JP2002160315A - Decorative sheet and decorative molded product using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet with which an elaborated decorative treatment is enabled, and a strain, unevenness, a crack, a break and the like in a picture or a pattern while molding, and further a wrinkle are prevented, and a decorative molded product using the sheet. SOLUTION: The decorative sheet S consists of a fiber sheet 4 laminated on a back surface of a thermoplastic resin sheet 1 to which a decorative treatment is applied. Based on the test condition of the test speed 200 mm/min in JISK7127 as a test condition, a modulus value of 2% measured in a dumbbell- shaped No.3 type test piece of 10 mm width in JISK6251 as a test piece is made so as to be 1.0 kgf or more at 150 deg.C. The fiber sheet is not stretched even at such a high temperature as in molding a fiber reinforced heat-curable resin, and rigidity is maintained. Thus, the strain, the unevenness, the crack, the break and the like in the picture or the pattern while molding are prevented, and the wrinkle generated by a fluxion of the fiber reinforced heat-curable resin is also prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to members constituting a living space such as walls, floors and ceilings such as kitchen members, bathroom members and interior members, furniture such as cabinets, and automobiles such as bumpers and side moldings. TECHNICAL FIELD The present invention belongs to the technical field of molded articles suitably used for members for use and the like, and more particularly to a decorative sheet and a decorative molded article using the same.

[0002]

2. Description of the Related Art Conventionally, when a decorative sheet is further laminated and bonded to the surface of a thermosetting resin molded product, it is difficult to bond the decorative sheet to the cured resin layer. At the same time, they were laminated and bonded. For example, a decorative sheet made of a thermoplastic resin may be laminated and adhered simultaneously with molding via an adhesive layer, an easy-adhesion primer layer, and the like as necessary (for example, JP-A-60-122149, No. 218832, Japanese Unexamined Patent Publication No. Hei 4-37508, etc., and a sheet in which a decorative sheet using heat-resistant and dimensionally stable paper is laminated and adhered simultaneously with molding (for example, Japanese Patent Publication No. 26-4540). No., JP-A-53-
No. 9872, Japanese Patent Application Laid-Open No. 62-152733, etc.) are known.

[0003]

However, when a decorative sheet made of a thermoplastic resin is used, precise printing without formation unevenness is possible, and the resulting molded article has good flexibility. Since the thermoplastic resin is softened by heating, the decorative sheet is deformed due to the heat generated during the molding of the thermosetting resin and the stress caused by the flow of the molding resin, and the decorative sheet is often deformed, and wrinkles and unevenness often occur. . Since these phenomena are also changed by variations in molding conditions, variations in molding resin lots, filling amounts and filling patterns, and variations in sheet lots, the quality is not stable.

Further, when paper having heat resistance and dimensional stability is used, no distortion or flow of the picture is generated, but the clearer and more precise printing is achieved by the former because of the unevenness and absorption of paper fibers. It is not possible, and the pattern tends to be uneven due to the uneven formation of the paper. This tendency is particularly pronounced when the picture is provided solidly over the entire surface. In addition, since the formed molded article has no flexibility and flexibility, there is also a problem that a crack or a crack is easily generated when a force such as a bending force or an impact force is applied.

Therefore, it is conceivable to use a decorative sheet made of a thermosetting resin. However, since the cured thermosetting resin sheet has no chemical reactivity, it does not have an adhesive property with other layers of the molded article. It is sufficient, and the decorative sheet itself is easily broken by heat and stress during molding, and the entire molded product is harder than the above, and there is nothing to reinforce or release stress. There is little possibility of practical application due to cracks and cracks.

As disclosed in JP-A-7-60911 and JP-A-8-118384, a decorative sheet in which a nonwoven fabric is lined with a thermoplastic resin sheet on which a picture is printed has also been used. . However, when this decorative sheet is used, the printability of the pattern at the time of printing is good, and the distortion, unevenness, cracks, and tear of the pattern at the time of molding are improved, but wrinkles are formed on the decorative sheet at the time of molding. The problem remains.

[0007] It is also considered to improve the flow resistance of the thermoplastic resin by using short glass fibers or reducing the molecular weight of the reactive resin, binder, or the like. When using fiber, usually a few cm
There is a problem that the strength of the molded product is reduced in contrast to the use of the above fibers, and when the molecular weight of the reactive resin, the binder, etc. is reduced, the shrinkage at the time of curing is large, and the molded product is damaged upon demolding after molding. However, there is a problem that the distortion of the product increases.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to enable a fine decoration processing, and to provide a distortion, unevenness, crack, tear, and the like of a pattern at the time of molding. The present invention aims to provide a decorative sheet that does not cause wrinkles and does not generate wrinkles, and also provides a decorative molded product using the same.

[0009]

Means for Solving the Problems In order to achieve the above object, a decorative sheet of the present invention is a decorative sheet obtained by laminating a fibrous sheet on the back surface of a decorative thermoplastic resin sheet. The test conditions were based on the test speed of 200 mm / min of "JIS K 7127", and the test pieces were 2% modulus values measured with a 10 mm wide dumbbell-shaped No. 1 test piece of "JIS K 6251". However, at 150 ° C., it is 1.0 kgf or more.

The decorative molded article of the present invention is a decorative molded article using the decorative sheet described above, wherein a cured product of a fiber-reinforced thermosetting resin is laminated on the fiber sheet side of the decorative sheet. It is characterized by becoming.

[0011]

Next, an embodiment of the present invention will be described.

FIG. 1 is a sectional view showing an example of a decorative sheet according to the present invention. As shown in the figure, the decorative sheet of the present invention basically has a decorative sheet S in which a decorative layer 2 composed of a pattern layer is formed on the back surface of a thermoplastic resin sheet 1 as a base material, It has a configuration in which a fibrous sheet 4 is laminated via an adhesive layer 3 so as to cover the layer 2. Of course, the decorative sheet of the present invention is not limited to the form shown in FIG. 1 and various other forms are possible.

FIG. 2 is a sectional view showing an example of a decorative molded product according to the present invention. This decorative molded product D uses the decorative sheet S shown in FIG. 1, and has a configuration in which a cured product 5 of a fiber-reinforced thermosetting resin is laminated on the fibrous sheet 4 side of the decorative sheet S. I have.

As the thermoplastic resin sheet, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Homopolymers of (meth) acrylates such as butyl acrylate, ethylhexyl (meth) acrylate, or these (meth) acrylates or (meth) acrylates
Acrylic resins such as copolymers of acrylates and other monomers such as styrene and ethylene (the notation of (meth) acrylates means "acrylates or methacrylates"), polyethylene Terephthalate, polyethylene naphthalate, polybutylene terephthalate, ethylene / isophthalate / terephthalate copolymer, polyester-based thermoplastic elastomer,
Polyester resin such as completely amorphous polyester (in addition,
The polyester-based thermoplastic elastomer is a block polymer using an aromatic polyester having a high crystalline and high melting point for a hard segment and an amorphous polyether having a glass transition temperature of −70 ° C. or less for a soft segment. For example, polybutylene terephthalate is used for the highly crystalline, high melting point aromatic polyester, and polytetramethylene ether glycol is used for the amorphous polyether, for example. As a completely amorphous polyester, a typical example is ethylene glycol-
Those comprising a 1,4-cyclohexanedimethacrylate / terephthalic acid copolymer are exemplified. ), Polyvinyl chloride, vinyl resins such as polyvinyl chloride / acrylic copolymer, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / vinyl acetate copolymer, polyethylene, polypropylene, polymethylpentene Polyolefin resin such as polybutene, ionomer, ethylene-propylene copolymer, olefin-based thermoplastic elastomer, fluorine resin such as polyvinyl fluoride, polyvinylidene fluoride, ethylene tetrafluoroethylene copolymer, polystyrene, acrylonitrile Styrene copolymers such as styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polycarbonate, nylon (polyamide),
Resins such as thermoplastic urethane resin, polyimide, polyphenylene sulfide, and polyetheretherketone are selected. The thickness of the thermoplastic resin sheet is usually 25 to 50.
It is about 0 μm.

Among them, those which have appropriate flexibility at the time of heating are preferable so as not to cause cracks or breakage due to the stress applied during molding. Further, in order to be able to suppress deformation of the fibrous sheet during molding, it is necessary that the thermoplastic resin sheet itself does not undergo flow deformation. Therefore, a thermoplastic resin sheet whose melting temperature is higher than the molding temperature is selected. The thermoplastic resin sheet is
Any of non-stretching, uniaxial stretching, and biaxial stretching may be used. When a decorative layer such as a picture layer is formed on the back surface of the thermoplastic resin sheet as shown in FIG. 1, a transparent thermoplastic resin sheet is used. When coloring the thermoplastic resin sheet itself or forming a decorative layer on the surface of the thermoplastic resin sheet, the thermoplastic resin sheet may be opaque. In the present invention, the surface refers to a side near the outermost surface in a state of a decorative molded product, that is, a side opposite to a cured product of the fiber-reinforced thermosetting resin.

The decorative treatment applied to the thermoplastic resin sheet is based on coloring or forming a decorative layer on the thermoplastic resin sheet itself. The decorative layer is composed of a picture layer or a metal thin film. The picture layer may be formed by a printing method such as gravure, offset, or silk screen. As the ink, a resin binder to which a coloring agent such as a pigment or a dye is added is used. As the resin binder, cellulose acetate, cellulose acetate propionate, cellulose resin such as nitrified cotton, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Acrylic resins such as homo- or copolymers of (meth) acrylates such as butyl acrylate and ethylhexyl (meth) acrylate, vinyl chloride / vinyl acetate copolymer, chlorinated polypropylene, two-part curable urethane resin Examples will be described later), a single type of polyester resin or a mixture of two or more types thereof.
Inorganic pigments such as graphite, titanium yellow, ultramarine, cobalt blue, titanium white, zinc white, carbon black, iron black, etc .; metallic pigments composed of flaky foil powders such as brass and aluminum; flaky foil powders of titanium dioxide coated mica Pearl pigments, organic pigments such as quinacridone red, polyazo yellow, isoindolinone yellow, phthalocyanine blue, etc.
A single species or a mixture of two or more species is used. The patterns to be printed include wood patterns, stone patterns, cloth patterns, sand patterns, leather crests, tiles, tiled bricks, and other natural products, geometric patterns, characters,
Any of a symbol, a solid surface, etc. may be used. The metal thin film is a thin film made of gold, silver, copper, chromium, aluminum, or the like, and is formed by vacuum deposition, sputtering, or the like. In addition, as for coloring the thermoplastic resin sheet itself, a coloring agent similar to that used for the above-described ink is added to the thermoplastic resin sheet to be colored to a desired color tone.

A woven or non-woven fabric is used as the fibrous sheet. The single fibers constituting the fibers may be either natural fibers or synthetic fibers. In the case of natural fibers, cotton, which is relatively commonly processed, is preferable. In the case of synthetic fibers, polyester resin which is relatively inexpensive and has good heat resistance is preferable. The material of the synthetic fiber is not limited, and any material can be used as long as it becomes a fibrous material. In addition to the polyester resin, for example, cellulose, rayon, acrylic resin, polyethylene, polypropylene, nylon (polyamide), Kevlar or the like can be used. Also, carbon such as glass and graphite (graphite) can be used.

The woven fabric includes a woven fabric and a knitted fabric. In the present invention, it is preferable to use a woven fabric as the fibrous sheet, and the knitted fabric is not preferable because it has stretchability.

The woven fabric is obtained by intersecting warp (warp) yarns and weft (weft) yarns at right angles.
ave design), the basic plain weave, Aya (Aya) weave,
Sushi weaving is called the three original organization. Of these, plain weave
As shown in FIG. 3, is a simple structure in which warp yarns and weft yarns intersect one by one. Since the yarns intersect closely, the fabric surface is flat and durable. As shown in FIG. 4, twill weave is a combination of three or more warp yarns and weft yarns, and represents a ridge in an oblique direction (called a ridge or oblique line). Glossier and softer than 1/2,
There are many types, such as 3/1, 2/2. As shown in FIG. 5, satin weave has a small number of texture points and has a long warp floating (warp satin) or a long weft floating (weft satin), and is flexible and glossy. There is. The simplest complete structure is composed of five warp and weft yarns, each of which is referred to as a five-sheet satin, such as an eight-sheet satin or a ten-sheet satin. Derivative weave is a derivative of the three original tissues, and rib weave is a plain weave that is expanded vertically or horizontally to show horizontal or vertical ridges. mat weave)
Is an enlarged plain weave with two or more threads in the vertical and horizontal directions. The steep weave represents an oblique line at an angle greater than 45 °, while the gentle weave has a gentler angle, all of which are twill weaves. Yamagata Oblique (Aya Sugi) is an oblique line expressed in Yamagata, which is herringbone serge. There are many changes in the texture of the satin weave, but the day and night shushi weave is a combination of this because of the difference in gloss between the front and back surfaces. It is. Further, as shown in FIG. 6, there is a structure in which yarns in three directions are crossed obliquely.

As described above, there are various types of woven fabrics, and the woven fabric used in the present invention may be the simplest plain weave. When a thermosetting resin-impregnated fiber described later is used, either or both of the warp and the weft may be used, and it is preferable that the fiber is used at least in the longitudinal direction of the mold at the time of molding.

Examples of the nonwoven fabric include acrylic resin, nylon, polyester resin, polyethylene, polypropylene, rayon, acetate, polyvinyl chloride, cellulose, pulp, organic fibers such as vinylon, glass fiber, asbestos, potassium titanate fiber, alumina fiber, and the like. Nonwoven fabrics and Japanese paper using inorganic fibers such as silica fibers and carbon fibers are used. In consideration of cost, physical properties, workability, strength, and the like, a polyester resin is preferable. The nonwoven fabric used in the present invention has a thickness of 0.2 mm or less and a tensile strength (rupture strength) of a normal molding temperature (12 mm).
(0-160 ° C.) and preferably at least 2.0 kg / 15 mm width. If the thickness of the non-woven fabric is larger than 0.2 mm, it will not be easily wrapped around the end or round portion of the molded product during molding, and if the tensile strength is less than 2.0 kg / 15 mm width, it will break and cause poor adhesion. . The nonwoven fabric and the thermoplastic resin sheet may be bonded by a known appropriate method. For example, there is a dry lamination method using an adhesive such as a two-component curable urethane resin or an epoxy resin.

In the present invention, the woven or non-woven fabric as described above is used as the fibrous sheet. However, the decorative sheet may be wrinkled or torn due to heat and stress when heating and pressing the fiber-reinforced thermosetting resin.
In order to prevent the distortion and unevenness of the picture, the 2% modulus value of the decorative sheet (thermoplastic resin sheet / fibrous sheet) is set as follows.

During SMC molding, in a heated mold, the decorative sheet is stretched by about 2% at a temperature of about 150 ° C. at the maximum. At this time, as the decorative sheet has higher resistance to elongation, wrinkles, breaks, cracks, and distortions of the pattern during the molding are less likely to occur. As a result of repeating the experiment and the trial production, the present inventor determined that the tension when the decorative sheet as a laminate was stretched by 2% at 150 ° C. was stretched at a test speed of 200 mm / JIS JIS K 7127 as a test condition.
min, and the test piece is "JIS
It has been found that there is a correlation between the magnitude of a value measured for a 10 mm-wide dumbbell-shaped test piece of K6251 "(referred to as a 2% modulus value) and the defect at the time of molding. . That is, the measured value is 1.0 k
It has been found that the above-mentioned defect can be solved if the value is equal to or more than gf. The thickness of the test piece is the thickness of the decorative sheet actually used for molding. This is to evaluate the behavior of the decorative sheet actually used.

In order to make the 2% modulus value equal to or more than 1.0 kgf, adjustment is made by selecting the material of the fibrous sheet and the basis weight of the rice among the layer constitution of the decorative sheet.
The reason is that, if the modulus value is increased, the moldability and shape followability of the dense continuous thermoplastic resin sheet cannot be exhibited, and if it is forcibly molded, cracks and tears occur. Therefore, the 2% modulus value of the thermoplastic resin sheet is set to less than 1.0 kgf, and the formability and the shape following property are shared with the value. Then, by bonding a fibrous sheet to the thermoplastic resin sheet, the 2% modulus value becomes 1.0 kgf or more as a whole of the decorative sheet. For that purpose, the fibrous sheet is preferably a woven fabric, more preferably a woven fabric, than a nonwoven fabric. When the fibers constituting the fibrous sheet are used without impregnation with a thermosetting resin, polyester fibers are preferable. In addition, the basis weight of the fibrous sheet is preferably 30 g / m ² or more when the fiber sheet is made of fibers impregnated with a thermosetting resin, and is preferably 80 g / m ² or more when the fibers are not impregnated with a thermosetting resin.

Examples of the thermosetting resin impregnated in the fibrous sheet include a two-component curable urethane resin, an epoxy resin, a melamine resin, an unsaturated polyester resin, a diallyl phthalate resin, a phenol resin, a urea resin, and a guanamine resin. . Above all, a two-component curable urethane resin is preferable from the viewpoint of compatibility between the flexibility of the decorative sheet and the deformation and wrinkle prevention performance at the time of heat and pressure molding.

The two-component curable urethane resin is a composition containing a polyol (polyhydric alcohol) as a main component and an isocyanate compound as a crosslinking agent (curing agent).

The polyol has two or more hydroxyl groups in the molecule, and is basically a polymer containing a monomer diol, a triol, etc., and a chain of alkylene repeating units mainly contributing to its molecular weight. Including diols and triols. Typical polymer polyols consist essentially of either linear or branched chains of the above repeating units terminated with hydroxy groups, preferably monomers having 2, 3, 4 or more hydroxy groups Contains polyol. For example, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, 1,2,6-hexanetriol, butenediol, sucrose, glucose, sorbitol, pentaerythritol, mannitol, triethanolamine, n-methyldimethanolamine, and Including cyclic aromatic and aliphatic and triols. Further, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.

On the other hand, as the isocyanate compound, a polyvalent isocyanate compound having two or more isocyanate groups in a molecule is used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate,
Polyphenylmethane polyisocyanate called crude MDI, aromatic isocyanate compound such as xylylene diisocyanate, isophorone diisocyanate,
Aliphatic or alicyclic isocyanate compounds such as 1,6-hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate and triphenylmethane triisocyanate; hydrogenated isocyanates such as hydrogenated tolylene diisocyanate and hydrogenated diphenylmethane diisocyanate Isocyanate-terminated low molecular weight adduct obtained by reacting a compound or a polyisocyanate compound with a low molecular weight glycol or triol, for example, dipropylene glycol, 1,6-hexanediol, 1,2,6 hexanetriol, trimethylolpropane Or an isocyanate multimer such as tolylene diisocyanate trimer.

The state in which the thermosetting resin penetrates into the fibers constituting the fibrous sheet and fills the interstices of the fibers is referred to as impregnation. Specific means for impregnation include roll coating, flow coating, and the like. Comma coat, dipping, brush printing,
There are running away.

As an example of a fiber-reinforced thermosetting resin, SMC
(Sheet molding compound). This is a sheet-like molding material obtained by mixing a resin uncured material (which may be partially cured) such as an unsaturated polyester resin, epoxy resin, or phenol resin which is a thermosetting resin, and a reinforcing material such as glass fiber. Yes, put in a mold and heat and press,
By molding and curing in a desired shape, a cured product of a fiber-reinforced thermosetting resin (this is also referred to as FRP) is obtained.

The production method is, for example, a method in which a resin prepolymer, a curing catalyst, an accelerator, a curing retarder, an air drying agent, and the like, calcium carbonate, talc, clay, and the like are coated on one surface of a first separator film such as a polyethylene film. A resin compound obtained by kneading a filler or the like is applied by a knife coating method or the like, and then a chop strand obtained by cutting a glass roving obtained by bundling glass fibers is sprayed, and a second such as a polyethylene film is formed. On one side of the separator film, the same resin compound as applied on one side of the first separator film is applied by the same application method, and then the first separator film and the second separator film are combined with the resin of both separator films. Through the chop strands where the compound application surfaces are sprayed Superposed so as to face, and impregnation and defoaming the chopped strands are sprayed resin compound by pressurizing a roll pressure, a method of curing are taken humidified. The resin used for producing the SMC is not particularly limited, but usually includes many unsaturated polyesters and epoxies.

FIG. 7 schematically shows an SMC molding method for producing an FRP article using the above-mentioned SMC. As shown,
Equipment capable of applying heat and pressure to a pair of opposing dies, usually a large heat press with a lower die 11 and an upper die 1
Use the one with 2 installed. And first, FIG.
As shown in (a), the SMC 10 is cut into required dimensions by peeling the film on the front and back, and placed on the lower mold 11 in a state where the SMC 10 is overlapped so that the fiber sheet side of the decorative sheet S and the SMC 10 are in contact with each other. After placing, as shown in FIG.
A drive device (not shown) such as a hydraulic cylinder connected to the dies 11 and 12 is driven to close the dies 11 and 12, and then heated and pressurized. Usually, the temperature is about 100-150 ° C,
The pressure is 30 to 200 kg / cm ² for 1 to 8 minutes while heating and pressurizing, and cured by a reaction such as cross-linking polymerization or addition polymerization to form SMC into FRP and to form into a desired shape defined by both molds. I do. Thereby, the decorative molded product D as shown in FIG. 7C is obtained.

The shape of the decorative molded product can be a flat plate, a curved plate or the like. If necessary, various substrates may be backed and laminated on the back surface (opposite the decorative sheet) of the molded article of the present invention. As the backing substrate, a plate or sheet of a synthetic resin, metal, wood, cement, or the like is appropriately used.

The decorative molded article of the present invention is manufactured by the above-described method of integrally forming a decorative sheet with FRP.
The decorative sheet may be bonded to an already cured FRP article by using an adhesive.

The decorative molded article of the present invention is obtained by laminating a backing substrate as required, and then applying to interior materials such as walls, floors and ceilings in bathrooms, kitchens and other general rooms, doors and window frames. , Door frames, rims, skirting boards and other fittings or building members, automotive parts such as bumpers and side moldings, cabinets for television receivers, housings or exterior materials for household appliances such as refrigerator doors, vehicles It can be used for applications such as interior materials and furniture surface materials.

[0036]

(Example 1) Transparent biaxially stretched polyethylene terephthalate having a thickness of 100 μm (hereinafter referred to as PET).
A two-component curable polyester resin consisting of polyester polyol and 1,6-hexamethylene diisocyanate is used as a binder on the back surface of a sheet (made by Toray Industries Inc.), and a pigment composed of titanium white, graphite, red stem and ultramarine blue A marble pattern was printed by gravure printing using an ink to which was added.

Then, an adhesive for dry lamination of a two-component curable urethane resin (manufactured by Dainichi Seika) comprising 100 parts by mass of polyester polyol and 6 parts by mass of 1,6-hexamethylene diisocyanate was applied to the printed surface of the PET sheet. It was applied at a dry weight of 20 g / m ² and a wet polyester nonwoven fabric (basis weight 100 g / m ² ) was attached to obtain a decorative sheet.

(Example 2) The same marble pattern was printed on the same PET sheet as in Example 1, the same adhesive as that in Example 1 was applied to the printed surface, and a polyester woven fabric (plain weave, basis weight 80 g / m ² ) to obtain a decorative sheet.

Example 3 A similar marble pattern was printed on the same PET sheet as in Example 1. On the other hand, a woven fabric (plain weave, basis weight 200 g / m ² ) impregnated with a two-part curable acrylic resin composed of 100 parts by mass of acrylic polyol and 6 parts by mass of 1,6-hexamethylene diisocyanate was prepared. Then, the same adhesive as in Example 1 was applied to the printing surface of the PET sheet, and the woven fabric was attached to obtain a decorative sheet.

Example 4 Transparent PET having a thickness of 25 μm
A sheet was prepared, and the same marble pattern as in Example 1 was printed on the back surface of the PTE sheet. Then, the same decorative fabric sheet as in Example 3 was obtained in the same manner.

Example 5 A transparent acrylic resin sheet (manufactured by Mitsubishi Rayon) having a thickness of 50 μm was prepared, and 100 parts by mass of acrylic polyol and 8 parts by mass of 1,6-hexamethylene diisocyanate were provided on the back surface of the acrylic resin sheet. A two-component curable acrylic urethane resin consisting of: titanium white, isoindolinone yellow,
A marble pattern was printed by gravure printing using an ink to which a pigment consisting of quinacridone red and phthalocyanine blue was added. Then, using the same non-woven fabric as in Example 1 on the printed surface, a laminated decorative sheet was similarly obtained.

(Comparative Example 1) A similar marble pattern was printed on the same PET sheet as in Example 1, and the same adhesive as that of Example 1 was applied on the printed surface thereof at a dry weight of 10 g / m ² to obtain a wet polyester nonwoven fabric. (Basis weight 30 g / m ² ) to obtain a decorative sheet.

(Comparative Example 2) The same marble pattern was printed on the same acrylic resin sheet as in Example 5, and the same adhesive as that of Example 1 was applied on the printed surface at a dry weight of 10 g / m ² to obtain a wet polyester resin. A decorative sheet was obtained by laminating a nonwoven fabric (basis weight 30 g).

Comparative Example 3 A decorative sheet was obtained by printing a marble pattern by gravure printing on the same PET sheet as in Example 1 using the same ink as in Example 5.

(Evaluation Method) The decorative sheet obtained in each of Examples 1 to 5 and Comparative Examples 1 to 3 was measured for a 2% modulus value. That is, the decorative sheet is formed to have a width of 10.0 m in conformity with the dumbbell-shaped No. 1 type defined in “JIS K6251”.
m and a tensile tester at 150 ° C.
K 7127 "at a test speed of 200 mm / min.

Then, using each decorative sheet, S
MC molding evaluation was performed. Here, an SMC resin (manufactured by Takeda Pharmaceutical Co., Ltd., made of unsaturated polyester prepolymer and glass fiber) was used to form a wall panel having a size of 800 mm × 2000 mm. Specifically, the decorative sheet was placed on a mold heated to 150 ° C. with the decorative surface facing downward, and the SMC resin was further placed thereon, and molded at a pressure of 80 kg / cm ² for 5 minutes. .

Table 1 shows the 2% modulus value of each decorative sheet and the results of SMC molding evaluation using each decorative sheet.
Shown in The non-defective rate was represented by the number of non-defective products obtained by molding 10 times under the same conditions.

[0048]

[Table 1]

[0049]

The decorative sheet of the present invention is a decorative sheet obtained by laminating a fibrous sheet on the back surface of a thermoplastic resin sheet which has been subjected to a decorative treatment. The test conditions are "JIS K7".
127 "and a test speed of 200 mm / min, and the test piece was a dumbbell-shaped No. 1 type test piece of 10 mm width according to" JIS K6251 ".
Since the modulus value is 1.0 kgf or more at 150 ° C., the fibrous sheet does not elongate and can maintain the rigidity even at a high temperature at which the fiber-reinforced thermosetting resin is molded. In addition to preventing distortion, unevenness, cracks, tears, and the like, wrinkles generated by the flow of the fiber-reinforced thermosetting resin can be prevented, and the molding yield can be improved. In addition, it is possible to provide a fine decoration.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating an example of a decorative sheet according to the present invention.

FIG. 2 is a sectional view showing an example of a decorative molded product according to the present invention.

FIG. 3 is an explanatory diagram of a plain weave among three original textures of a woven fabric.

FIG. 4 is an explanatory view of a twill weave among three original fabrics of the fabric.

FIG. 5 is an explanatory diagram of a satin weave of three original fabrics.

FIG. 6 is an explanatory view showing another material different from the three original textures of the woven fabric.

FIG. 7 is an SMC for manufacturing an FRP article using the SMC.
It is a schematic explanatory view of a molding method.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent thermoplastic resin sheet 2 Decorative layer 3 Adhesive layer 4 Fiber sheet 5 Cured material 10 SMC 11 Lower mold 12 Upper mold S Decorative sheet D Decorative molded article

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme coat ゛ (Reference) B29K 105: 08 B29C 67/14 B F Term (Reference) 4F100 AK01A AK01B BA02 BA10A BA10B BA15 DG12B DH02B GB08 GB32 HB31A JB13B JB16A JJ03A JK01A JK08 JL02 YY00A 4F205 AA24 AA41 AD19 AG01 AG03 AH24 AH49 AH51 HA14 HB01 HB13 HC05 HC06 HT03 HT13 HT26

Claims (4)

[Claims] 1. A decorative sheet obtained by laminating a fibrous sheet on the back surface of a thermoplastic resin sheet that has been subjected to a decorative treatment, and the test condition is a test speed of 2 according to “JIS K 7127”.
Based on the conditions of 00 mm / min and the test piece, the 2% modulus value of a 10 mm-wide dumbbell-shaped No. 1 test piece of "JISK 6251" was 150.
A decorative sheet characterized by being at least 1.0 kgf at a temperature of ° C. 2. The decorative sheet according to claim 1, wherein the fibrous sheet is a woven fabric. 3. The decorative sheet according to claim 1, wherein the fibrous sheet contains fibers which are impregnated with a thermosetting resin and cured. 4. A decorative molded article using the decorative sheet according to claim 1, wherein a cured product of a fiber-reinforced thermosetting resin is laminated on the fiber sheet side of the decorative sheet. A decorative molded product characterized by the above.