JP6172983B2 - Resin product and manufacturing method thereof - Google Patents

Description

  The present invention relates to a resin product and a method for producing the same, and more particularly to a resin product that can be suitably used as a resin glass (organic glass) and a method for advantageously producing such a resin product.

  Conventionally, resin products having both excellent moldability and light weight have been widely used as, for example, interior and exterior parts of vehicles such as automobiles, electrical, electronic parts, and building parts. Among these resin products, for example, highly transparent resin products made of polycarbonate molded products are superior in terms of lightness, impact resistance and workability compared to inorganic glass. As resin glass which substitutes for glass, it is used for the window glass of vehicles, such as a car, various displays, or the cover of various instruments, etc., for example.

  As is generally known, such polycarbonate resin products have problems in weather resistance such as discoloration and strength reduction when exposed to ultraviolet rays, and are more resistant to abrasion than inorganic glass. It also has the disadvantage of being inferior (wear resistance and scratch resistance). Therefore, if the resin product made of polycarbonate is used outdoors, such as a window glass of an automobile, and the surface damage is a serious defect, such resin is used. It was necessary to take measures to improve the weather resistance and abrasion resistance of the product.

  Under such circumstances, for example, in Japanese Patent Application Laid-Open No. 2010-253683 (Patent Document 1), as a resin product (referred to as a plastic laminate in the above publication) applied to a window glass of an automobile, polycarbonate or the like is used. An undercoat layer made of an acrylic resin rich in weather resistance is laminated on the surface of a resin base material made of a resin molded body, and a plasma CVD layer of a silicon compound having excellent abrasion resistance on the undercoat layer A structure obtained by further laminating a top coat layer made of However, in such a resin product, the topcoat layer may be peeled off from the undercoat layer by a weather resistance test in which ultraviolet rays are irradiated. That is, such a resin product cannot be said to have sufficient adhesion of the topcoat layer to the undercoat layer.

  On the other hand, a polyurethane resin is also known as a resin having high weather resistance. In addition, it has been confirmed by tests of the present inventors that a thin film made of polyurethane resin exhibits higher adhesion with a thin film made of silicon compound than a thin film made of acrylic resin. Therefore, in a resin product in which an undercoat layer and a topcoat layer made of a silicon compound are laminated on the surface of a polycarbonate resin base material, the undercoat layer is replaced with an acrylic resin with a polyurethane resin. If constituted, it is considered that sufficient adhesion between the undercoat layer and the topcoat layer can be secured in addition to excellent weather resistance and abrasion resistance.

  However, the present inventor conducted a heat resistance test on a resin product in which an undercoat layer and a topcoat layer made of polyurethane resin are laminated on the surface of a polycarbonate resin substrate under the condition of 110 ° C. × 24 hours. As a result, generation of cracks was observed in the topcoat layer. From this, resin products in which an undercoat layer made of polyurethane resin and a topcoat layer made of silicon compound are laminated on the surface of a polycarbonate resin base material have insufficient heat resistance. It has become clear that there is still room for improvement.

JP 2010-253683 A

  Here, the present invention was made in the background as described above, the place to be solved is an undercoat layer made of polyurethane resin on the surface of a polycarbonate resin substrate, An object of the present invention is to provide an improved structure so that sufficient heat resistance can be exhibited in a resin product in which a top coat layer made of a silicon compound is laminated. Another object of the present invention is to provide a method for advantageously producing a resin product having such a structure.

  In order to solve such a problem, the present inventor first sought the reason why cracks occur during heating in the topcoat layer formed on the undercoat layer made of polyurethane resin. As a result, an undercoat layer made of a polyurethane resin obtained by reacting a diisocyanate having a linear structure generally used for forming a polyurethane resin and a diol is stretched by heating as compared to a topcoat layer made of a silicon compound. Because the amount is large, the elongation during heating of the topcoat layer that is in close contact with the undercoat layer cannot follow the elongation of the undercoat layer, and it is believed that heating will cause cracks in the topcoat layer. I got a conclusion. As a result of further earnest research, the present inventor has obtained a cyclic compound formed of three isocyanate groups in order to obtain a polyurethane resin capable of forming an undercoat layer with a small extension amount upon heating. An undercoat layer made of a polyurethane resin obtained by reacting a diisocyanate isocyanurate having at least one of three atomic groups bonded to the cyclic compound having a cyclo ring and a polyol, It has been found that elongation during heating can be advantageously suppressed as compared with an undercoat layer composed of a polyurethane resin obtained by a reaction between a diisocyanate having a structure and a diol.

That is, the present invention has been completed based on such knowledge, and the gist thereof is that an undercoat layer made of a polyurethane resin is formed on the surface of a resin base material made of a polycarbonate resin molded product. The resin product is formed by laminating a top coat layer made of a silicon compound on the undercoat layer, and the polyurethane resin constituting the undercoat layer is an isocyanurate of isophorone diisocyanate in the resin product characterized and Turkey, such a reaction product of a polyol.

On the other hand , in the present invention, in order to solve the above-described problems, an undercoat layer made of polyurethane resin is laminated on the surface of a resin base material made of a polycarbonate resin molded product, and the undercoat layer is formed. A method for producing a resin product in which a top coat layer made of a silicon compound is further formed on a coat layer, the method comprising: (a) preparing the resin substrate; and (b) an isocyanurate of isophorone diisocyanate. And a polyol are mixed on the surface of the resin substrate, while the isocyanurate of isophorone diisocyanate and the polyol are reacted to form the mixture layer of the resin substrate. Curing on the surface and forming an undercoat layer made of the polyurethane resin on the surface; and (c) the undercoat The coating layer, a method for producing a resin product which comprises a step of laminating forming the top coat layer consisting of the silicon compound may, also, to its gist.

  In short, in the resin product according to the present invention, since the extension of the undercoat layer during heating is advantageously suppressed, the elongation of the topcoat layer cannot follow the extension of the undercoat layer during heating. It is possible to effectively prevent the top coat layer from being cracked. Therefore, in the resin product according to the present invention, excellent heat resistance that cannot be obtained by conventional products can be exhibited extremely effectively.

  Further, according to the method for producing a resin product according to the present invention, a resin product having excellent heat resistance can be produced very advantageously without performing a special process.

It is a fragmentary sectional view showing one embodiment of a resin product having a structure according to the present invention. It is explanatory drawing which shows an example of the process implemented when obtaining the resin product shown by FIG. 1, Comprising: It is explanatory drawing which shows the state which has laminated | stacked the undercoat layer on the surface of the resin base material. It is explanatory drawing which shows the process implemented following the process shown by FIG. 2, Comprising: The state which has further laminated | stacked the topcoat layer on the undercoat layer laminated | stacked and formed on the resin base material surface is shown. It is explanatory drawing.

  Hereinafter, in order to clarify the present invention more specifically, embodiments of the present invention will be described in detail with reference to the drawings.

  First, FIG. 1 shows a resin glass 10 for a rear window of an automobile in a partial cross-sectional form as an embodiment of a resin product having a structure according to the present invention. As is clear from FIG. 1, the resin glass 10 has a resin base material 12. And the undercoat layer 14 is laminated | stacked and formed on the surface and the back surface (upper surface and lower surface in FIG. 1) of this resin base material 12, respectively. Further, a top coat layer 16 is further laminated on the surface of each of the undercoat layers 14 and 14 opposite to the resin substrate 12 side. In the following, for convenience, the upper surface in FIG. 1 is referred to as the front surface, and the lower surface in FIG. 1 is referred to as the back surface.

  More specifically, the resin base material 12 has a transparent flat plate shape, and is formed of a resin molded product that is injection-molded using polycarbonate. The resin base material 12 may be molded by a method other than injection molding as long as it is a polycarbonate resin molded product. Moreover, the thickness of the resin base material 12 is not limited at all, and is appropriately determined according to the use and required characteristics of the resin glass 10. Here, the thickness is about 2 to 7 mm. Is done.

  The undercoat layer 14 covers the entire surface of the resin substrate 12 on both the front and back surfaces for the purpose of imparting weather resistance based on ultraviolet resistance or the like to the resin glass 10. As described above, each layer is directly laminated, and is formed of a polyurethane resin thin film. In addition, since the undercoat layer 14 is made of a polyurethane resin, the adhesion between the undercoat layer 14 and a topcoat layer 16 made of a silicon compound described later is sufficiently enhanced, so that it can be used in a high-temperature environment. The top coat layer 16 is prevented from peeling off from the undercoat layer 14 due to long-term use.

  The thickness of such an undercoat layer 14 is not particularly limited, but is generally about 1 to 40 μm. This is because if the thickness of the undercoat layer 14 is thinner than 1 μm, it is too thin and it may be difficult to impart sufficient weather resistance to the resin glass 10. On the other hand, even if the thickness of the undercoat layer 14 is thicker than 40 μm, it is difficult to further improve the weather resistance of the resin glass 10. On the other hand, material costs are wasted and the formation time of the undercoat layer 14 is This is because it may become long.

  And in the resin glass 10 of this embodiment, the polyurethane resin which comprises the undercoat layer 14 consists of a reaction product (polymer) of the diisocyanate isocyanurate body and polyol which have a special molecular structure.

  That is, here, as a curing agent for forming the polyurethane resin constituting the undercoat layer, a cyclic compound formed of three isocyanate groups, and the three isocyanate groups bonded to the cyclic compound, Is an isocyanurate form (trimer) of a diisocyanate having three atomic groups each containing a separate isocyanate group, wherein the three atomic groups bonded to the cyclic compound each have a cyclo ring Or two of the three atomic groups have a cyclo ring and the remaining one atomic group has a straight chain structure, or only one of the three atomic groups has a cyclo ring In addition, any one of the remaining two atomic groups having a linear structure is appropriately selected and used.

  Of the three types of isocyanurates of diisocyanates, three atomic groups bonded to a cyclic compound formed by three isocyanate groups each have a cyclo ring. An isocyanurate form of isophorone diisocyanate having a cyclo ring having the structure shown is exemplified.

  Of the three types of isocyanurates of diisocyanates, two of the three atomic groups bonded to the cyclic compound formed by three isocyanate groups have a cyclo ring, and the remaining one atomic group Examples of those having a linear structure include two isophorone diisocyanates having a structure represented by the following chemical formula 2 and one isocyanurate of hexamethylene diisocyanate having no cyclo ring.

  Furthermore, among the three types of isocyanurates of diisocyanates, only one of the three atomic groups bonded to the cyclic compound formed by the three isocyanate groups has a cyclo ring, and the remaining two Examples of the atomic group having a linear structure include an isocyanurate form of one isophorone diisocyanate and two hexamethylene diisocyanates having a structure represented by the following chemical formula 3.

The diisocyanate used as a curing agent among the polyurethane resin forming material constituting the undercoat layer 14 is one or a plurality of diisocyanate isocyanurates having the structure represented by the above chemical formulas 1 to 3. Isocyanurates of diisocyanates having a cyclo ring, isocyanurates of two of various diisocyanates having one or more cyclo rings and one of various diisocyanates having no cyclo rings, or one or more Either one of various diisocyanates having a cyclo ring and two isocyanurates of various diisocyanates having no cyclo ring can be used. Further, even in case of using the isocyanurate of a diisocyanate having the structure represented by the above formula 1-3 as a curing agent a methyl group (-CH ₃₎ to bind to a cycloalkyl ring, for example, hydroxyl groups (-OH ), An amino group (—NH ₂ ), an ethyl group (—CH ₂ CH ₃ ), or other functional groups. Furthermore, in the isocyanurate form of diisocyanate in which one or two of the three atomic groups bonded to the cyclic compound formed by three isocyanate groups have a linear structure, the atoms having the linear structure The bonding position of the group to the cyclic compound is not limited in any way, and can be appropriately changed.

  The polyol used as the main component of the polyurethane resin forming material constituting the undercoat layer 14 is not particularly limited, and is appropriately selected according to the type of isocyanurate of diisocyanate used as the curing agent. The For example, when using the isocyanurate of diisocyanate having the structure represented by the above chemical formulas 1 to 3 as the curing agent, co-polymerization of tetrafluoroethylene and vinyl alcohol (vinyl alcohol, allyl alcohol, etc.) as the main agent. Polyols made of polymers are generally used.

  And in the resin glass 10 of this embodiment, the undercoat layer 14 has a cyclic compound formed by three isocyanate groups, and at least of three atomic groups bonded to the cyclic compound. One is composed of a polyurethane resin obtained by reacting a diisocyanate isocyanurate having a cyclo ring and a polyol, and therefore composed of a polyurethane resin obtained by reacting a diisocyanate having a linear structure with a diol. Compared to the thin film, stretching during heating can be advantageously suppressed. This is considered to be due to the following reason.

  That is, in general, a compound having a cyclic structure as a molecular structure has a limited movement of the molecule when heated compared to a compound having a chain structure as a molecular structure. And the polyurethane resin which comprises the undercoat layer 14 of the resin glass 10 of this embodiment is made into the structure where the molecular structure has the cyclic structure part provided with the cyclic compound and the cyclo ring which three isocyanate groups couple | bonded. Yes. Therefore, the undercoat layer 14 composed of such a polyurethane resin has a molecular structure at the time of heating as compared with a polyurethane resin thin film obtained by the reaction of a diisocyanate having a linear molecular structure and a diol. It is thought that the movement is restricted, and as a result, stretching is suppressed. Further, the polyurethane resin constituting the undercoat layer 14 of the resin glass 10 of the present embodiment has a higher glass transition temperature than the polyurethane resin obtained by the reaction of a diisocyanate having a linear structure and a diol. This has been confirmed by the present inventor, and this is also considered to have some influence on the suppression of elongation during heating of the polyurethane resin constituting the undercoat layer 14. The polyurethane resin obtained by the reaction of a diisocyanate isocyanurate having a benzene ring and a polyol is also made to have a structure having a cyclic structure portion. Such a polyurethane resin has a benzene ring. Further, since the compatibility between the isocyanurate of diisocyanate and the polyol is poor, it becomes cloudy and has low transparency. Therefore, a polyurethane resin obtained by the reaction of a diisocyanate isocyanurate having a benzene ring and a polyol cannot be used as the undercoat layer 14 of the resin glass 10 that requires high transparency.

  The undercoat layer 14 may have a single layer structure or a multilayer structure in which a plurality of layers are stacked. However, even when the undercoat layer 14 has a multi-layer structure, the plurality of layers constituting the undercoat layer 14 are all made of a polyurethane resin having a special cyclic structure as described above. There is a need.

The top coat layer 16 is laminated and formed on the surface opposite to the substrate 12 side of the undercoat layer 14 so as to cover the entire surface in order to impart abrasion resistance to the resin glass 10. It takes the form of a thin film. Here, the top coat layer 16 is composed of a SiO ₂ plasma CVD layer that exhibits excellent abrasion resistance. The material for forming the top coat layer 16 is not particularly limited as long as it can provide sufficient abrasion resistance to the resin glass 10, but generally, in addition to SiO ₂ , SiON and Si A silicon compound such as ₃ N ₄ is used.

  The topcoat layer 16 may have a single layer structure or a multilayer structure in which a plurality of layers are laminated. And although the thickness of the topcoat layer 16 whole is not limited at all, Preferably, it is about 1-20 micrometers. Accordingly, it is possible to sufficiently impart abrasion resistance to the resin glass 10 without unnecessarily increasing the thickness of the top coat layer 16.

  By the way, the resin glass 10 having the structure as described above is manufactured, for example, according to the following procedure.

  That is, first, a flat resin substrate 12 is molded by performing injection molding using a polycarbonate resin or the like.

  Next, as a main agent comprising a polyol, a curing agent comprising a solution of a copolymer of ethylene tetrafluoride and vinyl alcohol (for example, a butyl acetate solution) and an isocyanurate of a diisocyanate having the special structure described above, Using a solution of an isocyanurate form of isophorone diisocyanate (for example, butyl acetate solution), they are mixed to obtain a liquid mixture.

  In addition, if the main ingredient which consists of polyol and the hardening | curing agent which consists of an isocyanurate body of the diisocyanate which has the above-mentioned special structure as a formation material of the polyurethane resin which comprises the undercoat layer 14, those main ingredients and hardening | curing agent are used. Regardless of the content ratios of the main agent and the curing agent in the polyurethane resin as the reaction product, the effect of suppressing the extension of the undercoat layer 14 when the resin glass 10 is heated is sufficiently obtained. Therefore, the mixing ratio (mixing ratio) of the main agent and the curing agent when mixing the main agent and the curing agent in this step is not particularly limited, and for example, a main agent composed of diol and a curing agent composed of diisocyanate. The ratio is approximately the same as the mixing ratio of the main agent and the curing agent that are generally employed when mixing and reacting to form the polyurethane resin.

  Subsequently, as shown in FIG. 2, a mixture layer 18 made of a liquid mixture of the main agent and the curing agent is formed on both the front surface and the back surface of the resin base material 12. Thereafter, the mixture layer 18 is cured, thereby forming the undercoat layers 14 on both surfaces of the resin base material 12. Thus, an intermediate product 20 is obtained in which the undercoat layer 14 is formed on each of the front and back surfaces of the resin base 12 (see FIG. 3).

  In addition, the formation method of the mixture layer 18 on both surfaces of the resin base material 12 is not limited at all. For example, a liquid mixture of a curing agent and a main agent is applied to both surfaces of the resin base 12 using a roller, a brush, or the like, sprayed using a spray gun or the like, or a dipping operation is performed. A method or the like is appropriately employed. And the hardening method of such a mixture layer 18 is also the main agent which comprises the mixture layer 18 from well-known methods, such as the method of heating the mixture layer 18, and the method of irradiating the mixture layer 18 with an ultraviolet-ray. Various selections are made depending on the type of curing agent and the like. When the mixture layer 18 is heated and cured, the heating temperature is set to a value in the range of about 80 to 130 ° C., for example.

  Then, when the intermediate product 20 is manufactured, the top coat layer 16 is laminated on the two undercoat layers 14 and 14 of the intermediate product 20. In forming the top coat layer 16, for example, a plasma CVD apparatus 22 having a structure as shown in FIG. 3 is used.

  As is apparent from FIG. 3, the plasma CVD apparatus 22 used here has the same basic structure as a conventional plasma CVD apparatus employing a parallel plate method. That is, the plasma CVD apparatus 22 has a vacuum chamber 24 as a reaction chamber. The vacuum chamber 24 has a bottomed cylindrical or casing-shaped chamber body 26 that opens upward, and the chamber. It further includes a lid body 28 that covers the upper opening of the main body 26 and hermetically seals the inside of the chamber main body 26.

  In addition, a pair of upper holders 30 and 30 are integrally provided on the lower surface of the lid body 28 so as to face each other. Further, support protrusions 32 are integrally provided on the opposing surfaces of the upper holders 30. The cathode electrode 34 housed in the chamber body 26 is held in a state of being supported by the support protrusions 32 by the pair of upper holders 30 and 30. Further, the cathode electrode 34 is electrically connected to a high frequency power supply 36 installed outside the vacuum chamber 24.

  On the upper surface of the bottom wall portion of the chamber main body 26 positioned opposite to the lower surface of the lid body 28, lower holders 38, 38 are integrally provided upright. On these lower holders 38, 38, upper support projections 40, 40 and lower support projections 42, 42 are provided integrally and projecting apart from each other. Then, the anode electrode 44 accommodated in the chamber body 26 faces the lower support protrusions 42, 42 in a state of facing the cathode electrode 34 held by the upper holders 30, 30 with a predetermined distance in the vertical direction. Supported by the lower holders 38 and 38. The anode electrode 44 is grounded. Further, the upper support protrusions 40, 40 of the lower holders 38, 38 are configured to support the intermediate product 20.

  An exhaust pipe 46 is installed on the side wall portion of the chamber body 26 so as to penetrate the inside and outside of the chamber body 26. A vacuum pump 48 is provided on the exhaust pipe 46. By the operation of the vacuum pump 48, the gas in the chamber body 26 is discharged to the outside through the exhaust pipe 46, and the chamber body 26 is decompressed.

  Further, first and second introduction pipes 50 a and 50 b are installed in the side wall portion of the chamber main body 26 so as to penetrate the side wall portion and open into the chamber main body 26 at one end portion. And the 1st cylinder 52a which accommodates silicon compound gas by the pressure exceeding atmospheric pressure is connected to the other end part of the 1st introduction pipe 50a. A second cylinder 52b that stores oxygen gas at a pressure exceeding atmospheric pressure is connected to the other end of the second introduction pipe 50b. Further, first and second on-off valves 54a and 54b are provided at the connection portions of the first and second cylinders 52a and 52b with the first and second introduction pipes 50a and 50b, respectively. As will be described later, the silicon compound gas accommodated in the first cylinder 52a is used as a raw material gas for forming the topcoat layer 16, and is accommodated in the second cylinder 52b. The oxygen gas is used as a reaction gas for forming the top coat layer 16.

The silicon compound constituting the silicon compound gas accommodated in the first cylinder 52a is not particularly limited, and generally, an inorganic silicon compound such as monosilane (SiH ₄ ) or disilane (Si ₂ H ₆ ) is used. Each of them is used alone or in combination. Moreover, it is also possible to use an organosilicon compound as this silicon compound. And as this organosilicon compound, siloxanes such as tetramethyldisiloxane, hexamethyldisiloxane, hexamethylcyclotrisiloxane, methoxytrimethylsilane, ethoxytrimethylsilane, dimethoxydimethylsilane, dimethoxydiethylsilane, dimethoxydiphenylsilane, Trimethoxysilane, trimethoxymethylsilane, trimethoxyethylsilane, trimethoxypropylsilane, triethoxymethylsilane, triethoxydimethylsilane, triethoxyethylsilane, triethoxyphenylsilane, tetramethylsilane, tetramethoxysilane, tetraethoxysilane Examples thereof include silanes such as hexamethyldisilazane and silazanes such as tetramethyldisilazane. And one of them is used alone, or two or more of them are used in combination. When two or more types of silicon compound gases are used, the plurality of types of silicon compound gases may be mixed and stored in one first cylinder 52a, or two or more types of silicon compound gases may be stored. May be separately accommodated in the plurality of first cylinders 52a.

When the top coat layer 16 is formed on the undercoat layers 14 and 14 laminated on both surfaces of the resin base material 12 using the plasma CVD apparatus 22 having such a structure, first, The intermediate product 20 obtained as described above is accommodated in the chamber body 26, supported by the upper support protrusions 40, 40 of the lower holders 38, 38, and held by the lower holders 38, 38. . Thereafter, the upper opening of the chamber body 26 is covered with a lid 28 and the vacuum chamber 24 is hermetically sealed, and then the vacuum pump 48 is operated. Thereby, the inside of the vacuum chamber 24 is depressurized so that the pressure becomes, for example, about 10 ⁻⁵ to 10 ⁻³ Pa.

  Next, when the pressure in the vacuum chamber 24 is reduced to a predetermined value, the first opening / closing valve 54a of the first cylinder 52a and the second opening / closing valve 54b of the second cylinder 52b are operated while the vacuum pump 48 is operated. Open each. Thereby, the silicon compound gas in the first cylinder 52a is introduced into the vacuum chamber 24 through the first introduction pipe 50a, and the oxygen gas in the second cylinder 52b is introduced into the vacuum chamber 24 through the second introduction pipe 50b. Introduce. Thus, the vacuum chamber 24 is filled with the silicon compound gas and the oxygen gas.

  When the vacuum chamber 24 is filled with the silicon compound gas and the oxygen gas, and the internal pressure of the vacuum chamber 24 reaches a predetermined value, the high-frequency power source 36 is turned on and the cathode electrode disposed in the vacuum chamber 24 is turned on. A high frequency current is supplied to 34. As a result, a discharge phenomenon is caused between the cathode electrode 34 and the anode electrode 44, and the silicon compound gas and the oxygen gas filled in the vacuum chamber 24 are turned into plasma, respectively. Are generated in the vacuum chamber 24.

Then, a reaction between the plasma of the silicon compound gas and the plasma of the oxygen gas (reaction by the plasma CVD method of the silicon compound gas and the oxygen gas) is caused in the space in the vacuum chamber 24 and the surface of the intermediate product 20, and SiO 2 ₂ and deposit it on the entire surface of the intermediate product 20. Thereafter, when a preset time has elapsed from the opening operation of the first and second opening / closing valves 54a, 54b, the first and second opening / closing valves 54a, 54b are closed. Thereby, the top coat layer 16 made of SiO ₂ is formed on the undercoat layers 14 and 14 formed on both surfaces of the resin base material 12 with a thickness corresponding to the opening time of the first and second opening / closing valves 54a and 54b. In FIG. Thus, the intended resin glass 10 having the structure as shown in FIG. 1 is obtained.

  As is clear from the above description, in the resin glass 10 of the present embodiment, the extension of the undercoat layer 14 made of polyurethane resin is advantageously suppressed when heated. Therefore, when the resin glass 10 is exposed to a high temperature environment for a long time, the extension amount of the topcoat layer 16 cannot follow the extension amount of the undercoat layer 14, which causes the topcoat layer 16 to be stretched. The occurrence of cracks can be effectively prevented. Therefore, in this resin glass 10, the excellent heat resistance which cannot be obtained by conventional resin glass or the like can be exhibited extremely effectively.

  Moreover, in this embodiment method, when the undercoat layer 14 made of a polyurethane resin is laminated on the surface of the resin substrate 12, a diisocyanate having a special molecular structure is used as a curing agent for forming the polyurethane resin. Although an isocyanurate body is used, the steps of forming the undercoat layer 14 and the topcoat layer 16 on the surface of the resin base material 12 are performed in the same operation procedure as that for producing a conventional resin glass. Therefore, according to the method of this embodiment as described above, the resin glass 10 having extremely excellent heat resistance can be manufactured very easily by the same operation as before without being subjected to a special work load. It can be done.

  Furthermore, in the method of the present embodiment, when the polyurethane resin constituting the undercoat layer 14 is formed, for example, an easily available curing agent made of an isocyanurate of isophorone diisocyanate or an isocyanurate of isophorone diisocyanate and hexamethylene diisocyanate are used. By using such a curing agent, the production of the target resin glass 10 is further facilitated.

  The specific configuration of the present invention has been described in detail above. However, this is merely an example, and the present invention is not limited by the above description.

  For example, in the above-described embodiment, the undercoat layer 14 and the topcoat layer 16 are laminated on both the front surface and the back surface of the resin base material 12, respectively, but only on one surface of the resin base material 12, The undercoat layer 14 and the topcoat layer 16 may be laminated.

  In the above embodiment, the top coat layer 16 is formed of a silicon compound plasma CVD layer. However, if the top coat layer 16 is formed of a silicon compound thin film layer, the formation method is as follows. There is no particular limitation. Therefore, the topcoat layer 16 made of a silicon compound can be constituted by a thin film layer formed by a so-called PVD method such as vapor deposition or sputtering, or a thin film layer formed by a CVD method other than the plasma CVD method. is there.

  In addition, in the said embodiment, although the specific example of what applied this invention to resin glass and its manufacturing method was shown, this invention is an undercoat which consists of a polyurethane resin on the surface of a polycarbonate resin base material. Of course, the present invention can be advantageously applied to any of a resin product in which a layer and a topcoat layer made of a silicon compound are laminated and a manufacturing method thereof.

  In addition, although not enumerated one by one, the present invention can be carried out in a mode to which various changes, modifications, improvements, etc. are added based on the knowledge of those skilled in the art. It goes without saying that all are included in the scope of the present invention without departing from the spirit of the present invention.

  Hereinafter, representative examples of the present invention will be shown to clarify the present invention more specifically, but the present invention is not limited by the description of such examples. It goes without saying. In addition to the following examples, the present invention includes various changes and modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention, in addition to the specific description described above. It should be understood that improvements can be made.

  First, using a commercially available polycarbonate resin, known injection molding was performed to obtain four transparent resin substrates made of rectangular flat plates having a length × width × thickness of 200 × 200 × 3.5 mm.

  Subsequently, as a main component of the polyurethane resin forming material constituting the undercoat layer, a predetermined amount of a commercially available butyl acetate solution of ethylene tetrafluoride and vinyl alcohol copolymer is prepared, and as a curing agent, A predetermined amount of a commercial butyl acetate solution of an isocyanurate form of isophorone diisocyanate was prepared. The main agent and the curing agent are mixed at a ratio of 1: 0.5 on a weight basis to prepare a predetermined amount of the mixture A, while the main agent and the curing agent are mixed at a ratio of 1: 1 on a weight basis. The mixture B is prepared in a predetermined amount, and the main agent and the curing agent are mixed at a ratio of 1: 2 on a weight basis to prepare the mixture C in a predetermined amount. Further, the main agent and the curing agent are further added by weight. A predetermined amount of the mixture D was prepared by mixing at a ratio of 1: 5 on the basis.

  Next, using the four types of mixtures A to D prepared as described above, each having different blending ratios of the main agent and the curing agent, and the four resin bases previously molded, Four types of mixtures A to D were separately applied to the surface of the resin substrate. Thereby, while forming the mixture layer which consists of a coating-film layer of the mixture A on the surface of one resin base material of four resin base materials, it is a mixture on the surface of another one resin base material. A mixture layer composed of a coating layer of B is formed, and a mixture layer composed of a coating layer of mixture C is formed on the surface of another resin substrate, and another resin group is formed. A mixture layer composed of a coating layer of mixture D was formed on the surface of the material.

  Thereafter, these four resin base materials are put into a heating furnace, heated at 120 ° C. for 10 minutes, the main agent and the curing agent in the mixture layer formed on the surface of each resin base material are reacted, Each mixture layer was cured. Thereby, although the same kind of main agent and curing agent are used, undercoat layers made of polyurethane resins having different mixing ratios of the main agent and the curing agent are formed on the surfaces of the four resin substrates, respectively. As a result, four kinds of intermediate products were obtained. And what formed the undercoat layer which the polyurethane resin which the mixture A hardened on the surface of the resin base material was made into the intermediate product A, and the polyurethane resin which the mixture B hardened formed Intermediate product B is an intermediate product B, and an intermediate product C is formed with an undercoat layer made of a polyurethane resin in which the mixture C is cured. did. The thicknesses of the undercoat layers of the four types of intermediate products A to D were all 5 μm. Moreover, the glass transition temperature of the polyurethane resin which comprises the undercoat layer of intermediate product AD was 76 degreeC.

  Next, using a plasma CVD apparatus having a structure as shown in FIG. 3, each of four kinds of intermediate products A to D is accommodated in a vacuum chamber of the plasma CVD apparatus, and monosilane gas and oxygen gas are introduced. Then, a plasma CVD method was performed. Thereby, the topcoat layer which consists of a plasma CVD layer of a silicon compound was each formed on the undercoat layer of four types of intermediate products AD. The thickness of the top coat layer was all 1 μm.

  Thus, although it is composed of a reaction product of a main agent composed of a copolymer of fluorinated ethylene and vinyl alcohol and a curing agent composed of an isocyanurate body of isophorone diisocyanate, the blending ratio of the main agent and the curing agent is different. Four types of resin glass each having an undercoat layer made of a polyurethane resin formed on the surface of the resin base material were obtained. Of these four types of resin glass, the one in which the top coat layer is formed on the undercoat layer of the intermediate product A is referred to as resin glass A, and the top coat layer is formed on the undercoat layer of the intermediate product B. The resulting product is a resin glass B, and a product obtained by forming a top coat layer on the undercoat layer of the intermediate product C is a resin glass C, and a top coat layer is formed on the undercoat layer of the intermediate product D. The thing was called resin glass D.

  For comparison, three transparent resin substrates made of rectangular flat plates having a length × width × thickness of 200 × 200 × 3.5 mm are obtained by performing known injection molding using a commercially available polycarbonate resin. Got. Furthermore, as a main component of the polyurethane resin forming material constituting the undercoat layer, a predetermined amount of a commercially available butyl acetate solution of ethylene tetrafluoride and vinyl alcohol copolymer is prepared, and as a curing agent, A predetermined amount of a commercially available butyl acetate solution of an isocyanurate of hexamethylene diisocyanate was prepared. The main agent and the curing agent are mixed at a ratio of 1: 0.5 on a weight basis to prepare a predetermined amount of the mixture E, while the main agent and the curing agent are mixed at a ratio of 1: 1 on a weight basis. The mixture F was prepared by a predetermined amount, and the main agent and the curing agent were mixed at a ratio of 1: 2 on a weight basis to prepare the mixture G by a predetermined amount.

  Then, using the three types of mixtures E to G prepared as described above and the three resin substrates molded in advance, the same as when obtaining four types of intermediate products A to D, 3 Got kinds of intermediate products. Of these three types of intermediate products, an intermediate product E having an undercoat layer made of a polyurethane resin cured with the mixture E formed on the surface of the resin base material, and an undercoat made of a polyurethane resin cured with the mixture F An intermediate product F was formed with a layer, and an intermediate product G was formed with an undercoat layer made of a polyurethane resin obtained by curing the mixture G. The thicknesses of the undercoat layers of these three types of intermediate products E to G were all 5 μm, the same as the thickness of the undercoat layers of the four types of intermediate products A to D. Moreover, the glass transition temperature of the polyurethane resin which comprises the undercoat layer of intermediate products EG was 51 degreeC.

  Next, using a plasma CVD apparatus having a structure as shown in FIG. 3, monosilane gas, and oxygen gas, the intermediate products E to E are formed in the same manner as when the top coat layer is formed on the undercoat layers of the intermediate products A to D. A topcoat layer was formed on each of the G undercoat layers. The thicknesses of the topcoat layers formed on the undercoat layers of the intermediate products E to G were all 1 μm, which is the same as the thickness of the topcoat layers of the four types of intermediate products A to D.

  Thus, although composed of a reaction product of a main agent composed of a copolymer of tetrafluoroethylene and vinyl alcohol and a curing agent composed of an isocyanurate of hexamethylene diisocyanate, the blend of these main component and curing agent Three types of resin glasses were obtained in which undercoat layers made of polyurethane resins having different ratios were formed on the surface of the resin substrate. Of these three types of resin glass, the one in which the top coat layer is formed on the undercoat layer of the intermediate product E is referred to as the resin glass E, and the top coat layer is formed on the undercoat layer of the intermediate product F. Resin glass F was used, and a product obtained by forming a topcoat layer on the undercoat layer of the intermediate product G was used as resin glass G.

  Subsequently, the seven types of resin glasses A to G manufactured as described above were subjected to a heat resistance test held at a temperature environment of 110 ° C. for 24 hours, and then the seven types of resin glasses A to G were used. It was visually examined whether or not cracks occurred in each of the top coat layers of G.

  As a result, in the resin resins A to D in which the undercoat layer is formed in the polyurethane resin composed of the reaction product of the polyol and the isocyanurate of the diisocyanate having a special molecular structure according to the present invention, all No cracks were generated in the topcoat layer. In contrast, resin glasses EG having an undercoat layer formed of a polyurethane resin made of a reaction product of a polyol and a diisocyanate isocyanurate having a molecular structure different from the special molecular structure according to the present invention. In both cases, cracks occurred in the topcoat layer. From this, the heat resistance of the resin glass is extremely effectively achieved by constituting the undercoat layer with a polyurethane resin comprising a reaction product of a diisocyanate isocyanurate having a special molecular structure according to the present invention and a polyol. It is clearly recognized that it can be enhanced.

DESCRIPTION OF SYMBOLS 10 Resin glass 12 Resin base material 14 Undercoat layer 16 Topcoat layer 18 Mixture layer 22 Plasma CVD apparatus

Claims (2)

An undercoat layer made of polyurethane resin is laminated on the surface of a resin substrate made of a polycarbonate resin molded product, and a topcoat layer made of a silicon compound is further laminated on the undercoat layer. A resin product,
Resin product polyurethane resin constituting the undercoat layer, characterized in the Turkey, such a reaction product of an isocyanurate form a polyol of isophorone diisocyanate. An undercoat layer made of polyurethane resin is laminated on the surface of a resin substrate made of a polycarbonate resin molded product, and a topcoat layer made of a silicon compound is further laminated on the undercoat layer. A resin product manufacturing method comprising:
Preparing the resin substrate;
A mixture layer formed by mixing an isocyanurate body of isophorone diisocyanate and a polyol is formed on the surface of the resin base material, while the isocyanurate body of the isophorone diisocyanate and the polyol are reacted to form the mixture layer. Curing on the surface of the resin substrate, and forming an undercoat layer made of the polyurethane resin on the surface;
A step of laminating and forming a topcoat layer comprising the silicon compound on the undercoat layer;
The manufacturing method of the resin product characterized by including.

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