D)] of 2 / It is preferable to use a combination in the range of 98 to 25/75, and it is more preferable that the mass ratio is 5/95 to 15/85.
When using in the said mass ratio, the said urethane (meth) acrylate (A1) obtained by using the polysiloxane (a1) which has the said polyalkylene oxide chain in a side chain as said urethane (meth) acrylate (A1). It is particularly preferable to use -1) in order to obtain a molded product having high hardness and excellent antifouling property against oil and dust.

  In the radical polymerizable resin composition (B), a polymerizable unsaturated monomer as a crosslinking component can be used as necessary.

  Examples of the polymerizable unsaturated monomer include styrene, α-methylstyrene, chlorostyrene, dichlorostyrene, divinylbenzene, tert-butylstyrene, vinyltoluene, vinyl acetate, diarylphthalate, triarylcyanurate, or Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meta ) Lauryl acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate 2-hydroxy Butyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (Meth) acrylate, ethylene glycol mono 2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate , Diethylene glycol mono 2-ethylhexyl Ether (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, polytetramethylene glycol dimethacrylate, 1,3-butylene glycol di (meth) acrylate, , 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy 1,3-dimethacryloxypropane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2 , 2-bis [4- (methacryloxy / diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy / polyethoxy) phenyl] propane, tetraethylene glycol di (meth) acrylate, bisphenol A ethylene oxide modified di (meth) ) Unsaturated monomers that can crosslink with resins, such as acrylates, isocyanuric acid ethylene oxide modified di (meth) acrylates, acrylic esters or methacrylic esters such as pentaerythritol di (meth) acrylate monostearate, etc. Unsaturated oligomers of the unsaturated monomer and the monomers.

  Furthermore, for the purpose of improving hardness, antifouling property and antifouling removal durability, abrasion resistance, scratch resistance, peristaltic resistance, chemical resistance, etc. of the cured product surface, a polyfunctional unsaturated monomer, preferably 3 It is preferable to use a functional or higher (meth) acrylic acid ester monomer. Specifically, trimethylolpropane tri (meth) acrylate, tetramethylol metal tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) Acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, isocyanuric acid ethylene oxide modified (n = 3) tri (meth) acrylate, isocyanuric acid ethylene oxide (n = 3) .epsilon.-caprolactone modified tri (meth) Polymerizable monomers such as acrylate, dipentaerythritol penta- and hexa- (meth) acrylate, and pentaerythritol tetra (meth) acrylate can be used in combination.

  The radical polymerizable resin composition (B) can be cured by any of curing methods such as curing by active energy rays, heat curing by using a peroxide, and room temperature curing by using a peroxide and a reducing agent. However, since a molding surface with higher hardness can be formed, heat curing or curing with active energy rays is most preferable. In the case of curing with an active energy ray, the mold (II) is preferably a transparent film or glass.

  When curing with active energy rays, it is preferable to use a photopolymerization initiator as a curing agent.

  Examples of the photopolymerization initiator include benzophenones such as benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone and 4-phenylbenzophenone; methyl orthobenzoylbenzoate; tert-butylanthraquinone, Anthraquinones such as 2-ethylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one , Benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino Acetophenones such as -1- (4-morpholinophenyl) -butanone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis Acylphosphine oxides such as (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; methylbenzoylformate; -Bisacridinyl heptane; 9-phenylacridine and the like can be used alone or in combination of two or more.

  When curing by active energy rays, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate together with the photopolymerization initiator as necessary. A known photosensitizer such as amyl 4-dimethylaminobenzoate or 4-dimethylaminoacetophenone may be used.

  When heat-curing using a peroxide, as a curing agent, for example, diacyl peroxide type, peroxy ester type, hydroperoxide type, dialkyl peroxide type, ketone peroxide type, peroxy ketal type, Peroxides such as alkyl peresters and percarbonates can be used.

  When the radical polymerizable resin composition (B) is cured at room temperature, the above peroxide and an organic metal salt such as cobalt naphthenate and cobalt octenoate as a curing accelerator, dimethylaniline, diethylaniline, and paratoluidine. Aromatic amine compounds such as can be used in combination.

  The curing agent is preferably used in a range of 0.1 to 10 parts by mass and more preferably in a range of 1 to 5 parts by mass with respect to 100 parts by mass of the radical polymerizable resin composition (B). preferable.

  A polymerization inhibitor may be used in the radical polymerizable resin composition (B) as necessary. Examples of the polymerization inhibitor include trihydroquinone, hydroquinone, 1,4-naphthoquinone, parabenzoquinone, toluhydronone, p-tert-butylcatechol, 2,6-di-tert-butyl-4-methylphenol, and the like. Can be mentioned. It is preferable that the usage-amount of a polymerization inhibitor is 10-1000 ppm in a radically polymerizable composition.

  Furthermore, the radical polymerizable resin composition (B) includes, for example, a filler, a fiber reinforcing material, a thixotropic agent as a sagging stopper, an ultraviolet absorber, a pigment, a thickener, a thickener, a low shrinkage agent, An anti-aging agent, a plasticizer, an aggregate, a flame retardant, a stabilizer, an antifoaming agent, a release agent and the like may be blended.

  Examples of the filler include calcium carbonate, aluminum hydroxide, aluminum oxide (alumina), calcium sulfate, and the like.

  Examples of the fiber reinforcement include glass fiber, aramid fiber, vinylon fiber, polyester fiber, nylon fiber, carbon fiber, and metal fiber. Further, the form of the fiber is not particularly limited as long as the reinforcing effect by the fiber is obtained. For example, a cloth, a roving cloth, a strand obtained by cutting a roving, a chopped strand mat, a roving cloth and a chopped strand are used. A pair mat that has been stitched together may be used.

Examples of the thixotropic material include amide compounds, silicon oxide (SiO ₂ ) powders having silanol groups represented by fumed silica, smectite, calcium sulfate whiskers, inorganic bentonite compounds, and the like. System compounds are preferred.

  When radically polymerizable resin composition (B) contains components other than the said compound (A), content of the said compound (A) in this composition (B) is 0.02-25 mass%. It is preferable that it is 0.2 to 20% by mass. By setting it as such a range, the effect of this invention is more fully acquired.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(Synthesis Example 1)
<Urethane (meth) acrylate (A-1) having a polysiloxane-derived structure having a polyalkylene oxide chain in the side chain and urethane having no structure derived from polysiloxane having a polyalkylene oxide chain in the side chain (meta ) Preparation of mixture (Z) with acrylate (E-1)>
In a 2 liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, polysiloxane having a polyalkylene oxide chain in the side chain (FZ-2191 manufactured by Toray Dow Corning Co., Ltd., 37 parts by mass (0.03 mol) of hydroxyl equivalent 1222) was charged, 206 parts by mass (1 mol) of norbornene diisocyanate was added, and the mixture was reacted at 80 ° C. for 2 hours while suppressing heat generation.

  After confirming that the NCO equivalent was 123, which was almost the same as the theoretical value when all the hydroxyl groups of the polysiloxane reacted with isocyanate groups, the mixture was cooled to 50 ° C. and 375 parts by mass of pentaerythritol triacrylate (1 .26 mol) and 122 parts by mass (1.05 mol) of 2-hydroxyethyl acrylate were added, 0.02 part by mass of tin catalyst was added as a reaction promoting catalyst, and the mixture was reacted at 90 ° C. for 7 hours in an air atmosphere.

  After NCO% becomes 0.3 mass% or less, by adding 0.1 part by mass of hydroquinone, urethane (meth) acrylate (A-1) having a polysiloxane-derived structure having a polyalkylene oxide chain in the side chain ) And urethane (meth) acrylate (E-1) having a polysiloxane-derived structure having a polyalkylene oxide chain in the side chain and having a mass ratio [(A-1) / (E-1)] of 7 A mixture (Z) of .5 / 92.5 was obtained.

(Synthesis Example 2)
<Preparation of unsaturated polyester (E-2) having no polysiloxane-derived structure having a polyalkylene oxide chain in the side chain>
In a 2-liter four-necked flask equipped with a thermometer, stirrer, inert gas inlet, and reflux condenser, 456 parts by mass of propylene glycol (6 mol), 310 parts by mass of ethylene glycol (5 mol), and 812 parts by mass of fumaric acid. (7 mol) and 444 parts by mass (3 mol) of phthalic anhydride were charged, and heating was started under a nitrogen stream. A dehydration condensation reaction is performed at an internal temperature of 200 ° C. by a conventional method. When the acid value reaches 30 KOH mg / g, the mixture is cooled to 180 ° C. and 0.06 part by mass of tolhydroquinone is added to thereby derive from polysiloxane. Unsaturated polyester (E-2) having no structure was obtained.

Example 1
Molded articles were produced according to the composition ratios shown in Table 1. That is, with respect to 40 parts by mass of the mixture (Z) prepared in Synthesis Example 1 and 60 parts by mass of pentaerythritol triacrylate, Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was replaced with the mixture (Z) and pentaerythritol triacrylate. The radical polymerizable resin composition (B) was prepared by dissolving so as to be 5% by mass with respect to the total amount. And this radically polymerizable resin composition (B) was apply | coated so that it might be set to 20 g / scale ² to the decorative paper side surface of the base material which consists of a plywood with which decorative paper was stuck. A mold made of a polyethylene terephthalate (PET) film that has been subjected to a silicon mold release process, which will be described later, is placed on the coated surface, and is uniformly spread by a rubber roller from above the mold, and a UV lamp 120W metal halide (UV irradiation amount 1000 mJ). / Cm ² ) to cure the radical polymerizable resin composition (B) and then remove the mold to obtain a molded product.

(Example 2)
Molded articles were produced according to the composition ratios shown in Table 1. That is, 12 parts by mass of the mixture (Z) prepared in Synthesis Example 1, 42 parts by mass of the unsaturated polyester (E-2) obtained in Synthesis Example 2, 18 parts by mass of pentaerythritol triacrylate, 28 parts by mass of styrene, 6% by mass A radical polymerizable resin composition (B) was prepared by mixing 0.5 parts by mass of cobalt naphthenate (Co-NAPHTHENATE 6%, manufactured by DIC Corporation) and 1 part by mass of methyl ethyl ketone peroxide (Permec N, manufactured by NOF Corporation). ) Was prepared. And this radically polymerizable resin composition (B) was apply | coated so that it might be set to 20 g / scale ² to the decorative paper side surface of the base material which consists of a plywood with which decorative paper was stuck. The radical polymerizable resin composition (B) is prepared by placing a mold made of a polyethylene terephthalate (PET) film that has been subjected to a silicon release treatment, which will be described later, on the coated surface, and causing a curing reaction at 25 ° C. for 90 minutes. After curing, a mold was obtained by removing the mold.

(Reference Example 1)
Molded articles were produced according to the composition ratios shown in Table 1. That is, with respect to 40 parts by mass of the mixture (Z) prepared in Synthesis Example 1 and 60 parts by mass of pentaerythritol triacrylate, Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was replaced with the mixture (Z) and pentaerythritol triacrylate. The radical polymerizable resin composition (B) was prepared by dissolving so as to be 5% by mass with respect to the total amount. And this radically polymerizable resin composition (B) was apply | coated so that it might be set to 20 g / scale ² on the decorative paper side surface of the base material which consists of a plywood with which decorative paper was stuck. A mold made of a silicon plate, which will be described later, is placed on the coating surface, and is uniformly extended from above the mold with a rubber roller, and the radical polymerizable property is obtained using a UV lamp 120W metal halide (UV irradiation amount 1000 mJ / cm ² ). After the resin composition (B) was cured, a molded product was obtained by removing the mold.

(Example 3)
Molded articles were produced according to the composition ratios shown in Table 1. That is, with respect to 40 parts by mass of the mixture (Z) prepared in Synthesis Example 1 and 60 parts by mass of pentaerythritol triacrylate, Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) was replaced with the mixture (Z) and pentaerythritol triacrylate. The radical polymerizable resin composition (B) was prepared by dissolving so as to be 5% by mass with respect to the total amount. And this radically polymerizable resin composition (B) was apply | coated so that it might be set to 20 g / scale ² on the decorative paper side surface of the base material which consists of a plywood with which decorative paper was stuck. A mold made of a polyethylene terephthalate (PET) film having an embossed pattern, which has been subjected to silicon release treatment described later, is placed on the coated surface, and uniformly spread by a rubber roller from the mold, and UV lamp 120W After the radical polymerizable resin composition (B) was cured using metal halide (UV irradiation amount 1000 mJ / cm ² ), the mold was removed to obtain a molded product with an embossed pattern on the surface. .

(Reference Example 2)
Molded articles were produced according to the composition ratios shown in Table 1. That is, 12 parts by mass of the mixture (Z) prepared in Synthesis Example 1, 42 parts by mass of the unsaturated polyester (E-2) obtained in Synthesis Example 2, 18 parts by mass of pentaerythritol triacrylate, 28 parts by mass of styrene, 6% by mass A radically polymerizable resin composition (B ) Was prepared. And this radically polymerizable resin composition (B) was apply | coated (200 g / m < ² >) on the surface of the type | mold which consists of the glass plate in which the silicon mold release process mentioned later was given, and it was left to stand for 30 minutes in a 25 degreeC environment. As a result, the radical polymerizable resin composition (B) was semi-cured to form a gel coat layer.

Next, an unsaturated polyester resin compound [(Sandoma TP-254, manufactured by DH Material Co., Ltd.) / (CWL-326S, manufactured by Sumitomo Chemical Co., Ltd.) / (Parkadox 16, Kayaku Akzo Co., Ltd.) is formed on the surface of the gel coat layer. (Made by Co., Ltd.) = 100/200/1] (mass ratio) was cast (1800 g / scale ² ), cured at 80 ° C. for 60 minutes, and then the mold was removed to obtain a molded product.

(Reference Example 3)
Molded articles were produced according to the composition ratios shown in Table 1. That is, in a mixture of 24 parts by mass of the mixture (Z) prepared in Synthesis Example 1, 24 parts by mass of the unsaturated polyester (E-2) obtained in Synthesis Example 2, 36 parts by mass of pentaerythritol triacrylate and 16 parts by mass of styrene, After casting a compound of 100 parts by mass of CWL-326S (manufactured by Sumitomo Chemical Co., Ltd.) and 1 part by mass of Parkardox 16 (manufactured by Kayaku Akzo Co., Ltd.) (1800 g / scale ² ) and curing at 80 ° C. for 60 minutes. The molded product was obtained by removing the mold.

Example 4
A molded product was produced in the same manner as in Example 1 except that the composition ratios shown in Table 2 were changed.
In Tables 1 and 2, “X-22-164A” is an ester (meth) acrylate (A2) having a polysiloxane structure manufactured by Shin-Etsu Chemical Co., Ltd.

(Comparative Examples 1-4)
A molded product was produced in the same manner as in Example 1 except that the composition ratios shown in Table 2 were changed.
In Tables 1 and 2, “FZ-2191” is a polysiloxane (a1) manufactured by Toray Dow Corning Co., Ltd., and corresponds to a polysiloxane compound having no double bond.

[Evaluation of antifouling and decontamination]
The surface of the molded product (demolded surface) was written using oil-based magic (Pentel Co., Ltd. pen, oil-based, medium black), and the appearance of the coating surface after wiping with a dry cloth was observed. . “O” indicates that no oil-based magic ink remains on the surface of the film, “△” indicates that some of the ink remains, and “△” indicates that the ink is practically usable. Was evaluated as “×”. The evaluation results are shown in Table 1.

[Evaluation of sustainability of antifouling and decontamination]
Write on the surface of the molded product (demolded surface) using the above-mentioned oil-based magic, and repeat the process of wiping it with a dry cloth at the same location on the surface of the coating. After wiping with, the number of times until the characters disappeared was examined to determine how long the antifouling property and decontamination property were maintained. The case where the number of times was 10 times or more was evaluated as “◯”, the case where it was 5 times or more and less than 10 times was evaluated as “Δ”, and the case where it was less than 5 times was evaluated as “X”. The evaluation results are shown in Table 1.

[Mold making]
(Production of silicon-treated PET film)
A resin composition containing 60 parts by mass of the mixture (Z) prepared in Synthesis Example 1, 40 parts by mass of methyl ethyl ketone, and 5 parts by mass of Irgacure 184 (manufactured by Ciba Japan Co., Ltd.) is applied to the surface of the polyethylene terephthalate (PET) film. PET film having a silicon coating by applying by a bar coating method, drying using a dryer (50 ° C., 1 minute), and then irradiating the coating surface with ultraviolet rays (UV irradiation amount 1000 mJ / cm ² ). (Silicon-treated PET film) was produced. This PET film was used as a mold for molding.

(Production of silicon-treated glass plate)
A glass plate having a silicon coating film (silicone) is applied by applying a silicone mold release agent (Chemlyss Corp., AF-7) to a glass plate using a cloth and baking using a dryer (120 ° C., 5 minutes). Treated glass plate). This glass plate was used as a mold for molding.

(Silicon plate)
A silicon sheet made by Togawa Rubber Co., Ltd. was used.

(Silicone-untreated PET film)
As the silicon-untreated PET film, the PET film before silicon treatment used for producing the silicon-treated PET film was used.

(Production of fluorinated PET film)
A PET film having a fluorine coating by spray-coating a fluorine-based mold release agent (Daikin Kogyo Co., Ltd., Die Free GA-6010) on the surface of the polyethylene terephthalate film and drying using a dryer (80 ° C., 3 minutes). (Fluorine-treated PET film) was produced. This PET film was used as a mold for molding.

[Creativity]
Of the designs imparted to the surface of the molded product, “mirror surface” indicates that a smooth surface is imparted, and “emboss” indicates that an emboss pattern having a fine uneven shape is imparted.

Claims (4)

  Compound (A) which is urethane (meth) acrylate having a structure derived from polysiloxane (a1) having a polyalkylene oxide chain in the side chain and a polymerizable unsaturated double bond on the surface of the substrate (C) and curing After forming a layer made of the radically polymerizable resin composition (B) containing an agent, the mold (in which the mold release treatment is performed on the surface of the uncured or semi-cured layer with the silicon mold release agent (I) ( II) is mounted, and then the radical polymerizable resin composition (B) is cured.   The compound (A) comprises a polysiloxane (a1) having a polyalkylene oxide chain in the side chain, and a polymerizable monomer (d) having a hydroxyl group and at least one polymerizable unsaturated double bond, The method for producing a molded article according to claim 1, which is urethane (meth) acrylate (A1) having a polyalkylene oxide chain in the side chain bonded through the group-containing compound (b).   The radical polymerizable resin composition (B) comprises a polysiloxane (a1) having a polyalkylene oxide chain in the side chain, a polymerizable monomer having a hydroxyl group and at least one polymerizable unsaturated double bond (d ) And a urethane (meth) acrylate (A1) having a polyalkylene oxide chain in the side chain and a polysiloxane having a polyalkylene oxide chain in the side chain (a1) bonded via the isocyanate group-containing compound (b) 3) The method for producing a molded article according to claim 1 or 2, which comprises urethane (meth) acrylate (D) having no structure derived from.   The polysiloxane (a1) having the polyalkylene oxide chain as a side chain is obtained by grafting a polyalkylene oxide chain as a side chain to a polysiloxane chain as a main chain, and the polyalkylene oxide chain is an alkylene oxide. It is a 2-15 mol addition product, The manufacturing method of the molded article as described in any one of Claims 1-3.