JP2007223154A - Decorating sheet and molded article furnished with the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sheet being good in the followability to a mold, friendliness to the environment, clearness of a figure and antiwear of a pattern, and to provide a molded article. <P>SOLUTION: A transparent uncured prepreg resin sheet and a pattern-provided sheet having, from the surface side, a pattern layer and a semi-cured thermosetting resin layer are put one upon the other and used at the time of molding to form the decorating sheet. The molded body is equipped, from the surface side, with the transparent prepreg resin layer, the pattern layer, the thermosetting resin layer and a substrate resin layer, all layers being cured. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a decorative sheet for FRP press molding used when forming a fiber-reinforced plastic molded article having a pattern, and a molded body formed using the sheet.

  Conventionally, fiber reinforced plastic molded products (FRP molded products) have been used as members constituting floors, walls, ceilings of bathroom units, floors of toilets, toilets, etc., top plates of sinks, etc. Ingenuity has been devised to enhance the design by adding marble and granite patterns and irregularities.

As a method for imparting design properties such as a pattern to the surface of an FRP molded product, a method of integrally molding a decorative sheet at the time of molding a molded body and imparting a pattern (see Patent Document 1), a method of spraying a pattern / pattern by painting, A non-cured resin sheet (prepreg resin sheet) that eliminates stickiness of the uncured resin by impregnating a liquid (for prepreg) uncured resin into a non-woven fabric with a pattern printed thereon and drying it, and a molding material There was a patterning method to form integrally.
JP-A-6-134784 JP 2004-251095 A Japanese Patent Laid-Open No. 5-220443

  However, in the method in which the decorative sheet is integrally formed and molded in the molding process, the manufactured sheet has already been cured by more than half. There was a problem that could not follow the mold that I have.

  As a method of spraying a pattern / pattern by painting, an arbitrary pattern could not be selected, and only a monotonous pattern such as a single color or multi-color spray or a stone tone by mixing particulate matter was obtained. Also, the pattern looks flat and has no depth or depth, making it difficult to obtain a high-class feeling. As described in Patent Document 3, a method of changing the appearance pattern can be taken by changing the substrate uneven pattern as described in Patent Document 3, but the overall appearance is still the same pattern pattern. Because there is, it becomes monotonous. In addition, there were concerns about a decrease in productivity due to increased processes due to post-coating, an increase in work time due to masking work, and an adverse environmental impact due to solvent evaporation. And, for post-coating, the application of the coating decoration method to the surface of the molded product having fine unevenness as described above fills the fine unevenness, changes in the appearance, and the characteristics of the mold transfer product with the fine unevenness The function of (hydrophilicity etc.) may be impaired.

  For a patterning method in which a non-woven fabric printed with a pattern is impregnated with a resin for prepreg to form a patterned sheet and integrally molded with a molding material in a high-temperature mold, after the prepreg resin has once melted on the mold The mold has good followability because it cures, but because the woven or non-woven fabric that is the printing substrate is discontinuous, the ink is not continuously applied, and the pattern becomes blurred and unclear. there were. Furthermore, since the fiber on which the pattern is printed is partially exposed to the surface of the molded body, there is a problem that the printed pattern disappears due to surface abrasion due to cleaning or the like.

  It is an object of the present invention to provide a sheet and a molded body having good mold followability, environmental consideration, pattern sharpness, and pattern wear resistance.

(1) A decorative sheet in which a transparent uncured prepreg resin sheet and a patterned sheet provided with a pattern layer and a semi-cured thermosetting resin layer from the surface side are overlapped during molding.
(2) Moreover, it is a molded body provided with a transparent prepreg resin layer, a pattern layer, a thermosetting resin layer, and a base resin layer after curing from the surface side.
(3) Moreover, it is a decorating sheet | seat which uses a transparent uncured prepreg resin sheet and the sheet | seat with a pattern provided with the semi-hardened thermosetting resin layer and the pattern layer from the surface side at the time of shaping | molding.
(4) Moreover, it is a molded body provided with a transparent prepreg resin layer, a thermosetting resin layer, a pattern layer, and a base resin layer after curing from the surface side.
(5) In addition, a decorative sheet in which a transparent uncured prepreg resin sheet and a patterned layer provided with a patterned layer, a semi-cured thermosetting resin layer, and a patterned layer are overlapped and used at the time of molding. It is.
(6) Moreover, it is a molded object provided with the transparent prepreg resin layer, the pattern layer, the thermosetting resin layer, the pattern layer, and the base resin layer after curing from the surface side.
(7) Moreover, the transparent uncured prepreg resin sheet is a decorative sheet according to (1), characterized in that it contains a diallyl phthalate resin.
(8) The cured prepreg resin layer after curing is a shaped article according to (2), characterized in that it contains diallyl phthalate resin.
(9) Moreover, the transparent uncured prepreg resin sheet is a decorative sheet according to (3), characterized in that it contains diallyl phthalate resin.
(10) The cured prepreg resin layer after curing is a molded article according to (4), characterized in that it contains diallyl phthalate resin.
(11) The transparent uncured prepreg resin sheet is a decorative sheet according to (5), characterized in that it contains diallyl phthalate resin.
(12) The transparent prepreg resin layer after curing contains the diallyl phthalate resin (6).

When the present invention is used, a transparent prepreg after curing from the surface side, a molded product comprising a transparent prepreg resin layer, a thermosetting resin layer, a pattern layer, and a base resin layer, or a cured prepreg after curing from the surface side. Molded body with resin layer, thermosetting resin layer, pattern layer, base resin layer, or transparent prepreg resin layer, pattern layer, thermosetting resin layer, pattern layer, base after curing from the surface side It is a molded body consisting of a resin layer, and by molding using a transparent uncured prepreg resin sheet on the surface, the resin in the transparent uncured prepreg resin sheet is once melted in the mold during heating and pressure molding. Since it follows the fine irregularities and cures in that state, the mold followability is good, so that the function such as hydrophilicity of the product surface obtained by the good mold followability is not impaired. Since the pattern layer is directly formed on the thermosetting resin layer, the pattern ink layer is formed without any gap on the resin surface, and the pattern becomes clear. Since the pattern layer can be seen through the transparent prepreg resin layer after curing, the transparent prepreg resin layer protects the pattern ink surface, and further, when the diallyl phthalate resin is included as the prepreg resin, only the polyester resin is used. Compared to resin blends, it has the feature of high surface hardness and is durable against abrasion. Since the decorative sheet and the molding material are integrally formed in the mold, there are few problems such as solvent volatilization and consideration for the human body and the environment is possible.
In the case of a transparent prepreg resin layer, a patterned layer, a thermosetting resin layer, and a base resin layer after curing, the thermosetting resin layer is opaque or uneven in hue because the pattern layer is applied on the resin layer. Even if it has a non-homogeneous appearance, it can be concealed with a pattern, so it can give a uniform pattern regardless of the appearance of the thermosetting resin layer, and various compounds can be added to the semi-curing thermosetting resin layer For example, it is possible to mix a hollow body into a molded product to provide functions such as heat insulation.
In the case of the transparent prepreg resin layer, thermosetting resin layer, pattern layer, and base resin layer after curing, the thickness from the surface to the pattern layer can be increased by the transparent prepreg resin layer + base resin layer. , The depth of the pattern increases and the sense of quality is improved. Furthermore, by coloring the thermosetting resin layer semi-transparent or thin enough to show the pattern, it becomes two layers of the thermosetting resin layer with different transparency and texture of the transparent uncured prepreg resin sheet. Since it is formed, a further high-class feeling can be obtained.
In the case of the structure of the transparent prepreg resin layer, the pattern layer, the thermosetting resin layer, the pattern layer, and the base resin layer after curing, the pattern is lifted because the pattern layer is applied above and below the thermosetting resin layer. Various high relief effects can be obtained, and a high-class feeling can be obtained.

The resin used for the transparent uncured prepreg resin sheet of the present invention is not particularly limited as long as it is once melted in a heated mold, followed by curing and then cured. As an example, a blend of diallyl phthalate resin + polyester resin or / and acrylic resin or / and melamine resin or the like can be considered. In addition, some single resins such as polyester resin, epoxy resin, and acrylic resin are once melted in a heated mold and cured after following the mold. Alternatively, there is a method of increasing the viscosity of the liquid thermosetting resin and enabling handling, but there are portions where the handling, transparency, storage stability, etc. are insufficient. The compound of diallyl phthalate resin + polyester resin is stable with little change in the flow characteristics of the material even when stored for more than one year at room temperature, and other characteristics such as chemical resistance are not changed. Has low stickiness in the prepreg state, and is flexible enough to prevent the resin from cracking, making it easy to handle and other features that are not found in phenol, urea, melamine, epoxy, and polyester resin Have
As the transparency of the resin used for the transparent resin for prepreg, there is no problem as long as the transparency is such that a pattern can be seen through the transparent prepreg resin layer.

  As a mold shape having fine irregularities described in the present invention, as an example, the ratio Sm / Ry between the average interval Sm of irregularities and the maximum height Ry described in Patent Document 2 (where Ry and Sm) Is a value measured with a laser microscope with the resolution in the XY (horizontal and vertical) direction set to 0.2913 μm, the resolution in the Z (height) direction set to 0.5 μm, and the measurement length set to 298 μm) And the like are 5 or less. When a molded product is molded using a mold of this shape, hydrophilicity is obtained when water is sprayed onto the surface of the molded product if the followability to the mold is good, and hydrophilicity is provided if the followability is insufficient. Cannot be obtained.

The method for forming the transparent uncured prepreg resin sheet of the present invention is not particularly limited, but the liquid transparent uncured prepreg resin is applied onto a base plate or film, and is not sticky after being dried. A method in which a solid prepreg is used and then peeled off from a base plate or film. There is a method in which a woven fabric or a non-woven fabric is prepared in advance, impregnated with a liquid transparent uncured prepreg resin, and dried to obtain a solid prepreg sheet. Also in the method of applying the prepreg resin onto the base plate or film, the prepreg resin layer applied onto the base may be impregnated with a woven fabric or a non-woven fabric.
The prepreg described here does not proceed with a curing reaction in which a curing agent and a resin are mixed in advance, but has a solid form at a temperature of −10 to 50 ° C. or a temperature assumed in a working environment, and is handled in work. Insert a resin in such a state that is possible. When used, the resin is melted once by heating above the melting point of the resin and the reaction temperature of the blended curing agent, and then the shape is changed along the desired shape such as a mold, and then the curing reaction proceeds to complete curing. . Therefore, shape followability is good.
Usually, the prepreg resin is diluted with a solvent or the like to form a liquid, and then applied to an object, and the solvent is dried to be used as a solid sheet. Specifically, as described above, the prepreg resin solution once diluted with a solvent is coated on a base plate or film, dried and used as a sheet, or impregnated into a woven fabric or non-woven fabric. And a method of using the sheet by drying it, or a method of forming a layer by directly spraying the sheet to be used.

  The method for forming a resin layer on a base plate or film is not particularly limited, such as spray gun spraying, brush coating, film coating, roll coating, dip coating, bar coating, curtain coating, and flow coating. Moreover, you may form by casting or extrusion. Furthermore, in order to enable easy peeling onto the base plate or film, an internal release agent may be mixed into the surface treatment with a release agent or the like, or into the prepreg resin.

  The method for impregnating the prepreg resin into the woven fabric or non-woven fabric is not particularly limited, but a dip coat method and a base in which a pre-prepared impregnated base material is dipped into a container containing the prepreg resin and then coated is applied. A roll coater system in which a reinforcing substrate is placed on a plate and forcedly impregnated by applying pressure with a stretching roller, etc., spraying with a spray gun, brush coating, film coat, bar coater, curtain coater, flow coat, A knife coat etc. can be used.

The woven fabric or non-woven fabric in the transparent uncured prepreg resin sheet of the present invention is not particularly limited, but a woven fabric or non-woven fabric made of organic fibers selected from materials such as polyester resin, acrylic resin, pulp, glass, etc. A woven fabric or a non-woven fabric made of an inorganic fiber can be used. When the resin is impregnated, the resin becomes transparent or translucent and the pattern can be seen through the sheet. Alternatively, a method of intentionally coloring the fiber to form a pattern is possible, but in any case, the underlying pattern must be visible.
The basis weight of the woven or non-woven fabric is not particularly limited as long as the pattern can be seen through the sheet, but is preferably 15 to 50 g / square meter, more preferably 25 to 30 g / square meter. When the thickness is less than 15 g / square meter, handling properties such as when the substrate is impregnated with resin and when the sheet is handled gradually deteriorate. When it becomes thicker than 50 g / square meter, the pattern gradually becomes unclear when a slightly turbid translucent resin is used.

  Although there is no restriction | limiting in particular as an adhesion amount with respect to the base material of resin for prepregs of this invention, In the state formed into the prepreg resin sheet, it is 50-200 g / square meter, Preferably, it is 100-140 g / square meter.

  When the resin adhesion amount is less than 50 g / square meter, the base fiber is exposed on the surface of the resin layer for prepreg after molding, fluffing and roughening gradually occur, the appearance is deteriorated, and dirt is difficult to remove. Furthermore, when used around water, moisture may enter between the base fiber and the cured prepreg resin, which may accelerate the deterioration of the molded product.

  When the resin adhesion amount is more than 200 g / sq.m., When the prepreg resin placed on the surface mold melts at the time of heating and pressure molding, the surface mold and the pattern layer that comes to the next layer On the other hand, the frictional force between the thermosetting resin layer having the pattern layer and the molding material used for the base material layer is reduced to the frictional force between the sheets. When winning, both the prepreg resin layer and the thermosetting resin layer having the pattern layer may be destroyed during molding. However, the range of this adhesion amount is only a guideline because the results obtained vary depending on the type of resin for the prepreg, the type of resin used for the thermosetting resin layer that comes to the next layer, the curing agent composition, and the molding conditions. .

  The method for applying the pattern layer is not particularly limited, but a plate or film having one side patterned with an ink soluble in the thermosetting resin in the next layer is prepared in advance on the base plate or film. , A thermosetting resin placed on top of it, cured, leaving the pattern ink on the resin layer side, and transferring the pattern by peeling the plate or film, spray coating, curtain coating, flow coating, dip There are methods such as coating, wire bar coating, screen printing method, letterpress printing method, gravure printing method, and the like to directly apply a pattern to the thermosetting resin layer.

  The plate or film used as the base plate or film patterned on one side with ink is not particularly limited as long as it has releasability and is insoluble in thermosetting resin, but polyethylene resin, polypropylene resin A plastic film such as a nylon resin, a polyester resin, or a fluororesin, or a paper or plastic film coated with a releasable resin is used. In addition, it is preferable that the thickness of a film is about 10-100 micrometers in order to stretch | stretch a block-shaped thermosetting resin uniformly.

  The patterning ink used for the base plate or film patterned on one side with ink is selected from those compatible with the thermosetting resin. As such an ink, there are inks obtained by mixing pigments, paints, dyes or the like with unsaturated polyester resins, acrylic resins, nitrified cotton (nitrocellulose) resins, and the like. Here, the pattern may be a floral pattern, a geometric pattern, or other various patterns, but may be a non-pattern or a single-color pattern. Or, it is possible to add a pulverized product of natural minerals such as mica or inorganic materials such as metals into a thermosetting resin, thermosetting resin or prepreg resin. It is.

The ink layer of the patterning ink may be either a single layer or a multilayer. In the case of multiple layers, the surface pattern ink layer, intermediate pattern ink layer, back pattern ink layer, base plate or film are formed in this order, and the back pattern ink layer, intermediate pattern ink layer, surface pattern ink There are two ways in which layers, base plates and films are formed in this order.
The surface pattern ink layer and the intermediate pattern ink layer may be spot print, and the back pattern ink layer may be solid print covering the entire surface or spot print.
If the resin layer is transparent or translucent, the pattern can be seen through the resin layer.
(1) Single ink layer sheet (2) In the case of multiple layers,
(2-1) In the case of a transparent prepreg resin sheet layer, a thermosetting resin layer, a pattern layer, and a base resin layer, the former is used in the case of backside solid printing, and the latter is used in the case of backside printing, or
(2-2) In the case of the configuration of the transparent prepreg resin sheet layer, the pattern layer, the thermosetting resin layer, and the base resin layer, the latter ink configuration is used for back side solid printing, and the latter latter transfer is used for back side spot printing. Possible to use film,
(2-3) In the case of a transparent prepreg resin sheet layer, a pattern layer (upper), a thermosetting resin layer, a pattern layer (lower), and a base resin layer, the pattern layer (upper) and the pattern layer (lower) There are combinations of one layer + multilayer backside spot or solid printing, multilayer backside spot printing + multilayer solids printing, multilayer backside spot printing + multilayer backside spot printing.
If the thermosetting resin layer is opaque, the pattern cannot be seen through the thermosetting resin layer.
(1) Single layer ink layer sheet (2) In the case of multiple layers, the transparent prepreg resin sheet layer, the pattern layer, the thermosetting resin layer, and the base resin layer are composed of one layer and multiple layers. Only the latter ink configuration can be used for backside solid printing, and the former ink configuration can be used for spot printing.

  The resin used for the thermosetting resin layer is not particularly limited, but it is an unsaturated polyester resin, vinyl ester resin, acrylic resin, etc., and an additive such as a curing agent and a chain transfer agent may be added. A fiber-reinforced thermosetting resin sheet that suppresses polymerization by appropriate selection of types, combinations, addition amounts, and curing conditions, and stops the polymerization at an arbitrary degree of curing as a first-stage curing, and is in a semi-cured state. Can be obtained. The arbitrary degree of cure means that the fiber-reinforced thermosetting resin sheet retains its shape and the surface is not sticky, has good handling properties, and does not cause outflow or crack breakage during heating and pressure molding. And, it has the flexibility that can follow the mold shape having the uneven surface pattern and joints. The second stage curing, i.e., complete curing, leaves reactive groups that allow adhesion to thermosetting fiber reinforced molding materials such as sheet molding compounds (SMC), bulk molding compounds (BMC) and the like. The state is referred to, and the degree of curing is preferably in the range of 60 to 90%.

  When the degree of cure is less than 60%, the strength of the fiber-reinforced thermosetting resin sheet is insufficient, and in some cases, the fiber-reinforced thermosetting resin sheet may be broken during heating and pressure molding. On the other hand, if it exceeds 90%, followability to the surface mold and adhesion to the molding material used for the transparent prepreg resin sheet layer and the reinforcing resin layer may not be obtained.

  The chain transfer agent for stopping the curing of the thermosetting resin used in the present invention to an arbitrary degree of curing is preferably by using 4-methyl-2,4 diphenylpentene-1 (α-methylstyrene dimer). The polymerization reaction is suppressed by appropriately selecting the addition amount, the type, combination, and curing conditions of the curing agent, and the polymerization is stopped at an arbitrary degree of curing (polymerization addition rate). Here, the cured state of the thermosetting resin stopped by the action of the chain transfer agent is mainly due to metal crosslinking between the unsaturated polyester and the divalent metal oxide found in the compound formation of SMC, BMC, etc. Compared to a decrease in viscosity due to pressurization and the expectation of compound flow), a three-dimensional network structure is formed by copolymerization of unsaturated dibasic and polymerizable monomers in unsaturated polyester, that is, cross-linking between molecules. In order to form partly, the fiber reinforced thermosetting resin sheet retains its shape, the surface is not sticky, and follows the uneven shape of the surface mold, the joint part at the time of heating and pressure molding by press, outflow, It has a strength and flexibility that does not cause crack breakage and the like, and remains in a state in which a reactive group (crosslinking point) that allows adhesion to another molding material is left at the time of complete curing.

  Furthermore, by mixing the hollow body into the thermosetting resin, it is possible to have an effect of reducing the coldness at the time of contact. The hollow body to be used is not particularly limited, but glass balloons, silica-based balloons, and the like that can obtain adhesiveness with the thermosetting resin to be used are preferable. As for the diameter of a hollow body, about 10-120 micrometers is desirable, Preferably it is about 40-70 micrometers. When the diameter of the hollow body is reduced, the voids are reduced and the strength is improved, but the effect of reducing the coldness is lowered. When the diameter of the hollow body is increased, the cold reduction effect is improved, but the strength tends to be reduced.

  The addition amount of the hollow body has no upper limit of 5 parts by weight or more with respect to 100 parts by weight of the resin, but is usually preferably about 5 to 30 parts by weight. When the amount added is less than 5 parts by weight, no difference is obtained in the cooling reduction effect by sensory evaluation. When it exceeds 30 parts, the strength of the sheet is insufficient, and in some cases, it is destroyed during heating and pressure forming by a press. There are things to do. Moreover, the handling may become difficult due to an increase in the viscosity of the resin paste mixed with the hollow body.

  The thickness of the base layer of the woven or non-woven fabric in a semi-cured state when the hollow body is mixed is 0.5 mm or more, preferably 1 mm or more. If it is 0.5 mm or less, depending on the material and diameter of the hollow body to be added, there may be a case where a large difference cannot be obtained in the cooling reduction effect.

  When a hollow body is added to the resin for prepreg, it is possible to further improve the cold reduction effect.

  In order to form a semi-cured thermosetting resin layer, a woven fabric or a non-woven fabric is impregnated with a thermosetting resin, but the substrate used is not particularly limited, but a polyester resin, an acrylic resin Organic fiber woven fabric made of a material such as pulp, non-woven fabric or mat or knit, or inorganic fiber woven fabric such as glass, non-woven fabric or mat or knit is preferred. Although there is no restriction | limiting in particular as a fabric weight of a woven fabric or a nonwoven fabric, Preferably it is 15-50 g / square meter, More preferably, it is about 25-30 g / square meter. Furthermore, when a hollow body or the like is added to the resin to provide functionality such as a cooling reduction effect, the weight per unit area is preferably 100 g / square meter or more, and a suitable material is used depending on the application.

  The plate or film used on the other side, different from the base plate or film patterned on one side with ink, used in the present invention, has releasability and is a thermosetting resin If it is insoluble, there is no particular limitation, and usually the same material as the base plate or film can be used.

A typical base material used for the reinforcing layer is a fiber reinforced resin plate (FRP). As the fiber, inorganic fibers such as glass fiber, alumina fiber, carbon fiber, silica fiber, polyester fiber, nylon fiber are used. Organic fibers such as these are used, and these may be woven or non-woven. Furthermore, it is not necessary to use fibers.
Examples of the resin used for the reinforcing layer include thermosetting resins such as unsaturated polyester resins and dicyclopentadiene resins. It is also possible to manufacture the reinforcing layer using a thermosetting fiber reinforcing material such as SMC or BMC.
When reinforcing fibers are used for the reinforcing layer, the content is not limited, but is preferably 10 to 30% based on the total weight.

An embodiment of the present invention will be described below with reference to FIGS.

(A-1)
As shown in FIG. 1, an organic solvent-based dispersion containing a diallyl phthalate resin and an unsaturated polyester (Fuji Polymer Co., Ltd.) at one end on the surface of a base film 1 made of a polyester film having a thickness of 50 μm as shown in FIG. Manufactured; 20 parts diallyl phthalate resin, 30 parts unsaturated polyester resin, 40 parts acetone, 1 part curing agent, 0.01 part polymerization inhibitor, 0.1 part internal release agent, 3 parts filler (hereinafter referred to as DAP + UP) The dispersion 2) was placed, and the resin 2 was stretched in one direction using a stretching jig 4 to which a spacer 3 was attached. The stretched resin had a uniform film thickness of 5, and a polyester film 6 coated with DAP + UP dispersion was obtained.

  The polyester film 6 coated with the DAP + UP dispersion was left in a curing furnace maintained at 100 ° C. for 10 minutes to volatilize the solvent (at this point, the curing reaction of the resin layer 5 has not yet proceeded). Then, after cutting to a predetermined size, the base film was peeled off to obtain a sheet (transparent uncured prepreg resin sheet) 7 coated with a solid DAP + UP dispersion having good handling.

(A-2)
A glass substrate (trade name: Gravest; manufactured by Olivest Co., Ltd.) having a basis weight of 30 g / square meter is attached to the impregnation apparatus as shown in FIG. Then, the base material 8 was fed, and the base material was dipped into a container containing the DAP + UP dispersion 2 and pulled up to obtain a DAP + UP dispersion-impregnated nonwoven fabric base material 10.

  The DAP + UP dispersion-impregnated nonwoven fabric base material 10 was left in a curing furnace maintained at 100 ° C. for 10 minutes to evaporate the solvent and solidify. Then, it cut | disconnected to the predetermined dimension and obtained the solid DAP + UP dispersion liquid impregnation base material (transparent uncured prepreg resin impregnation base material sheet) 11 with favorable handling.

(B-1)
As shown in FIG. 3, a glass fiber nonwoven fabric 12 having a basis weight of 30 g / m ² is laminated as a reinforcing fiber on the surface of a base film 1 made of a polyester film having a thickness of 50 μm, and transparent at one end on the surface. 100 parts by weight of uncured isophthalic acid unsaturated polyester resin, 1.0 part by weight of Parroyl TCP (manufactured by Nippon Oil & Fats Co., Ltd., trade name) as a curing agent in advance, and 4-methyl-2,4 as a chain transfer agent Thermosetting resin 13 to which 0.5 part by weight of fujenylpentene-1 (α-methylstyrene dimer) (manufactured by Nippon Oil & Fats Co., Ltd., trade name Nofmer MSD) was added was placed in a lump. On the other hand, a film (transfer film) made of a polyester film having a thickness of 50 μm, on which one side of the thermosetting resin is patterned with a pattern layer 14 patterned on one side (back surface ink layer, surface ink layer) , 15 in the order of film layers). The end of the patterning surface of the transfer film 15 is pressed against the block-shaped thermosetting resin 13, and then pressed from one end of the glass fiber nonwoven fabric 12 on the base film 1 by the roller 16 to block the block-shaped thermosetting. The thermoplastic resin 13 was stretched and defoamed uniformly, and simultaneously superimposed on the thermosetting resin 13 while impregnating the glass fiber nonwoven fabric 12.

  Next, polymerization of the resin was allowed to proceed for 30 minutes in a curing furnace in which the stretched thermosetting resin 13 was maintained at 60 ° C. The polymerization was completed while the polymerization was stopped at a curing degree of 80%. Then, after cutting to an appropriate size, when the film 1 of the transfer film 15 on the roller stretching side and the film 1 on the base side are peeled off, the pattern 14 is transferred onto the upper surface of the semi-cured thermosetting resin 12 + 13. A fiber-reinforced thermosetting resin sheet 17 was formed. This fiber reinforced thermosetting resin sheet 17 had no surface stickiness and was excellent in handling properties.

As shown in FIG. 4, after placing the transparent prepreg resin sheet 7 or the transparent prepreg resin impregnated base material 11 produced according to FIG. 1 or 2 onto the surface mold 18, the fiber reinforced thermosetting resin sheet 17 is placed. The pattern 14 is placed on the surface mold 18 side, and finally, SMC is superimposed on the fiber reinforced thermosetting resin sheet 17 as the thermosetting fiber reinforced molding material 19, and the back mold 20 is mounted. Clamped and pressurized (100 g / cm ² ) and heated (front surface mold: 150 ° C., back surface mold: 145 ° C.). The transparent prepreg resin sheet or transparent prepreg resin-impregnated base material 17 produced according to FIG. 1 or FIG. 2 and the semi-cured fiber reinforced thermosetting resin sheet 17 are cured by SMC flowing in the mold. As a result, it was completely cured and integrated, and curing was completed. The molded product was removed from the mold, and the FRP molded product 21 shown in FIG. 5 having a granite-like pattern on the surface and transferring the fine uneven pattern of the mold was obtained.

(B-2)
As shown in FIG. 6, a glass fiber nonwoven fabric 12 having a basis weight of 30 g / m ² is laminated as a reinforcing fiber on the surface of a base film 1 made of a polyester film having a thickness of 50 μm, and transparent at one end on the surface. 100 parts by weight of uncured isophthalic acid unsaturated polyester resin, 1.0 part by weight of Parroyl TCP (manufactured by Nippon Oil & Fats Co., Ltd., trade name) as a curing agent in advance, and 4-methyl-2,4 as a chain transfer agent Thermosetting resin 13 to which 0.5 part by weight of fujenylpentene-1 (α-methylstyrene dimer) (manufactured by Nippon Oil & Fats Co., Ltd., trade name Nofmer MSD) was added was placed in a lump. On the other hand, a transfer film made of a polyester film having a thickness of 50 μm, on which one side of the thermosetting resin is patterned with an ink soluble in the thermosetting resin (surface ink layer, back surface ink layer, film) 23 prepared in order). The end side of the patterning surface of the transfer film 23 is pressed against the block-shaped thermosetting resin 23, and then pressed from one end of the glass fiber nonwoven fabric 12 on the film 23 by the roller 16, so that the block-shaped thermosetting resin is pressed. The glass fiber nonwoven fabric 12 was impregnated with the glass fiber 13 while being uniformly stretched and defoamed and superimposed on the thermosetting resin 13.

  Next, polymerization of the resin was allowed to proceed for 30 minutes in a curing furnace in which the stretched thermosetting resin 13 was maintained at 60 ° C. The polymerization was completed while the polymerization was stopped at a curing degree of 80%. Then, after cutting to an appropriate size, when the film 1 of the transfer film 23 on the roller stretching side and the film 1 on the base side are peeled off, the sketch pattern 22 is transferred onto the upper surface of the semi-cured thermosetting resin 12 + 13. A fiber-reinforced thermosetting resin sheet 24 was formed. This fiber reinforced thermosetting resin sheet 24 had no surface stickiness and was excellent in handling properties.

As shown in FIG. 7, after placing the transparent prepreg resin sheet or transparent prepreg resin-impregnated substrate produced according to FIG. 1 or 2 onto the surface mold 18 having fine irregularities, the fiber reinforced thermosetting resin The sheet 24 is placed on the surface mold 18 with the pattern 22 facing away from the surface mold 18, and finally SMC is used as the thermosetting fiber reinforced molding material 19 and the fiber reinforced thermosetting resin sheet 24. The back surface mold 20 was fastened and pressed (100 g / cm ² ) and heated (front surface mold: 150 ° C., back surface mold: 145 ° C.). The transparent prepreg resin sheet 7 or the transparent prepreg resin-impregnated base material 11 produced according to FIG. 1 or FIG. 2 and the semi-cured fiber reinforced thermosetting resin sheet 24 are cured by SMC flowing in the mold. Along with this, it was completely cured and integrated with SMC, and curing was completed. The molded product was taken out of the mold, and the FRP molded product 25 shown in FIG. 8 having a granite-like pattern on the surface and transferring the fine uneven pattern of the mold was obtained.

  Since the patterned fiber reinforced thermosetting resin sheet in the above-described embodiment can be stored in a semi-cured state for a certain period, there is an advantage that an FRP molded product having a pattern on the surface can be efficiently manufactured.

  The fiber-reinforced thermosetting resin sheet comprising a base layer of a woven fabric or a non-woven fabric impregnated with a thermosetting resin having a pattern layer in the above examples is easily cured by the action of a chain transfer agent. Therefore, there is an advantage that the surface is not sticky and easy to handle, has flexibility and strength that can withstand press molding in the production of a molded product, and can be integrated with a molding material. Furthermore, since it is semi-cured, when it is integrally formed with a transparent uncured thermosetting resin by heating and pressurizing, it is possible to obtain a material having good adhesion.

  The FRP molded product in the above example has no color unevenness due to ink bleeding, the boundary of the clear portion is clear and looks good, and the pattern has no restrictions on the pattern or hue, and the fine irregularities also follow. It is possible to obtain a molded article that has good appearance and does not impair the hydrophilic expression function due to floor irregularities.

In the present invention, as a method for obtaining a sheet and a molded body having good mold transferability, environmental consideration, pattern sharpness, and pattern abrasion resistance, the object can be achieved by using the following means. The headline and the present invention were completed.
That is, when the present invention is used, from the surface side, after curing, a molded product composed of a transparent prepreg resin layer, a thermosetting resin layer, a pattern layer, a base resin layer, or from the surface side, after curing, A transparent prepreg resin layer, a thermosetting resin layer, a pattern layer, a molded body provided with a base resin layer, or a transparent prepreg resin layer, a pattern layer, a thermosetting resin layer, a pattern layer after curing from the surface side , A molded body composed of a base resin layer, and by molding using a transparent uncured prepreg resin sheet on the surface, the resin in the transparent uncured prepreg resin sheet once in the mold during heating and pressure molding Since it melts and follows the fine irregularities and cures in that state, the mold followability is good and the functions such as hydrophilicity of the product surface obtained by the good mold followability are not impaired. Since the pattern layer is directly formed on the thermosetting resin layer, the pattern ink layer is formed without any gap on the resin surface, and the pattern becomes clear. Since the pattern layer can be seen through the transparent prepreg resin layer after curing, the transparent prepreg resin layer protects the pattern ink surface, and further, when the diallyl phthalate resin is included as the prepreg resin, only the polyester resin is used. Compared to resin blends, it has the feature of high surface hardness and is durable against abrasion. Since the decorative sheet and the molding material are integrally formed in the mold, there are few problems such as solvent volatilization and consideration for the human body and the environment is possible.
In the case of a transparent prepreg resin layer, a patterned layer, a thermosetting resin layer, and a base resin layer after curing, the thermosetting resin layer is opaque or uneven in hue because the pattern layer is applied on the resin layer. Even if it has a non-homogeneous appearance, it can be concealed with a pattern, so it can give a uniform pattern regardless of the appearance of the thermosetting resin layer, and various compounds can be added to the semi-curing thermosetting resin layer For example, it is possible to mix a hollow body into a molded product to provide functions such as heat insulation.
In the case of the transparent prepreg resin layer, thermosetting resin layer, pattern layer, and base resin layer after curing, the thickness from the surface to the pattern layer can be increased by the transparent prepreg resin layer + base resin layer. , The depth of the pattern increases and the sense of quality is improved. Furthermore, by coloring the thermosetting resin layer semi-transparent or thin enough to show the pattern, it becomes two layers of the thermosetting resin layer with different transparency and texture of the transparent uncured prepreg resin sheet. Since it is formed, a further high-class feeling can be obtained.
In the case of the structure of the transparent prepreg resin layer, the pattern layer, the thermosetting resin layer, the pattern layer, and the base resin layer after curing, the pattern is lifted because the pattern layer is applied above and below the thermosetting resin layer. Various high relief effects can be obtained, and a high-class feeling can be obtained.

Method for forming transparent uncured prepreg resin sheet used in the present invention Method for forming transparent uncured prepreg resin-impregnated substrate sheet used in the present invention Process drawing which shows the manufacturing procedure of the sheet with a pattern (thing using the transfer film comprised in order of the back pattern ink layer, the surface pattern ink layer, and the film) used by this invention Process drawing which shows the procedure of carrying out the heating and pressurization integral formation of the sheet | seat with a pattern obtained in FIG.1 or FIG.2, and FIG. 3, and a reinforcement layer. Molded product obtained from FIG. Process drawing which shows the manufacturing procedure of the sheet with a pattern (thing using the transfer film comprised in order of the surface pattern ink layer, the back surface pattern ink layer, and the film) used by this invention Process drawing which shows the procedure of carrying out the heating and pressurization integral formation of the sheet | seat with a pattern obtained in FIG.1 or FIG.2, and FIG. 6, and a reinforcement layer. Molded product obtained according to FIG.

Explanation of symbols

1: Film (polyester film)
2: Organic solvent dispersion containing diallyl phthalate resin and unsaturated polyester (DAP + UP dispersion)
3: Spacer 4: Stretched jig 5: DAP + UP dispersion with uniform film thickness 6: Polyester film coated with DAP + UP dispersion 7: Sheet coated with semi-dried DAP + UP dispersion (transparent uncured prepreg resin sheet)
8: Substrate for impregnation of DAP + UP dispersion (glass fiber)
9: Substrate feeding device for impregnation of DAP + UP dispersion 10: DAP + UP dispersion impregnation nonwoven fabric (glass fiber) substrate 11: Semi-dried DAP + UP dispersion impregnation substrate (transparent uncured prepreg resin impregnation substrate sheet)
12: Fibrous substrate (glass fiber nonwoven fabric)
13: Thermosetting resin 14: Picture (ink) pattern (configured in the order of back pattern ink layer, front pattern ink layer (→ film side))
15: Transfer film (constituted in order of back pattern ink layer, surface pattern ink layer, film)
16: Stretching / impregnation means (roller)
17: Patterned fiber reinforced thermosetting resin sheet (configured in the order of back pattern ink layer, surface pattern ink layer, and fiber reinforced base material impregnated resin layer)
18: Surface mold having fine irregularities 19: Molding material (BMC or SMC)
20: Mold for back 21: Pattern can be seen through the molded product (washing floor for bathroom) 7 or 11.
22: Pattern (ink) pattern (constituted in the order of the surface pattern ink layer and the back pattern ink layer (→ film side))
23: Transfer film (constituted in the order of a surface pattern ink layer, a back pattern ink layer, and a film)
24: Patterned fiber reinforced thermosetting resin sheet (configured in the order of a surface pattern ink layer, a back pattern ink layer, and a fiber reinforced base material impregnated resin layer)
25: A pattern can be seen through the molded article (washing floor for bathroom) 7 or 11 and 12 + 13.

Claims (12)

  A decorative sheet in which a transparent uncured prepreg resin sheet and a sheet with a pattern provided with a pattern layer and a semi-cured thermosetting resin layer are overlapped and used at the time of molding.   A molded body provided with a transparent prepreg resin layer, a pattern layer, a thermosetting resin layer, and a base resin layer after curing from the surface side.   A decorative sheet in which a transparent uncured prepreg resin sheet and a sheet with a pattern provided with a semi-cured thermosetting resin layer and a pattern layer are overlapped and used from the surface side during molding.   A molded body provided with a transparent prepreg resin layer, a thermosetting resin layer, a pattern layer, and a base resin layer after curing from the surface side.   A decorative sheet in which a transparent uncured prepreg resin sheet and a patterned layer having a patterned layer, a semi-cured thermosetting resin layer, and a patterned layer are overlapped and used at the time of molding.   A molded body comprising a transparent prepreg resin layer, a pattern layer, a thermosetting resin layer, a pattern layer, and a base resin layer after curing from the surface side.   2. The decorative sheet according to claim 1, wherein the transparent uncured prepreg resin sheet contains diallyl phthalate resin.   The molded article according to claim 2, wherein the cured transparent prepreg resin layer contains diallyl phthalate resin.   4. The decorative sheet according to claim 3, wherein the transparent uncured prepreg resin sheet contains diallyl phthalate resin.   The molded article according to claim 4, wherein the cured prepreg resin layer contains diallyl phthalate resin.   6. The decorative sheet according to claim 5, wherein the transparent uncured prepreg resin sheet contains diallyl phthalate resin. The molded product according to claim 6, wherein the cured transparent prepreg resin layer contains diallyl phthalate resin.

Images