JP2002166438A - Method for in-mold decoration molding for frp - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an FRP decoration material provided with surface physical properties such as scratch resistance and design properties. SOLUTION: The FRP decoration material D is obtained by a process in which (A) on the transfer layer 2 of a transfer sheet T having a decorative layer 3 on a support sheet 1 as the transfer sheet, the incompletely cured layer 4 of a curable resin which is uncured and does not flow at room temperature is laminated to form a laminated sheet L; (B) a decorative sheet S obtained by peeling off the support sheet 1 from the laminated sheet is laid on an uncured FRP 6 to overlap each other with a fibrous sheet 7 arranged appropriately between them; (C) it is heated/pressurized, the incompletely cured layer is cured or left uncured, and the uncured FRP is cured to form an FRP layer 8 and simultaneously laminated/integrated with the decorative sheet; and (D) after heating/pressurization, the incompletely cured layer, when uncured, is cured to form a surface protective layer 9. The incompletely cured layer may be cured incompletely in the state of (A) or (B), or an uneven pattern may be formed by a mold during heating/pressurization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an FRP used for floor materials and wall materials of buildings, floor materials and wall materials of bathrooms, vanity tables and the like.
(Fiber reinforced plastic) A method of decorating a molded article.
In particular, the present invention relates to a decorating method that can simultaneously impart surface properties such as scratch resistance.

[0002]

2. Description of the Related Art Conventionally, FRP (fiber reinforced plastic)
There were the following methods as a decorating method for decorating the surface. For example, in Japanese Patent Application Laid-Open No. 8-118384, a decorative sheet formed by printing a decorative layer on the back side of a biaxially stretched polyethylene terephthalate film and backing it with a non-woven fabric is referred to as an uncured FRP SMC. (Sheet Molding Compound) and then heating and pressurizing to harden the SMC and at the same time to laminate and integrate with the decorative sheet.

[0003]

However, the product obtained by the above-described decorating method had insufficient scratch resistance because the surface was a polyethylene terephthalate film, and was particularly susceptible to scratching when used on floors and the like. It is also possible to apply a hard coating film on the surface of the polyethylene terephthalate film, but there were difficulties in increasing the number of steps and cracking during hot press lamination. Also, because it is difficult to make unevenness due to embossing,
The product surface was smooth and slippery for floor use. Of course, if a resin sheet with a lower softening temperature is used instead of polyethylene terephthalate, embossing becomes easier, but instead, the scratch resistance becomes increasingly weaker.
Neither scratch resistance nor embossing suitability were compatible. Particularly, in the case of a bathroom floor, it is particularly slippery and dangerous when wet with water. Therefore, it could not be used for such a purpose. On the other hand, if the FRP such as SMC is directly exposed on the surface, even if the abrasion resistance is satisfactory, the design feeling by the picture or the like is hardly expected.

[0004]

Therefore, in order to solve the above-mentioned problems, the present invention provides a method of decorating a FRP simultaneously with molding, the method comprising: On the transfer layer of the transfer sheet formed by forming at least a transfer layer including a decorative layer on the body sheet, an incompletely cured layer of a curable resin that is non-flowable at room temperature in an uncured state is laminated to form a decorative sheet. (B) Then, the decorative sheet obtained by peeling the support sheet from the laminated sheet is
On the release surface side, it overlaps with the uncured FRP, (C)
By heating and pressing, the incompletely cured layer is cured or uncured, and the FRP uncured material is cured to form an FRP layer, which is simultaneously laminated and integrated with the decorative sheet. When the cured layer was not cured, it was cured to form a surface protective layer. By using such a decorating method, it is possible to decorate a design with a printed pattern or the like, and to impart surface properties such as scratch resistance to the product surface. In addition, the surface protective layer providing the surface properties and the FRP layer can be laminated and integrated with good adhesion, and since the decorative layer is between the surface protective layer and the FRP layer, the wear resistance is also good.

Further, in the method for simultaneously decorating and molding a FRP according to the present invention, in the above method, when a decorative sheet is overlapped with an uncured FRP material, a fibrous sheet is interposed between the decorative sheet and the decorative sheet. The FRP layer and the FRP layer were laminated and integrated via a fibrous sheet therebetween. By doing so, the decorative sheet composed of the surface protective layer and the decorative layer and the FRP layer can be laminated with good adhesion, and the dimensional stability of the obtained product increases. In addition, distortion and flow of the pattern of the decorative layer hardly occur.

Further, the method of simultaneously decorating a FRP according to the present invention is the method of any of the above methods, wherein the state of the laminated sheet in the step (A) or the state of the decorative sheet in the step (B) is used. After the curing reaction of the curable resin was advanced to such an extent that the curing of the incompletely cured layer of the curable resin was not completely completed, the step (C) and the subsequent steps were performed. In this way, the incompletely cured layer of the curable resin serving as the surface protective layer is subjected to a curing reaction within a range that does not result in complete curing, and then heated and pressed to laminate and integrate the decorative sheet and the FRP layer. By doing so, the distortion and flow of the picture due to the flow and deformation of the incompletely cured layer due to heat and stress at the time of heating and pressurization can be made hard to occur.

Further, in the method for simultaneously decorating and molding a FRP according to the present invention, in any one of the above-mentioned methods, a concavo-convex pattern is formed into an incompletely cured layer by a forming die simultaneously with heating and pressing.
Thereafter, the incompletely cured layer was completely cured.
By doing so, good unevenness can be imparted to the surface of a hard product having scratch resistance. Therefore, for example, a slip prevention effect suitable for floor use can be obtained. In addition, a design feeling due to surface matting and uneven patterns can be imparted.

[0008]

Embodiments of the present invention will be described below with reference to the drawings.

[Summary] FIG. 1 is a conceptual diagram conceptually illustrating a method of simultaneously decorating a FRP according to the present invention. In the present invention, first, as a transfer sheet T as shown in FIG. 1A, a sheet including at least a decorative layer 3 as a transfer layer 2 on a support sheet 1 is prepared. Then, as shown in FIG. A transfer sheet T and an incompletely cured layer 4 of a curable resin that is non-flowable at room temperature in an uncured state are laminated so that the transfer layer 2 and the incompletely cured layer 4 are in contact with each other. L.
The lamination of the incompletely cured layer 4 and the transfer sheet T is performed by, for example, as shown in FIG. 1B, by setting a curable resin in a fluidized state by heating on a transfer sheet T with the transfer layer 2 facing upward. The incompletely cured layer 4 is formed by coating or the like. Laminated sheet L
May have a configuration in which the separator sheet 5 is temporarily laminated as necessary on the upper side (the side opposite to the lamination surface of the transfer sheet, which is the surface in the final product).

In the present invention, a laminate in which at least the incompletely cured layer 4 and the transfer sheet T are laminated is referred to as a laminated sheet L. The laminated sheet L is shown in FIG.
As shown in (B), a configuration in which the separator sheet 5 is further laminated may be used. In addition, the laminate having the configuration after the transfer sheet-derived support sheet 1 is peeled from such a laminate sheet L is referred to as a decorative sheet S in distinction. Therefore, the separator sheet 5 may be included as a component of the decorative sheet S in some cases.

Then, as shown in FIG. 1C, the support sheet 1 is peeled off from the laminated sheet L as described above to form a decorative sheet S, and the decorative sheet S and the uncured FRP 6 are laminated. Of course, at this time, as shown in FIG. 1 (C), the decorative sheet S
It piles up toward P uncured material 6 side. At this time, FIG.
As shown in (C), it is also preferable to insert a fibrous sheet 7 made of a nonwoven fabric or a woven fabric between the decorative sheet S and the uncured FRP 6 in terms of adhesion and reproduction of a picture. When there is no fiber sheet, a form in which the fibrous sheet 7 is not inserted may be used.

Prior to the heating and pressurizing step (FIG. 1 (D)), a step of causing the curing reaction of the incompletely cured layer to proceed to such an extent that it does not reach complete curing (this is called a preliminary curing step). In the case where the decorative sheet S is provided, the step of mounting the decorative sheet S on the FRP uncured material as shown in FIG. 1C from the step of FIG. At the appropriate stage before the mounting). Pre-curing, when the curable resin is a thermosetting resin, irradiation by infrared (including near-infrared and far-infrared) irradiation, heating in a heating atmosphere, etc., and when the curable resin is an ionizing radiation-curable resin, When the curable resin is a resin which is cured by both heat and ionizing radiation, the curing is performed by heating or irradiation of ionizing radiation.

Next, as shown in FIG. 1 (D), the decorative sheet S and the uncured FRP 6 are heated and pressurized to cure the uncured FRP 6 to form the FRP layer 8. At the same time, the decorative sheet S is bonded and laminated on the FRP layer 8 to be integrated. As shown in FIG. 1 (D), the heating and pressurizing may be performed by placing these materials on top of each other in the forming mold Ma and the forming mold Mb, then clamping and heating the forming molds Ma and Mb. . In the description of FIG. 1, as shown in FIG. 1C, the fibrous sheet 7 is interposed therebetween, and the FRP uncured material 6 is impregnated into the fibrous sheet 7 by hot pressure. The layer 8 is provided with the decorative sheet S via the fibrous sheet 7.
Will be integrated into a stack. However, if the fiber sheet 7 is not provided, the decorative sheet S and the FRP layer 8 have sufficient adhesive force, and if the decorative layer is not distorted or flows, the insertion of the fiber sheet 7 is omitted. Can be done. The incompletely cured layer 4 may be cured at the same time as the heating and pressing to form the surface protective layer 9, or may be cured after the heating and pressurizing to become the surface protective layer 9. However, if the incompletely cured layer 4 is also cured at the same time as the heating and pressurizing, the post-curing step for the layer can be omitted.

Then, as shown in FIG. 1E, when the heating and pressurizing are released and the incompletely cured layer 4 has not been completely cured yet, heat or ionizing radiation such as ultraviolet rays or electron beams is further applied. When the curing is completed by the curing means C to form the surface protective layer 9, the transfer layer 2 including at least the decorative layer 3 (as the decorative sheet S) and the surface protective layer 9 are laminated on the FRP layer 8 in this order. The FRP decorative material D having the above configuration is obtained. In addition,
When the separator sheet 5 is still laminated on the decorative sheet S, the separator sheet 5 is peeled off. The separation and removal of the separator sheet 5 may be performed at any time after the heat and pressure release. It may be immediately after the release of the heating and pressurizing, immediately before the application of the FRP decorative material to the floor or the like, or after the completion of the application. If the separation is performed after the completion of the construction, the separator sheet can also be used to prevent dust adhesion during the construction.

When it is desired to provide an uneven pattern on the surface of the surface protective layer 9, as shown in FIG. 2A, the separator sheet 5 is provided with an uneven pattern on the surface in contact with the incompletely cured layer 4. After the incompletely cured layer 4 is cured by using the resulting material as the shaping mold 11, it is peeled and removed, or as shown in FIG. 2 (B), when the separator sheet is laminated on a decorative sheet, After peeling off or when heating and pressing (from above) with the separator sheet laminated, a metal plate or the like provided with a concavo-convex pattern on one surface is shaped into a shaping mold 11.
It is only necessary that the shaping mold 11 be removed after the heating and pressurizing is performed after the insertion into contact with the surface of the incompletely cured layer 4. 2 (A) and 2 (B) conceptually show a case where shaping is performed by heating and pressing with flat pressure using pressurizing plates Pa and Pb of a hot press.

Hereinafter, the present invention will be described in more detail in order from the transfer sheet.

[Support Sheet] The support sheet 1 is not particularly limited as long as it has a releasability from the transfer layer 2 and the incompletely cured layer 4. However, as a typical method of laminating an incompletely cured layer serving as a surface protective layer with a transfer sheet, a curable resin to be used as an incompletely cured layer is formed by heating melt coating or as a solvent dilution solution. It is formed by coating. Therefore, the support sheet is heated at that time,
Alternatively, a material having heat-resistant dimensional stability or solvent resistance is preferable so that the pattern of the decorative layer constituting the transfer layer is not distorted by the solvent. Such a heat-resistant dimensional stability, and a solvent-resistant support sheet, for example, polyethylene terephthalate, polyethylene naphthalate, polyester resin such as polyarylate, resin sheet such as vinylon,
Metal foil, paper, or a laminated sheet thereof is used. The laminated sheet is, for example, a sheet in which polypropylene is laminated on relatively uniform paper such as high-quality paper, parchment paper, parchment paper, or the like. Above all, a biaxially stretched polyethylene terephthalate film is typical. The thickness of the support sheet is usually about 20 to 200 μm.

The support sheet may be provided with a release layer as a component of the support sheet, if necessary, on the transfer layer side in order to improve the releasability from the transfer layer. The release layer is removed from the transfer layer as a part of the support sheet when the support sheet is released. As the release layer, for example, silicone resin, melamine resin, polyamide resin,
A simple substance such as a urethane resin or a mixture containing these is used.

[Transfer Layer] The transfer sheet T has at least a decorative layer 3 as a transfer layer 2 on a support sheet 1.
In addition, as the transfer layer 2, a release layer, an adhesive layer, or the like may be further provided as appropriate in addition to the decorative layer. The transfer layer may be formed by a conventionally known printing method, coating method, or any other forming means such as hand-drawing, depending on the content.

The decorative layer 3 is made of a conventionally known method such as gravure printing, silk screen printing, offset printing, or ink jet printing, a pattern layer obtained by printing a pattern or the like with a material, or a metal such as aluminum, chromium, gold, or silver. A metal thin film layer or the like formed partially or over the entire surface by using a vapor deposition method or the like, which is used according to the application. The pattern is a stone pattern,
A tile pattern, a grain pattern, a cloth pattern, a brick pattern, a leather pattern, a character, a geometric pattern, a solid surface, a combination thereof, or the like is used. The ink for the picture layer is usually composed of a vehicle such as a binder, a coloring agent such as a pigment or a dye, and various additives appropriately added thereto. As the resin of the binder, an acrylic resin, a vinyl chloride-vinyl acetate copolymer, a polyester resin, a cellulosic resin, a urethane resin, or the like, or a mixture containing them is used. Colorants include inorganic pigments such as titanium white, zinc white, carbon black, iron black, red iron oxide, vermilion, graphite, titanium yellow, cobalt blue, ultramarine blue, aniline black, quinacridone red, isoindolinone yellow, and phthalocyanine blue. And other organic pigments, brilliant pigments such as aluminum foil powder, brass foil powder, mica foil powder coated with titanium dioxide, fluorescent pigments, and other dyes.

The decorative layer may be a functional layer such as a conductor layer or a magnetic layer. That is, the decoration in the present invention includes not only simply providing a picture or the like, but also providing functionality. For example, a conductive material such as graphite powder or silver powder is used in place of the colorant for the conductive layer, and a magnetic material such as ferric oxide is used in place of the colorant for the magnetic material layer. Or it may be contained in it. These functional layers may be used also as the picture layer.

Although the release layer is not essential, it may be provided as needed to adjust the release property between the support sheet and the transfer layer. For the release layer, for example, a resin or the like used for the binder described above in the picture layer is used.
Note that the release layer is a part of the transfer layer, and the entire release layer normally moves to the transfer-receiving body side during transfer.

Although the adhesive layer is not essential, it may be provided as necessary to improve the adhesion between the decorative layer and the incompletely cured layer. The adhesive layer is not particularly limited, and may be a resin that can be laminated with good adhesion according to the resin content of the decorative layer and the incompletely cured layer. For example, an acrylic resin, a polyester resin, a urethane resin, a polyamide resin, an epoxy resin, or the like is used. In addition, the resin is usually used as a curable resin, but is preferable in terms of durability of adhesion.

[Incompletely Cured Layer] The incompletely cured layer 4 is a layer which is finally cured to form the surface protective layer 9, and when applied to decorating simultaneously with molding, it is uncured in a non-cured state at room temperature. It is made of a flowable curable resin. The above-mentioned incomplete curing refers to a state in which curing has not progressed at all, or a state in which curing has progressed (or has proceeded) but has not been completed, that is, a state in which curing has not completely completed (uncured state) ). Further, this incompletely cured layer is preferably a layer that does not contain fibers contained in the case of FRP. If the incompletely cured layer contains fibers, it is inevitable that the fibers will come out to the surface when the incompletely cured layer is cured and becomes a surface protective layer, This is because a fibrous uneven pattern emerges.

The non-fluidity may be a non-sticky solid or a sticky state. The normal temperature refers to a molding (simultaneous decorating) operation in which a decorative sheet in which a transfer layer including a decorative layer and an incompletely cured layer are laminated is inserted into a molding die so as to be laminated and integrated with an uncured FRP material. Means the indoor (or outdoor) ambient temperature at which the process is performed. The specific value varies depending on the climate and working environment, but is usually in the range of 10 to 40 ° C. The heating temperature during molding is higher than normal temperature. Curing for forming a surface protective layer is most preferably cross-linking in terms of surface strength, but may be non-cross-linking as long as required physical properties are satisfied.

The resin used for the incompletely cured layer is not particularly limited as long as it has the above-mentioned characteristics. Therefore, the curing by the curable resin may be either crosslinking curing or non-crosslinking curing. However, cross-linking curing is preferable to non-cross-linking curing because surface strength is easily obtained. The curing reaction mode may be any of addition polymerization, polyaddition, and condensation polymerization. The energy for curing is heat,
Any of ionizing radiation and the like may be used. However, the use of at least heat is efficient in that the curing reaction is performed simultaneously with the uncured FRP in the heating and pressurizing step, and a dedicated curing step is omitted. Note that, as the ionizing radiation, an ultraviolet ray and an electron beam are representative.

Examples of the resin as described above include a thermosetting resin such as an unsaturated polyester resin, a curable acrylic resin, an epoxy resin, a diallyl phthalate resin, a melamine resin, a urethane resin, an ionizing radiation curable resin, or a thermosetting resin. For example, a resin or the like that cures with both ionizing radiation and ionizing radiation can be used.
The resin used for the incompletely cured layer is usually used as a composition obtained by adding various additives such as a curing catalyst, a pigment, and a filler to a single resin. Therefore, the property of being non-flowable at room temperature in an uncured state may be provided as a resin alone or as a composition. Also, for example, as the curing catalyst,
When an unsaturated polyester resin is used as the thermosetting resin, a thermal polymerization initiator such as benzoyl peroxide and methyl ethyl ketone peroxide is added.

As the ionizing radiation-curable resin, for example, the following ionizing radiation-curable resins (I) and (II) can be used.

(I) having a radically polymerizable unsaturated group,
The following two types of thermoplastic resins (1) or (2). (1) Those having a radical polymerizable unsaturated group in a polymer having a glass transition temperature of 0 to 250 ° C. More specifically, the following (1-1) to (1-8) were polymerized or copolymerized, and radically polymerizable unsaturated groups were introduced by methods (a) to (d) described below. Can be used. In the following, for example, (meth) acrylate is used to mean acrylate or methacrylate. (1-1) a monomer having a hydroxyl group; N-methylol (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2
-Hydroxy-3-phenoxypropyl (meth) acrylate and the like. (1-2) Monomers having a carboxyl group: (meth) acrylic acid, (meth) acryloyloxyethyl monosuccinate and the like. (1-3) Monomers having an epoxy group; glycidyl (meth) acrylate and the like. (1-4) Monomers having an aziridinyl group: 2-aziridinylethyl (meth) acrylate, allyl 2-aziridinylpropionate and the like. (1-5) Monomers having an amino group: (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the like. (1-6) A monomer having a sulfone group; 2- (meth) acrylamido-2-methylpropanesulfonic acid and the like. (1-7) Monomer having isocyanate group; addition of diisocyanate such as adduct of 2,4-toluene diisocyanate and 2-hydroxyethyl (meth) acrylate in a ratio of 1 mol to 1 mol and radical polymerizable monomer having active hydrogen. Things. (1-8) a monomer other than the above (1-1) to (1-7) which is copolymerizable with the monomer of the above (1-1) to (1-7); this monomer is a glass of the obtained copolymer Used as a copolymer component to control the transition temperature and physical properties. For example, methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, isobutyl (meth) acrylate, te
rt-butyl (meth) acrylate, isoamyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.

Next, the polymer or copolymer obtained as described above is reacted by the following methods (a) to (d) to introduce a radically polymerizable unsaturated group. (a) In the case of a polymer or copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group such as the above-mentioned (1-2) (meth) acrylic acid is subjected to a condensation reaction. (b) In the case of a polymer or copolymer of a monomer having a carboxyl group or a sulfone group, the monomer having a hydroxyl group described in (1-1) is subjected to a condensation reaction. (c) In the case of a polymer or copolymer of a monomer having an epoxy group, an isocyanate group, or an aziridinyl group, the monomer having a hydroxyl group described in (1-1) or the aforementioned
The addition reaction of the monomer having a carboxyl group of (1-2) is performed. (d) In the case of a polymer or copolymer of a monomer having a hydroxyl group or a carboxyl group, the monomer having an epoxy group of the above (1-3) or the monomer having an aziridinyl of the above (1-4) or the above (1-4) -7) is subjected to an addition reaction with a monomer having an isocyanate group such as a 1 to 1 mole adduct of a diisocyanate compound and a hydroxyl group-containing acrylate monomer. In order to carry out the above reaction, it is desirable to add a trace amount of a polymerization inhibitor such as hydroquinone and to carry out the reaction while sending dry air.

(2) A compound having a melting point of 20 ° C. to 250 ° C. and having a radically polymerizable unsaturated group. Specifically, triazine (meth) acrylate, stearyl (meth) acrylate, triacryl isocyanurate, cyclohexanediol di (meth) acrylate, spiroglycol di (meth) acrylate, spiroglycol (meth)
Acrylate and the like.

The above (1) and (2) can be used as a mixture. Furthermore, the above (1) or (2), or (1) and
A radical polymerizable monomer can be added as a reactive diluent to the mixture of (2). This radical polymerizable monomer increases the crosslink density by irradiation with ionizing radiation and improves heat resistance. Examples of the monomer include, in addition to the above-mentioned monomers (1-1) to (1-8), ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and hexanediol di (meth) acrylate.
Acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, polyethylene glycol diglycidyl ether di (meth) acrylate, propylene glycol diglycidyl ether di (meth) acrylate, polypropylene glycol diglycidyl ether di (meth) acrylate, sorbitol Tetraglycidyl ether tetra (meth) acrylate or the like can be used. The compounding amount is preferably 0.1 to 100 parts by mass based on 100 parts by mass of the resin of the above (1) or (2) alone or as a mixture. Further, a non-crosslinked resin described in (b) below can also be added.

(II) An ionizing radiation curable resin obtained by mixing a non-crosslinkable resin which is a thermoplastic solid at normal temperature with an ionizing radiation curable resin which is liquid at normal temperature. (A) Ionizing radiation curable resin which is liquid at ordinary temperature; a composition comprising a simple substance or a mixture of a prepolymer or monomer having a radical polymerizable unsaturated group in a molecule. Alternatively, it is a composition comprising a prepolymer or monomer having a cationically polymerizable functional group. Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, and melamine (meth) acrylate. Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers such as methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Phenoxyethyl (meth) acrylate and the like. Also, as polyfunctional monomers, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylpropane tri (meth)
There are acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like. Examples of prepolymers having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol epoxy resins and novolak epoxy compounds, and vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers.

(B) The non-crosslinkable resin is a room temperature solid thermoplastic resin which does not contribute to the crosslinking and curing reaction due to ionizing radiation. Examples thereof include an acrylic resin, a cellulose resin, a polyester resin, a urethane resin, and a vinyl acetate resin. ,
Vinyl resins such as vinyl chloride-vinyl acetate copolymers and butyral resins. For example, acrylic resin, as its monomers, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate,
N-butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, n-hexyl (meth) acrylate, (meth) acrylic acid
Alkyl (meth) acrylates such as n-octyl and lauryl (meth) acrylate; alkyl (meth) acrylates such as 2-chloroethyl (meth) acrylate and 3-chloropropyl (meth) acrylate ,
2-Hydroxyethyl (meth) aclurate, (meth)
(Meth) acrylates having a hydroxyl group such as 2-hydroxypropyl acrylate, halogenated (meth) acrylates such as α-methyl (meth) acrylate, ethyl α-chloro (meth) acrylate, ( Meta)
It is composed of one or more of α-alkyl (meth) acrylates having a hydroxyl group such as 1-chloro-2-hydroxyethyl acrylate and (meth) acrylic monomers such as glycidyl (meth) acrylate. It is a homopolymer or a copolymer.

When curing with ultraviolet light or visible light, a photopolymerization initiator is further added to the ionizing radiation-curable resin of the above (I) or (II). In the case of a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ethers can be used alone or in combination as a photopolymerization initiator. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoinsulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to. The amount of addition of these photopolymerization initiators is 0.1 to 100 parts by mass of the ionizing radiation-curable resin.
It is about 1 to 10 parts by mass.

As the ionizing radiation, electromagnetic waves or charged particles having energy capable of polymerizing or crosslinking molecules in the ionizing radiation-curable resin are used. Usually, ultraviolet rays or electron beams are used, but it is also possible to use visible rays, X-rays, ion beams or the like. As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, and a metal halide lamp is used. As a wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm is usually mainly used. As the electron beam source, various types of electron beam accelerators such as Cockcroft-Walton type, Van degraft type, resonance transformer type, insulating core transformer type, or linear type, dynamitron type, high frequency type, etc. are used, preferably 100 to 1000 keV, preferably. A device that irradiates electrons having an energy of 100 to 300 keV is used.

A typical example of a resin that cures with both heat and ionizing radiation is a resin that cures with light such as ultraviolet light or visible light and heat. Specifically, a resin obtained by adding both a photopolymerization initiator and a thermal polymerization initiator to a radical polymerizable resin such as an unsaturated polyester resin or a diallyl phthalate resin is used.

As the photopolymerization initiator, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ethers and the like are used. Examples of the thermal polymerization initiator include organic peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, isopropyl peroxide, t-butyl peroxybenzoate, azobisisobutyronitrile, and azobiscarbonamide. An azo compound or the like is used. The addition amounts of these photopolymerization initiators and thermal polymerization initiators are all the same for the radical polymerizable resin 100, respectively.
It is about 0.01 to 10 parts by mass in parts by mass.

Various additives can be added to the incompletely cured layer using the above-mentioned curable resin as needed. As these additives, for example,
They include coloring agents, abrasives, fillers, ultraviolet absorbers, light stabilizers, antibacterial agents, fungicides, and other additives.

For example, as the above-mentioned coloring agent, known additives listed in the above-mentioned decorative layer can be used. When a coloring agent is added, it is usually colored and transparent so that the pattern of the lower decorative layer can be seen. In addition, since the incompletely cured layer eventually becomes a surface protective layer, the addition of a lubricating agent is particularly effective for floor materials and the like. In addition, as an abrasive, powder such as alumina (α-alumina), silica, aliminosilicate, mica, and the like can be used. The particle size of these lubricants is usually from 1 to 100.
In μm, the particle shape is sphere, polyhedron, scale, etc. The amount of the lubricating agent is usually about 5 to 50% by mass relative to the resin component. As the filler, powders such as calcium carbonate, clay and talc can be used. The particle size of the filler is about 0.1 to 10 μm, and the amount added is 5
About 50% by mass. Also, benzotriazole-based, benzophenone-based, ultrafine cerium oxide-based and the like can be used as an ultraviolet absorber, and a hindered amine-based radical scavenger and the like can be used as a light stabilizer.

In order to laminate an incompletely cured layer made of a curable resin as described above with a transfer sheet, the curable resin in a fluidized state is usually coated on the transfer sheet, depending on its thickness. It is formed by applying and solidifying by a construction method. In order to obtain a fluidized state, the resin may be heated and melted or dissolved in a solvent. Although a certain thickness can be ensured by repeating coating even when a solvent is used, heating is preferred because it is thicker and easier to form. The coating may be performed by a known method such as extrusion coating (extruded lamination), cast coating, fountain coating, comma coating and the like. In addition, the thickness of the incompletely cured layer may be appropriately set according to the application, required physical properties, and the like, but is usually about 10 to 500 μm.

When the incompletely hardened layer is thermally hardened, the timing of promoting the hardening of the incompletely hardened layer can be simultaneous with the hardening of the FRP uncured material. Further, in the case where curing by means other than heat (for example, ionizing radiation) is required for complete curing of the incompletely cured layer, curing may be performed after heating and pressing. Further, even in the case of performing complete curing by thermal curing, the curing may be completed by performing only heating after heating and pressing, without proceeding to complete curing during heating and pressing.

[Separator sheet] Separator sheet 5
Is appropriately used as necessary, but by using the sheet, it is possible to prevent scratches and dust from being attached to the front surface of the incompletely cured layer whose surface is still easily damaged before curing. Can be protected. In addition, when the incompletely cured layer exhibits tackiness, the laminated sheet or the decorative sheet can be easily used. In addition, if the incompletely cured layer is soft and it is difficult to handle the decorative sheet in a state of a decorative sheet after the support sheet has been peeled off from the laminated sheet, if the separator sheet is left attached, the separator sheet can be used. It plays the role of a support for the incompletely cured layer, and can maintain the strength as a decorative sheet and facilitate handling. Further, as described later, a shaping die for forming irregularities can be used.

When a separator sheet is used, FIG.
As shown in (B), when the separator sheet 5 is laminated on the incompletely cured layer 4 formed on the transfer sheet T using a roller or the like so as not to trap air, a laminated sheet L is obtained. good. Alternatively, it is also possible to apply a curable resin on a separator sheet to form an incompletely cured layer, and then laminate a transfer sheet thereon to form a laminated sheet. This method is
In particular, it is preferable to use the separator sheet also as the shaping mold. Of course, even when the separator sheet is also used as a shaped form, the incompletely cured layer and the transfer sheet may be laminated, and then the separator sheet may be laminated thereon.

The separator sheet as described above is not particularly limited as long as it is a sheet that can be peeled off from the incompletely cured layer when it becomes unnecessary. For example, the sheet described as the support sheet of the transfer sheet can be used. Therefore, further description is omitted here. However, when the separator sheet is peeled off after heating and pressing, use a heat-resistant material that can withstand the heat at that time.

[FRP Uncured Material] The FRP uncured material 6 may be a conventionally known FRP molding material, and in the case of the present invention, among others, SMC (sheet molding compound) and BMC (bulk molding compound) Etc. are typically used. In particular, since SMC is already formed into a sheet, it is suitable for forming a flat FRP decorative material. The uncured FRP is cured by heating. As the resin of the FRP uncured material, an unsaturated polyester resin is typical, but other resins, for example, (curable) acrylic resin, epoxy resin,
So-called thermosetting resins such as diallyl phthalate resin, melamine resin and urethane resin can also be used. The fiber as a reinforcing material of FRP is typically glass fiber, but inorganic fiber such as carbon fiber and potassium titanate fiber, or synthetic resin fiber such as polyester fiber, nylon fiber and vinylon fiber is also used. In addition, fillers such as silica, alumina and calcium carbonate, coloring agents such as pigments and dyes, curing catalysts, thickeners, stabilizers, plasticizers, lubricants, A material to which a flame retardant, a thermoplastic resin or the like is added is used.

The uncured FPR becomes an FRP layer when heated and pressed by a molding die or a press machine in a state of being superimposed on a decorative sheet comprising an incompletely cured layer and a decorative layer. Laminated and integrated with the sheet. The heating and pressurizing conditions are conditions according to the resin used for the uncured FPR and the incompletely cured layer. For example, when an SMC made of an unsaturated polyester resin or the like is used for the uncured FRP, the temperature is usually 120 to 160 ° C., 1 to 10 MPa, and the heating and pressing time is about 5 to 20 minutes.

[Fibrous Sheet] It is a preferable embodiment of the present invention that a fibrous sheet is interposed between the uncured FRP and the decorative sheet during the heating and pressurizing. Due to the fibrous sheet, the adhesion and dimensional stability are increased, and the fibrous sheet is interposed even when the FRP uncured material flows at the time of heating and pressing, so that the pattern of the decorative layer is distorted,
Flow or cracks are less likely to occur. Examples of the fibrous sheet include synthetic resin fibers made of acrylic, nylon, polyester, polypropylene, rayon, acetate, vinylon, polyvinyl chloride, and the like, and natural organic fibers such as cellulose, pulp, and wool, or glass. Inorganic fibers made of asbestos, potassium titanate, alumina, silica, carbon and the like are used. In particular, when imparting heat resistance (deformation) to a fibrous sheet, a fiber sheet impregnated with a thermosetting resin such as a two-component curable urethane resin, an epoxy resin, or a thermosetting acrylic resin is used as the fibrous sheet. Is preferred. In addition, a woven fabric, a nonwoven fabric, or a knitted fabric is used as a form of gathering the fibers. The nonwoven fabric made of cellulose is paper, and examples of the paper include high-quality paper, kraft paper, and Japanese paper. Above all, in consideration of cost, physical properties, adhesion, impregnation performance, followability to a curvature portion, and the like, a nonwoven fabric of a synthetic resin fiber having a thickness of 0.2 mm or less is preferable.

[Shaping of Concavo-convex Pattern] In the simultaneous decorating method of the present invention, a concavo-convex pattern may be formed on the surface of the surface protective layer. The uneven pattern is, for example, a grain, a satin finish, a hairline, a linear groove, a concave and convex pattern of a cleavage surface of granite, a wood grain conduit groove, a wood grain annual ring pattern, a texture of a cloth grain, a leather squeezing, a character, a geometric pattern, or This is a joint groove pattern when two-dimensionally arranging tiles, bricks, stones, or the like, or a combination pattern thereof. In particular, in flooring applications, uneven patterns such as grain are effective in preventing slippage.

In order to form the concavo-convex pattern, as shown in the conceptual diagram of FIG. 2, the FRP uncured material 6 and the decorative sheet S are formed by an appropriate forming means such as press plates Pa and Pb of a hot press machine. The heating and pressurization may be performed in a state where the shaping mold 11 is in contact with the incompletely cured layer 4 serving as the surface protective layer. FIG. 2 (A) shows that the separator sheet 5 described above is
1 and FIG. 2 (B) shows a case where the shaping mold 11 is inserted at the time of heating and pressing (not laminated and integrated with the incompletely cured layer 4 in advance). As the shaping mold 11 in FIG. 2B, the same one as the separator sheet S as described above can be used, and a known metal shaping mold and the like can also be used. After the heating and pressurization, if the shaping mold is removed, an uneven pattern is formed on the surface of the incompletely cured layer 4. If the incompletely cured layer has not been completely cured at the time of heating and pressurizing, the shaping mold may be removed after completely curing to form a surface protective layer.

When the separator sheet 5 is used as the shaping mold 11, irregularities may be formed on the sheet surface by a known method. For example, by using an ink that uses a resin having releasability from the surface protective layer (for example, using a two-component curable urethane resin, a silicone resin, a melamine resin, or an ionizing radiation-curable resin), emboss printing by silk screen printing or the like. May be used to form a shaping layer, or to form surface irregularities by sandblasting or the like.

[Use of FRP decorative material]
Although the use of the RP decorative material is not particularly limited, it is used for various purposes, for example, as a decorative panel or a decorative member. Preferably, it is used for applications that make use of its surface properties such as scratch resistance. For example, flooring and wall materials for buildings, flooring and wall materials for bathrooms, housing equipment such as vanities, handrails, doors and other fittings, furniture, home appliance cabinets, cars, trains, aircraft,
It can be used in various fields such as interior materials for vehicles such as ships and containers. The shape of the FRP decorative material may be a three-dimensional shape in addition to a flat shape.

[0053]

Next, the present invention will be described in more detail by way of examples.

Example 1 First, a transfer sheet T was prepared by baking and coating a melamine resin on one surface of a biaxially stretched polyethylene terephthalate film having a thickness of 50 μm to form a release layer having a thickness of 0.5 μm. Was used as a support sheet 1. Then, a decorative layer 3 was formed as a transfer layer 2 on the surface of the support sheet on the release layer side by gravure printing [FIG.
(A)]. As the decorative layer, the binder resin is a mixed resin of an acrylic resin and a vinyl chloride-vinyl acetate copolymer in a ratio of 1: 1 by mass, and titanium white, quinacridone red, isoindolinone yellow, and phthalocyanine blue are used as coloring agents. A marble-like marble pattern layer was formed by printing using the ink.

Then, as the incompletely cured layer 4, the unsaturated polyester prepolymer (containing styrene monomer) 100
1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 1”) was used as a photopolymerization initiator with respect to parts by mass.
84 ", manufactured by Ciba-Geigy Co., Ltd.) and a resin composition to which 1 part by mass of benzoyl peroxide was added as a thermal polymerization initiator was melt-extruded from a T-die so as to have a thickness of 200 μm, and room temperature was 20 ° C. And cooled and solidified to obtain a laminated sheet L as a non-adhesive solid [see FIG. 1 (B)].

Next, the decorative sheet S obtained by peeling the support sheet 1 from the laminated sheet L is placed in the molds Ma and Mb.
With a 2 mm thick FRP uncured product 6 with a nonwoven fabric made of polyester fiber interposed therebetween as a fibrous sheet 7
After superimposition with three SMCs (to become unsaturated polyester resin and glass fiber) (see FIG. 1 (C)), 140
The molding was performed by heating and pressing under heat and pressure conditions of 7 ° C. and 7 MPa for 5 minutes, and the decorative sheet S was integrally laminated on the surface of the uncured FRP layer 6 simultaneously with the molding. FRP uncured material 6 is cured and FR
It became the P layer 8. Further, the incompletely cured layer 4 was partially cured by heat (see FIG. 1D).

Then, after being removed from the mold, the incompletely cured layer is irradiated with ultraviolet rays using a high pressure mercury lamp to further cure the incompletely cured layer so as to form the surface protective layer 9, and the unreacted portion of the incompletely cured layer is completely removed. And FRP decorative material D was obtained. FRP
The cosmetic material D is provided on the FRP layer 8 via the fibrous sheet 7.
As the decorative sheet S, the decorative layer 2 which was the transfer layer 2 and the surface protective layer 9 which was the incompletely cured layer 4 were laminated (see FIG. 1 (E)). The obtained FRP decorative material had a high design with a stone-patterned decorative layer in addition to surface properties with good scratch resistance.

[0058]

(1) According to the method of simultaneously decorating an FRP according to the present invention, it is possible to decorate a design with a printed pattern or the like, and to provide a product surface with surface properties such as scratch resistance. Can also be provided. In addition, the surface protective layer providing the surface properties and the FRP layer can be laminated and integrated with good adhesion, and since the decorative layer is between the surface protective layer and the FRP layer, the wear resistance is also good. (2) Further, when a laminate (decorative sheet) of an incompletely cured layer and a decorative layer to be a surface protective layer and an uncured FRP are laminated, a fibrous sheet made of a nonwoven fabric or a woven fabric is sandwiched therebetween. Molding allows for good lamination and also increases the dimensional stability of the resulting product. In addition, the pattern of the decorative layer is hardly distorted. (3) If the incompletely cured layer is allowed to undergo a curing reaction within a range that does not result in complete curing, and then heated and pressed to perform lamination and integration of the decorative sheet and the FRP layer, heating and heating can be performed. The distortion and flow of the picture due to the flow and deformation of the incompletely hardened layer due to the heat and stress at the time of pressing can be less likely to occur. (4) If the uneven pattern is formed on the incompletely cured layer by the forming die at the same time as the heating and pressing at the time of molding, good unevenness can be imparted to the surface of a hard product having scratch resistance. Therefore, for example, a slip prevention effect suitable for floor use can be obtained.
In addition, a design feeling due to surface matting and uneven patterns can be imparted.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram conceptually illustrating a method for simultaneously decorating a FRP according to the present invention.

FIG. 2 is a conceptual diagram conceptually illustrating a method of forming a concavo-convex pattern on a surface simultaneously with molding.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Support sheet 2 Transfer layer 3 Decorative layer 4 Incompletely cured layer 5 Separator sheet 6 FRP uncured material 7 Fibrous sheet 8 FRP layer 9 Surface protective layer 11 Shaping type C Hardening means D FRP decorative material Ma, Mb Mold L Laminated sheet Pa, Pb Pressing plate of heat press machine S Decorative sheet T Transfer sheet

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F204 AA13K AA15E AA15K AA18E AA18K AA21K AA36 AA41 AB25 AH48 FA01 FB01 FB11 FB19 FB24 FE06 FF06 FG02 FN11 FN15 FN17 FQ01 FQ15 FW06 FW15 FW15 FW15 FW15

Claims (4)

[Claims] 1. A method for decorating the surface of a FRP simultaneously with the molding of the FRP, comprising: (A) forming an uncured state on a transfer layer of a transfer sheet having at least a transfer layer including a decorative layer formed on a support sheet; (B) Then, a decorative sheet obtained by peeling the support sheet from the laminated sheet is laminated on the peeled surface of the incompletely cured layer of a curable resin which is non-flowable at room temperature. (C) Then, by heating and pressurizing, the incompletely cured layer is cured or remains uncured, and the FRP uncured material is cured to obtain an FR.
A method for simultaneously decorating and molding a FRP, wherein the P layer is simultaneously laminated and integrated with the decorative sheet, and (D) after heating and pressing, if the incompletely cured layer is not cured, it is cured to form a surface protective layer. 2. When the decorative sheet is overlapped with the uncured FRP material, the decorative sheet and the FRP layer are laminated and integrated via the fibrous sheet between the laminated decorative sheet and the FRP layer. 2. The method for simultaneously decorating a FRP according to 1 above. 3. In the state of the laminated sheet in the step (A) or the state of the decorative sheet in the step (B), the incompletely cured layer of the curable resin is cured so that curing is not completely completed. The method for simultaneously decorating and molding a FRP according to claim 1 or 2, wherein after the curing reaction of the curable resin proceeds, the step (C) and subsequent steps are performed. 4. The method according to claim 1, wherein the concavo-convex pattern is formed into an incompletely cured layer by a shaping mold simultaneously with the heating and pressurization, and thereafter, the incompletely cured layer is completely cured. The simultaneous molding and decorating method for FRP according to the above item.