JP2003053908A - Sheetlike laminated structure having high design effect and utilization thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheetlike laminated structure having a continuous hue change along the surface thereof and having excellent aesthetic appreciation properties and design effect, and various products utilizing the same. SOLUTION: The sheetlike laminated structure having high design effect is constituted of at least two kinds of layers (1) formed from a thermoplastic resin and the outer layer (2) on at least the single surface of the laminated structure is a layer (B) formed from a transparent resin. At least one kind of the layer (3) constituting the laminated structure contains a dye, a pigment or a light diffusing agent and has a monotonous thickness change at least in one direction of the sheet surface of the laminated structure and the continuous hue change (4) is recognized along the sheet surface of the laminated structure when the laminated structure is visually observed from the outside surface of the layer (B) formed from the transparent resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated structure made of a sheet-shaped thermoplastic resin having excellent aesthetics and design, and its use. More specifically, the present invention relates to a sheet-shaped laminated structure in which a continuous change in color tone is observed along the surface of the sheet when observed from the outside, and its use.

[0002]

2. Description of the Related Art In recent years, there has been a demand for product design, especially for resin molded products, to achieve high added value. One of them is high designing by continuous color tone change (gradation color). As one of such designing methods, a molding method such as an insert molding method in which a film or sheet on which a gradation pattern is printed is previously mounted in a mold and injection molding is used. However, these molding methods require many steps such as sheet production, printing, and trimming, and are not sufficiently attractive in terms of design.

On the other hand, in JP-A-53-83884 and JP-A-56-123235, the thicknesses of the outer layer and the inner layer are changed, and the outer layer is composed of a resin containing a coloring agent, and the vertical direction. And a method of forming the same have been proposed. However, the molded article (container) obtained by the method described in the above publication is a container having a relatively simple color tone in which the direction of change in gradation color is vertical due to its constitution and the upper or lower part is deeply colored. However, it was difficult to apply a three-dimensional pattern (such as letters and figures) to the interface portion of the layer. Thus, it has high designability, continuous color tone change can have not only one direction but also various directions, and it can have a clear three-dimensional pattern at the interface portion of the layer, and has a relatively thick wall. The flat laminated structure has never been provided.

[0004]

Therefore, the first object of the present invention is to have a plurality of layers formed of a thermoplastic resin which are excellent in aesthetics and design and have a continuous change in color tone. It is to provide a sheet-like laminated structure. A second object of the present invention is that the continuous color tone change is not limited to one direction along the sheet surface, but can be in various directions, and a sheet-like laminate capable of combining several kinds of colors is provided. To provide a structure. A third object of the present invention is to provide a sheet surface having a continuous change in color tone,
It is to provide a sheet-like laminated structure having a three-dimensional pattern such as clear characters and figures. Another object of the present invention is to provide a transparent or semi-transparent sheet-shaped laminated structure having a continuous shape change, having a thickness having sufficient shape retention.

Still another object of the present invention is to provide a decorative glass window, an interior member, a glass window for a showcase, a partition, a door, a window glass for a vehicle, a vehicle outer panel, a lamp cover, an ornament, an instrumental panel for a vehicle and a center. Panels, interior and exterior moldings and garnishes for vehicles, display devices, display plates, light guide plates, signboards, windbreak plates, roofing materials, furniture, housing members in various office automation equipment such as computers and mobile terminals, mobile phones and portable acoustics. To provide a sheet-shaped laminated structure having practical strength that can be advantageously used as a member of a housing in various electric devices such as devices, a panel for electric decoration such as a slot machine, and a material for sundries and the like. .
Yet another object of the present invention is to provide a highly illuminating fixture that utilizes a transparent or semi-transparent continuous color tone change.

[0006]

According to the studies made by the present inventors, the above-mentioned objects of the present invention are: (1) a sheet-like laminate composed of at least two kinds of layers formed of a thermoplastic resin. (2) the outer layer on at least one surface of the laminated structure is a layer (B) made of a transparent resin, and (3) at least one layer constituting the laminated structure. Contains a dye, a pigment or a light diffusing agent and has a monotonic thickness change in at least one direction of the sheet surface of the laminated structure, and (4) the laminated structure is formed of a transparent resin. When visually observed from the outer surface of the formed layer (B), a continuous change in color tone is recognized along the sheet surface,
It has been found that this can be achieved by a high design sheet-like laminated structure characterized by the above.

The laminated structure of the present invention will be described in more detail below. The laminated structure of the present invention has many combinations depending on the number of layers constituting the layer, the shape of each layer, the presence or absence of coloring of each layer, the color of coloring, and the like. The aesthetics and design change depending on the direction and the direction of the light source. These are the sources from which the features and advantages of the laminated structure of the present invention are expressed, and for the understanding of the laminated structure of the present invention, they will be described below with reference to the drawings.

FIG. 1 is a schematic view showing the shape of a right-angled cross section in the sheet surface of the sheet-like laminated structure of the present invention. The structure of FIG. 1 shows an example of a structure having a basic and simple shape for the purpose of explanation. The laminated structure 1 in FIG. 1 is composed of two layers (2 and 3) and
In this example, each of the two layers is made of a transparent resin. Further, FIG. 1 shows a laminated structure in which the change in the thickness of the two layers is linear. Further, in the case of FIG. 1, it has a laminated structure on which characters or figures (4) are applied. Such FIG.
In the case of the laminated structure of, the following aspects 1 to 5 are included.

Mode 1 Layer 2 (layer (A)) is formed of a transparent resin containing a dye or a pigment (hereinafter, these may be abbreviated as "coloring agent"), and the coloring agent is contained in the resin. It is contained almost uniformly in concentration. On the other hand, the layer 3 (layer (B)) is formed of a transparent resin containing no colorant. In the case of the laminated structure of Embodiment 1, when observed in the direction of the arrow, a change in color tone is observed depending on the thickness of the layer 2. In other words, from the thickest edge (right side in FIG. 1) to the thinnest edge (left side in FIG. 1) of the layer 2, the color tone gradually (continuously) gradually changes from dark to light. Characters or figures (hereinafter these are “designs”)
4, the thickness of the layer 2 is locally increased, so that the pattern is recognized in a relatively dark color tone. In this embodiment, when a fluorescent colorant is used as the colorant, a laminated structure having a more vivid color tone change is obtained.

Aspect 2 The resin forming layers 2 and 3 is configured in the opposite manner to that of aspect 1. That is, the layer 2 is made of a resin containing no colorant, and the layer 3 is made of a resin containing a colorant. In the case of the laminated structure of this aspect 2, the change in color tone is almost the same as that in aspect 1, but the direction of shading is opposite. However, since the thickness of the layer 2 which does not contain the colorant locally increases in the pattern 4, the color tone is relatively light (white state).
Will be recognized in.

Aspect 3 The resins forming the layers 2 and 3 each contain a colorant, but the layers 2 and 3 contain different colorants. For example, not only the color tone but also the change in color is continuously observed on the left and right depending on the type and combination of the colors of the colorants contained in the layers 2 and 3. An example thereof is shown in Table 1 below.

[0012]

[Table 1]

The colors of the colorants in each layer in Table 1 above are combinations of three colors of red, yellow and blue, but are not limited to this example. The combination of the layers 2 and 3 may be reversed. One of the preferable modes in this mode 3 is that one layer is formed of a transparent resin containing a fluorescent dye and has a monotonous change in thickness in at least one direction of the sheet surface, and the other layer is A sheet-shaped laminated structure formed of a transparent resin containing a dye or a pigment having a color different from that of the layer.

Aspect 4 The layer 2 is formed of a resin containing light diffusing particles (light diffusing agent), and the layer 3 is formed of a resin containing a colorant. The laminated structure of this aspect 4 is semitransparent as a whole. Its transparency decreases continuously from the thin part of layer 2 to the thick part (from left to right). The laminated structure of this aspect 4 makes the whole feel a fantastic (skeleton-like) image due to the action of the light diffusing particles. The image feeling varies widely depending on the type of colorant.

Aspect 5 Layer 2 is formed of a resin containing highly reflective particles (a highly reflective agent), and layer 3 is formed of a resin containing a colorant. In the laminated structure of this aspect 5, since the layer 2 is formed of a resin containing a high light reflecting agent, it is opaque as a whole, and the color of the colorant of the layer 3 is milky white and continuously changes. Becomes Further, in the above-mentioned Modes 4 and 5, when a design is applied to the interface between the layer 2 and the layer 3, the design is emphasized and a three-dimensional image is presented. Particularly in the embodiment 5, a three-dimensional pattern is developed. As will be described later, in Embodiment 1 (in the case of a fluorescent colorant) and Embodiments 4 and 5, the position of the light source, the type of the colorant (in particular, the fluorescent colorant), the action of the light diffusing particles, the light highly reflective particles, etc. Also, the three-dimensional image of the design becomes more prominent, and the image is fantastic. In this case, the edge light on the side surface (left side or right side in FIG. 1) of the laminated structure produces a more prominent stereoscopic image or a fantasy image than the position of the light source is the backlight with respect to the visual direction. To achieve. That is, the effect of the present invention can be made more remarkable when light is incident in parallel to the direction in which the thickness changes.

The laminated structure of the present invention is composed of a plurality of layers, at least one layer containing a dye, a pigment or a light diffusing agent, and in at least one direction along the sheet surface of the structure. By having a monotonous change in thickness, a continuous change in color tone is developed and formed. In the following description, the term "colored layer" means a layer containing one or more of the dye, pigment or light diffusing agent. This colored layer needs to have a monotonous change in thickness, which means that when the laminated structure is visually observed, a continuous change in color tone is recognized along the sheet surface. What is done. Therefore, it is desirable that the change in thickness is not stepwise but is gentle or linear. However, when a pattern such as a character or a figure is formed, fine unevenness is locally formed at that portion. Excluded from.

Next, the mode of monotonous change in thickness of the colored layer in the laminated structure of the present invention will be described. For simplification of description, a case where the laminated structure is a rectangle having a certain thickness (a quadrangle in which all corners are right angles) will be described as an example. The four corners of the rectangle are sequentially A, B,
Let C and D. Thus, side AB and side CD are parallel to each other, and side BC and side DA are also parallel to each other. Examples of changes in the thickness of the colored layer are listed below. (I) As shown in FIG. 1, there is a monotonous change in thickness from one side toward the other side (for example, from side AB toward side CD). (Ii) It has a monotonic change in thickness in the diagonal direction from the corner A to the corner C. (Iii) Center of rectangle (portion where two diagonals intersect)
To side A-B, side B-C, side C-D and side D-A have a monotonic change in thickness (quadrangular pyramid shape or inverted quadrangular pyramid shape). (Iv) A monotonic change in thickness from the center line of the rectangle (for example, the center line portion parallel to the sides AB and the side CD) toward the opposite sides (for example, the sides AB and the side CD). Have (V-shaped or inverted V-shaped). (V) The center line is one diagonal line having a rectangle, and the two corners facing each other from the center line (for example, the corner A and the corner C).
From the center line connecting the points toward corners B and D).

The above examples (i) to (v) are for the purpose of explanation, and these modified forms may be used.
For example, the center portion or center line does not necessarily have to be accurate, and even if they are offset, there is no problem. Further, it may be an appropriate combination of the above (i) to (v), and may include a part where there is no change in thickness. The laminated structure of the present invention may be in the form of a sheet, and is not limited to the rectangular shape described above. Here, the sheet shape is basically a flat plate shape, but also includes various forms obtained by deforming it.

The laminated structure of the present invention does not necessarily need to have a uniform thickness, but it is practical and preferable that the thickness is substantially the same. A thickness of 1 to 50 mm, preferably 2 to 20 mm, particularly preferably 3 to 15 mm is suitable. Examples of the form include a flat plate shape, a semi-spherical shape and a semi-cylindrical shape. It is also possible to take a spherical shape or a cylindrical shape by combining hemispheres. The flat plate-like form has
Is it a plate-like body whose both surfaces form straight lines that are substantially parallel to each other?
It may be a curved flat plate or a flat plate having a curved surface with a radius of curvature of 5 cm or more, preferably 15 cm or more, and particularly preferably 30 cm or more. Further, it may be a flat plate having a slight change in thickness. In any of the forms, the surface may be smooth, or fine irregularities may be provided on either surface to impart an effect of diffusing light. The number of layers of the laminated structure is 2 to 5, preferably 2 or 3, with 2 being particularly preferred.

When the laminated structure is composed of two layers, the change ratio of the thickness of each layer is 0.02 to 0.98 when the total thickness of the laminated structure is 1. ,
A range of 0.1 to 0.9 is advantageous. The laminated structure of the present invention, in which each layer is formed of a transparent resin and is wholly transparent or semi-transparent, is effective in further developing the aesthetic appearance and design due to continuous color tone change. In addition, in the case where a design made up of characters or figures is applied, the design is visually or stereoscopically observed from the surface where the color tone changes continuously. It is possible to change the stereoscopic effect and the sharpness of this pattern depending on the viewing direction and the position of the light source. Especially when a fluorescent colorant, a light diffusing agent or a high light reflecting agent is mixed in one layer, the light source is a side surface of the laminated structure (a surface perpendicular to the end of the sheet surface).
When located at, the stereoscopic effect becomes more remarkable.

In particular, in Embodiments 1 to 4, when a fluorescent coloring agent or a light diffusing agent (particularly, a fluorescent coloring agent) is blended, the sheet-like laminated structure of the present invention has a light source position with respect to the visual direction as a backlight. By doing so, the design becomes flat, and by making the light source position on the side surface of the laminated structure, the design becomes three-dimensional or fantastic. By utilizing this, for example, by switching between two light sources (backlight and edge light), it is possible to alternately display the pattern in a planar or three-dimensional manner or in a planar or fantasy manner.

In the laminated structure of the present invention, it is preferable that each layer constituting the laminated structure is formed of a transparent resin, and the entire laminated structure has transparency, so that the design is excellent. When the entire laminated structure has transparency, the total light transmittance is preferably in the range of 10 to 90%, preferably 20 to 70%, and the haze is 0.1 to 15%, preferably 0.1. Advantageously, it is in the range of 15 to 10%. Next, the thermoplastic resin used to form the laminated structure of the present invention will be described. As described above, the laminated structure of the present invention, as long as the colored layer is formed of at least transparent resin,
The type of resin forming the other layers is arbitrarily selected. However, it is desirable that all layers are made of a relatively transparent resin. The plurality of layers to be laminated may be the same resin or different resins. However, it is preferable that they are formed of the same resin in terms of processing, physical properties and applications.

As the transparent resin, JIS K7 is used.
A resin having a total light transmittance of 10% or more, preferably 20% or more, and more preferably 30% or more in a plate-shaped molded product having a smooth surface and a thickness of 2 mm measured according to 105. In a transparent resin containing a dye or a pigment, the composition ratio of the dye or the pigment is preferably 0. 0 per 100 parts by weight of the thermoplastic resin.
001 to 2 parts by weight, more preferably 0.005 to 1 part by weight, still more preferably 0.005 to 0.5 part by weight. Similarly, in the case of a transparent resin containing a fluorescent colorant exhibiting high designability, its composition ratio is preferably 0.001 to 2 parts by weight, more preferably 0.1 part by weight per 100 parts by weight of the thermoplastic resin. 005 to 1 part by weight, more preferably 0.005 to 0.5 part by weight.

The transparent resin containing a light diffusing agent has a total light transmittance of 1 in a plate-shaped molded article having a smooth surface of 2 mm and measured according to JIS K7105.
Those having 0 to 93% and a haze of 20 to 90% are preferable. More preferable total light transmittance is 30 to 90%, particularly 50 to 90%, and more preferable haze is 30 to 9
It is 0%. Further, as the resin containing a light high-reflecting agent, the total light reflectance in a plate-shaped molded product having a smooth surface of 2 mm at a wavelength of 450 to 800 nm is preferably 80% or more, more preferably 90% or more, and further preferably Those which are 95% or more can be mentioned.

Examples of the thermoplastic resin used in the laminated structure of the present invention include polyethylene resin, polypropylene resin, polystyrene resin, high-impact polystyrene resin, hydrogenated polystyrene resin, polyacrylstyrene resin, ABS resin, AS resin. , AES resin, A
General-purpose plastics represented by SA resin, SMA resin, polyalkylmethacrylate resin, polyphenylene ether resin, polyacetal resin, polycarbonate resin, polyalkylene terephthalate resin, polyamide resin, poly-4-methylpentene-1 (TPX resin), Fluorine resin, phenoxy resin, cyclic polyolefin resin, polyarylate resin (amorphous polyarylate,
So-called super engineering plastics such as engineering plastics represented by liquid crystal polyarylate), various thermoplastic polyimides represented by polyetheretherketone, polyetherimide, polyamideimide, etc., polysulfone, polyethersulfone, polyphenylene sulfide, etc. What is called a su can also be used. Furthermore, styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer,
A thermoplastic elastomer such as a polyamide-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, or a polyurethane-based thermoplastic elastomer can also be used.

The mixing and use of the above-mentioned thermoplastic resins can be appropriately selected depending on the purpose of use of the composition. In the present invention, at least one layer needs to have transparency, and therefore, it is preferable that the resin forming any one layer is a transparent thermoplastic resin. As the transparent thermoplastic resin, polystyrene resin, high-impact polystyrene resin, hydrogenated polystyrene resin, polyacrylstyrene resin, ABS resin, AS resin, AES resin,
ASA resin, SMA resin, polyalkylmethacrylate resin, polyphenylene ether resin, polycarbonate resin, amorphous polyalkylene terephthalate resin, amorphous polyamide resin, poly-4-methylpentene-1, cyclic polyolefin resin, amorphous polyarylate Examples thereof include resins, polyether sulfones, and thermoplastic elastomers such as styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers.

Among these, polyalkylmethacrylate resins such as polymethylmethacrylate which are excellent in transparency, polycarbonate resins, cyclic polyolefin resins,
Amorphous polyarylate resins and the like can be preferably mentioned. Examples of the alkyl methacrylate resin include those containing methyl methacrylate as a main constituent unit. Usually, a copolymer with an alkyl acrylate is used, but as the other copolymer component, an acrylic imide structural unit or a methylcyclohexyl methacrylate structural unit may be copolymerized in order to improve heat resistance. . It is also possible to use a copolymer of α-methylstyrene.

As the cyclic polyolefin resin, APO resin manufactured by Mitsui Chemicals, Inc., Arton manufactured by JSR Co., Ltd.,
Examples include ZEONEX, ZEONORE, and hydrogenated-α-olefin-dicyclopentadiene copolymer manufactured by Nippon Zeon Co., Ltd. It is preferable that at least one layer constituting the laminated structure of the present invention is formed of a polycarbonate resin from the viewpoint of mechanical strength and heat resistance of the laminated structure. Most preferred is a laminated structure in which all layers are made of polycarbonate resin.
The polycarbonate resin will be specifically described below.
Polycarbonate resin is usually obtained by reacting a dihydric phenol and a carbonate precursor by an interfacial polymerization method, a melt polymerization method, a carbonate prepolymer polymerized by a solid-state transesterification method, or a cyclic carbonate. It is obtained by polymerizing a compound by a ring-opening polymerization method.

Typical examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-
Dimethyl) phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis {(4-hydroxy-3-methyl)
Phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl}
Propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4
-Bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-
Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α , Α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m
-Diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,
3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide,
4,4'-dihydroxydiphenyl ketone, 4,4'-
Examples thereof include dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl ester, which may be used alone or in admixture of two or more.

Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
-Hydroxyphenyl) -3,3,5-trimethylcyclohexane and a homopolymer obtained from at least one bisphenol selected from the group consisting of α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene or Copolymers are preferred, especially homopolymers of bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane with bisphenol A, 2,2-bis {(4-hydroxy- A copolymer with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene is preferably used. Most preferred is a bisphenol A homopolymer.

As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples thereof include phosgene, diphenyl carbonate or dihaloformate of dihydric phenol.

When the polycarbonate resin is produced by reacting the above dihydric phenol with the carbonate precursor by the interfacial polymerization method or the melt polymerization method, the catalyst, the terminal terminator, and the oxidation of the dihydric phenol are prevented as necessary. You may use the antioxidant for this. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic difunctional carboxylic acid, It may also be a mixture of two or more of the obtained polycarbonate resins.

Examples of trifunctional or higher polyfunctional aromatic compounds include phloroglucin, phloroglucide, or 4,6-
Dimethyl-2,4,6-tris (4-hydrodiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ) Ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, and the like.
1-tris (4-hydroxyphenyl) ethane, 1,
1,1-Tris (3,5-dimethyl-4-hydroxyphenyl) ethane is preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.

When a polyfunctional compound which produces such a branched polycarbonate resin is contained, such a proportion is 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, and particularly preferably, the total amount of the aromatic polycarbonate. 0.01
Is about 0.3 mol%. Further, particularly in the case of the melt polymerization method, a branched structure may occur as a side reaction, and the amount of the branched structure is
0.001 to 1 mol%, preferably 0.005 to 0.5
It is preferably a mol%, particularly preferably 0.01 to 0.3 mol%. The ratio is ¹ H-N
It can be calculated by MR measurement.

The reaction by the interfacial polymerization method is usually a reaction between a dihydric phenol and phosgene, which is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Also,
To promote the reaction, for example, triethylamine, tetra-n
It is also possible to use a catalyst such as a tertiary amine such as -butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound. At that time, the reaction temperature is usually 0 to
40 ° C, reaction time about 10 minutes to 5 hours, pH during reaction
Is preferably 9 or more.

Further, in such a polymerization reaction, a terminal terminating agent is usually used. Monofunctional phenols can be used as such an end terminator. Monofunctional phenols are commonly used as molecular terminating agents for molecular weight control, and the resulting polycarbonate resins are compared to those that do not because the ends are blocked by groups based on monofunctional phenols. Excellent thermal stability. Such monofunctional phenols are generally phenols or lower alkyl-substituted phenols, and can be monofunctional phenols represented by the following general formula (1).

[0037]

[Chemical 1]

(In the formula, A is a hydrogen atom or 1 to 9 carbon atoms.
Is a linear or branched alkyl group or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3. ) Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

As other monofunctional phenols,
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be shown. Among these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

[0040]

[Chemical 2]

(In the formula, X is -R-CO-O- or-
R-O-CO-, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and n represents an integer of 10 to 50. ) N is 1 as the substituted phenols of the general formula (2).
0 to 30, particularly 10 to 26 are preferable, and specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol,
Examples thereof include docosylphenol and triacontylphenol.

As the substituted phenols of the general formula (3), compounds in which X is —R—CO—O— and R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26.
Are preferred, and specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Mention may be made of tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

It is desirable that the terminal terminator is introduced into at least 5 mol%, preferably at least 10 mol% of the ends of the obtained polycarbonate resin. More preferably, the terminal terminator is introduced in an amount of 80 mol% or more with respect to all the ends, that is, the hydroxyl group (OH group) at the end derived from the dihydric phenol is more preferably 20 mol% or less, and particularly preferably. 90 mol% or more of a terminal stopper is introduced to all terminals, that is, O
This is the case where the H group is 10 mol% or less. Moreover, you may use a terminal terminator individually or in mixture of 2 or more types.

The reaction by the melt polymerization method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and an alcohol produced by mixing the dihydric phenol and the carbonate ester while heating in the presence of an inert gas. Alternatively, it is carried out by a method of distilling phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system was set to 1.33 × 10 ^{3 to} 13.3.
The alcohol or phenol produced by reducing the pressure to about Pa is easily distilled. The reaction time is usually about 1 to 4 hours.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like, with diphenyl carbonate being preferred.

Further, a polymerization catalyst can be used for accelerating the polymerization rate, and examples of such a polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt of dihydric phenol and potassium salt, and water. Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkoxides of alkali metals and alkaline earth metals , Alkali metal or alkaline earth metal organic acid salts, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds Cancer compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalyst may be used alone or in combination of two or more kinds. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁸ to 1 × with ^respect to 1 mol of the dihydric phenol as a raw material.
It is selected in the range of 10 ⁻³ equivalent, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalent.

In the polymerization reaction, in order to reduce the number of phenolic end groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate may be added after or at the end of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenyl phenyl carbonate,
It is preferred to add compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate and ethoxycarbonylphenylphenyl carbonate. Among them 2-
Chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred, and 2-methoxycarbonylphenylphenyl carbonate is particularly preferred.

Further, in the melt polymerization method, it is desirable to neutralize the activity of the catalyst remaining after the polymerization with a deactivator. As such a quenching agent, benzenesulfonic acid,
p-toluene sulfonic acid, methyl benzene sulfonate,
Ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, methyl p-toluene sulfonate, ethyl p-toluene sulfonate, butyl p-toluene sulfonate,
Sulfonic acid esters such as octyl p-toluene sulfonate and phenyl p-toluene sulfonate; and further, trifluoromethane sulfonic acid, naphthalene sulfonic acid, sulfonated polystyrene, methyl acrylate-sulfonated styrene copolymer, dodecylbenzene sulfonic acid- 2-
Phenyl-2-propyl, dodecylbenzenesulfonic acid-2-phenyl-2-butyl, octylsulfonic acid tetrabutylphosphonium salt, decylsulfonic acid tetrabutylphosphonium salt, benzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetraethylphosphonium salt , Dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetrahexylphosphonium salt, dodecylbenzenesulfonic acid tetraoctylphosphonium salt, decylammoniumbutylsulfate, decylammoniumdecylsulfate, dodecylammoniummethylsulfate,
Dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl dimethyl ammonium methyl sulfate, tetramethyl ammonium hexyl sulfate, decyl trimethyl ammonium hexadecyl sulfate, tetrabutyl ammonium dodecyl benzyl sulfate, tetraethyl ammonium dodecyl benzyl sulfate ,
Examples thereof include compounds such as tetramethylammonium dodecylbenzyl sulfate, but are not limited thereto, and these compounds may be used in combination of two or more kinds.

Of these, phosphonium salt or ammonium salt type compounds are preferable. The amount of such a catalyst is preferably 0.5 to 50 mol based on 1 mol of the remaining catalyst, and 0.01 to 500 ppm based on the polycarbonate resin after polymerization, and more preferably 0. 0.01 to 300 ppm, particularly preferably 0.01 to
Used at a rate of 100 ppm.

Although the molecular weight of the polycarbonate resin is not specified, when the viscosity average molecular weight is less than 10,000, the high temperature characteristics and the like are deteriorated, and when it exceeds 40,000, the moldability is deteriorated, so that the viscosity average molecular weight is low. The molecular weight is preferably 10,000 to 40,000, and 1
Those of 4,000 to 30,000 are particularly preferable. Also, two or more polycarbonate resins may be mixed. In this case, it is naturally possible to mix with a polycarbonate resin having a viscosity average molecular weight outside the above range.

Particularly, a mixture with a polycarbonate resin having a viscosity average molecular weight of more than 40,000 prevents drawdown performance which is important for blow molding, anti-drip performance for improving flame retardancy, and jetting during injection molding. In order to exert an excellent effect on the melting property modification performance,
It can be appropriately mixed depending on the purpose. It is more preferably a mixture with a polycarbonate resin having a viscosity average molecular weight of 80,000 or more, and further preferably 10
It is a mixture with a polycarbonate resin having a viscosity average molecular weight of 10,000 or more. That is, it is possible to use 2 by a method such as GPC (gel permeation chromatography).
Those having a molecular weight distribution above the peak can be preferably used.

In the present invention, the viscosity-average molecular weight is 100 ml of methylene chloride and 0.7 g of polycarbonate resin at 20 ° C.
Insert the specific viscosity (η _SP ) obtained from the solution dissolved in step 1 into the following equation.

Η _SP /c=[η]+0.45×[η] ² c
(However, [η] is an intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7 A release agent can be added to the thermoplastic resin of the present invention. It gives a preferable result in that the distortion during molding can be suppressed. Saturated fatty acid ester is generally used as a mold release agent, for example, monoglycerides such as stearic acid monoglyceride, diglycerides, triglycerides such as triglyceride stearate, polyglycerin fatty acids such as decaglycerin decastearate and decaglycerin tetrastearate. Esters, lower fatty acid esters such as stearic acid stearate, higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used. In addition, an organosiloxane compound having an aromatic group or the like can be preferably used because the resin composition has good transparency and excellent heat resistance. The release agent is 0.0 per 100 parts by weight of the thermoplastic resin.
1 to 1 part by weight is used.

If necessary, a phosphorus-based heat stabilizer can be added to the thermoplastic resin of the present invention. As the phosphorus-based heat stabilizer, phosphite compounds and phosphate compounds are preferably used. Examples of the phosphite compound include triphenylphosphite, trisnonylphenylphosphite, tris (2,4-di-tert).
-Butylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenyl Phosphite, monooctyldiphenylphosphite, bis (2,6-di-ter
t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite,
Examples of the phosphite compound include bis (nonylphenyl) pentaerythritol diphosphite and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite. Of these, tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite are preferable.

On the other hand, examples of the phosphate compound used as the heat stabilizer include tributyl phosphate,
Trimethyl phosphate, tricresyl phosphate,
Examples include triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and among them, triphenyl phosphate and trimethyl phosphate. preferable.

Further, as another phosphorus-based heat stabilizer,
Tetrakis (2,4-di-tert-butylphenyl)
-4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3 '
-Biphenylene diphosphonite, tetrakis (2,4-
Phosphonite compounds such as di-tert-butylphenyl) -3,3′-biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -4-biphenylenephosphonite can also be preferably used.

The phosphorus-based heat stabilizer may be used alone or in combination of two or more kinds. The phosphorus-based heat stabilizer is 0.0 per 100 parts by weight of the thermoplastic resin.
001 to 0.5 parts by weight, preferably 0.001 to 0.0
It is suitable to use within the range of 5 parts by weight.

To the thermoplastic resin, a generally known antioxidant can be added for the purpose of preventing oxidation. Examples thereof include phenolic antioxidants, and specifically, for example, triethylene glycol-bis (3- (3
-Tert-butyl-5-methyl-4-hydroxyphenyl) propionate), 1,6-hexanediol-
Bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl -3- (3,5-di-tert-butyl-4-
Hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert)
-Butyl-4-hydroxybenzyl) benzene, N, N
-Hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5- J-te
rt-Butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis {1,1-dimethyl-2- [β-
(3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4
8,10-tetraoxaspiro (5,5) undecane and the like can be mentioned. The preferred range of addition of these antioxidants is 0.000 with respect to 100 parts by weight of the thermoplastic resin.
It is 1 to 5 parts by weight, preferably 0.001 to 0.5 parts by weight.

For the purpose of improving weather resistance and cutting off harmful ultraviolet rays, an ultraviolet absorber and a light stabilizer can be further added to the thermoplastic resin. Examples of such an ultraviolet absorber include a benzophenone-based ultraviolet absorber typified by 2,2′-dihydroxy-4-methoxybenzophenone, and 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl)- 5-chlorobenzotriazole, 2- (3,5-di-tert-butyl-2
-Hydroxyphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-
Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- [2-hydroxy-
3,5-bis (α, α-dimethylbenzyl) phenyl]
-2H-benzotriazole and 2- (3,5-di-
Examples thereof include benzotriazole-based ultraviolet absorbers represented by tert-amyl-2-hydroxyphenyl) benzotriazole. Further, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- [4,6-bis (2,4)
-Dimethylphenyl) -1,3,5-triazine-2-
Preferable examples also include hydroxyphenyltriazine compounds such as yl] -5-hexyloxyphenol.
Further, hindered amine light stabilizers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate are also used. It is possible. These may be used alone or in combination of two or more. The preferable range of the amount of the ultraviolet absorber and the light stabilizer added is 0.0001 to 100 parts by weight of the thermoplastic resin.
10 parts by weight, preferably 0.001 to 5 parts by weight.

Further, the transparent thermoplastic resin of the present invention may be blended with a bluing agent in order to cancel the yellow tint due to an ultraviolet absorber or the like. It is particularly useful for polycarbonate resins. As a specific bluing agent, for example, a general name Solvent Vio
let13 [CA.No (color index No) 6
0725; Trade name Bayer's "Macrolex Violet B", Mitsubishi Chemical Co., Ltd. "Dialesin Blue G", Sumitomo Chemical Co., Ltd. "Sumiplast Violet B"], generic name Solvent Violet31
[CA. No. 68210; Trade name "Mitsubishi Resin Co., Ltd." Dialesin Violet D "], general name Solve"
nt Violet33 [CA. No. 60725; trade name Mitsubishi Chemical Corporation's "Dialesin Blue J"], general name Solvent Blue 94 [CA. No. 615]
00; Trade name "Mitsubishi Resin Co., Ltd." Dialesin Blue N "], general name Solvent Violet36 [C
A. No. 68210; Trade name Bayer's "Macrolex Violet 3R"], general name Solvent Bl
ue97 [trademark name "Macrelex Blue RR" manufactured by Bayer Co., Ltd.], general name Solvent Blue87 [trademark name manufactured by Arimoto Chemical Industry Co., Ltd. "Plast Blue 858"
0 "] and the common name Solvent Blue 45 [C
A. No61110; Trade name "Terrazol Blue RLS" manufactured by Sand Co.], Macrolex Violet and Terrazol Blue R of Ciba Specialty Chemicals
LS and the like, in particular, Macrolex Violet, Terrazol Blue RLS, Macrolex Blue R
R and Plast Blue 8580 are preferred.

The thermoplastic resin may further contain other conventional additives such as reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass beads, and the like).
Glass balloon, milled fiber, glass flake,
Carbon fiber, carbon flake, carbon bead, carbon milled fiber, metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, ceramic particle, ceramic fiber, aramid particle, aramid fiber, polyarylate Fibers, graphite, conductive carbon black, various whiskers, etc.), flame retardants (halogen-based, phosphoric ester-based, metal salt-based, red phosphorus, silicon-based, fluorine-based, metal hydrate-based, etc.), heat-resistant agents, fluorescent Whitening agent, antistatic agent, flow modifier,
Inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), impact modifiers typified by graft rubber, infrared absorbers typified by phthalocyanine compounds and carbon black, and photochromic agents. It can be blended.

Among these, glass-based fillers, which can maintain transparency by reducing the difference in refractive index from the resin, are particularly suitable, and such glass-based fillers are widely known. It is preferable that the glass-based filler has a refractive index difference with the resin of 0.015 or less, preferably 0.010 or less. With such a filler, it becomes possible to obtain a sheet-like laminated structure having high transparency and high rigidity and strength.

Further, as the thermoplastic resin in the present invention, it is possible to use a resin already formed as a product or a part, that is, a so-called recycled material. In many cases, such recycled materials are provided with coatings for coloring, various functional coatings such as abrasion resistance, antistatic property and heat ray absorption, and laminated films such as metal films formed by vapor deposition, sputtering and plating. These can be used with the laminated film attached, or can be used with part or all of the laminated film removed.

For example, when an optical information recording medium (CD, DVD, MD, etc.) having a polycarbonate resin as a substrate is used as a recycle material, these are crushed and used as they are, and those crushed. , And can be used by mixing with other thermoplastic resin materials and / or recycled materials of other thermoplastic resin materials. On the other hand, from the optical information recording medium to the information recording layer,
Selectively remove the reflective layer and protective coat layer from the resin substrate,
It is also possible to collect and use the resin itself, and a method conventionally proposed as such a removing method can be used.

Next, the dyes, pigments, light diffusing agents, and light high-reflecting agents to be incorporated in at least one layer constituting the laminated structure of the present invention will be described. Those known per se as colorants or additives for resins are used, and the desired color can be determined by selecting the kind of resin, dispersibility in resin, processing temperature and the like. Two or more kinds of colorants can be used in combination.

Examples of agents for coloring include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as dark blue, perinone dyes, quinoline dyes, quinacridone dyes. Examples thereof include organic colorants such as dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes, and carbon black. Among these, transparent organic colorants are preferable. More preferable examples include anthraquinone dyes, perinone dyes, quinoline dyes, perylene dyes, coumarin dyes, and thioindigo dyes.

Specific examples of the dye include CI Solve
nt Red 52, CI Solvent Red
149, CI Solvent Red 150, CI
Solvent Red 191, CI Solve
nt Red 151, CI Solvent Red
135, CI Solvent Red 168, CI
Disperse Red 22, CI Solve
nt Blue 94, CI Solvent Blu
e 97, CI Solvent Blue 87, CI
Solvent Violet 13, CI Sol
VentViolet 14, CI Disperse
Violet 28, CI Solvent Gre
en 3, anthraquinone dyes known as CI Solvent Green 28, and quinoline dyes include CI Solvent Yellow 33,
CI Solvent Yellow 157, CI
Disperse Yellow 54, CI Dis
Perse Yellow 160 and the like can be mentioned. CI Solven as a perinone dye
t Red 135, CI Solvent Red
179, CI Solvent Orange 60 and the like. These can be used alone or in combination of two or more and can be colored according to the purpose.

Fluorescent colorants can also be used, examples of which include fluorescent dyes and fluorescent organic pigments such as phthalocyanine complexes and naphthalocyanine complexes.

Various fluorescent dyes can be used. For example, perylene fluorescent dye, coumarin fluorescent dye, benzopyran fluorescent dye, anthraquinone fluorescent dye, thioindigo fluorescent dye, xanthene fluorescent dye,
Examples include xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among them, it is preferable that the perylene fluorescent dye, the coumarin fluorescent dye, and the benzopyran fluorescent dye are contained in an amount of 5% by weight or more based on 100% by weight of the fluorescent dye, from the viewpoint of fluorescence durability (weather resistance).

Various kinds of coumarin-based dyes can be used, and specific examples thereof include MACROLEX Fluorescent from Bayer.
Yellow 10GN (CI Solvent Y
elllow 160: 1), and MACREX
Fluorescent Red G etc. can be mentioned. Various kinds of benzopyran-based fluorescent dyes can be used, and specific examples thereof include, for example,
Red B as Fluorol series manufactured by BASF
K and Red GK can be mentioned.

Various kinds of perylene fluorescent dyes can be used, and specific examples thereof include CI.
Vat Red 15, CI Vat Orange
7, CI Solvent Green 5 and B
F Ora as LUMOGEN series made by ASF
nge240, F Red300, F Yellow0
83, F Red 339, F Violet 570 and the like. Among the above, those containing 5 wt% or more of the perylene fluorescent dye in 100 wt% of the total amount of the fluorescent dye can be preferably used. Perylene fluorescent dye,
Specific examples of the fluorescent dye other than the coumarin-based fluorescent dye and the benzopyran-based fluorescent dye include the followings.

As the anthraquinone type dye, CIV
at Orange 9, CI Vat Orange
2, CI Vat Orange 4, a pyranthrone type anthraquinone dye, known as CI Vat
Blue 20, CI Vat Blue 19, CI
Vat Blue 22, CI Vat Green
4, and the dibenzanthrone-type anthraquinone dye known as CI Vat Green 12;
CI Vat Violet 1, CI Vat Vi
Olet 9, CI Vat Violet 10, and CI Vat Green 1, isodibenzanthrons anthraquinone dyes, CI
Vat Orange 1, CI Vat Yellow
An example is a dibenzpyrenequinone anthraquinone dye known as w 4. Examples of anthraquinone dyes include CI Vat Blue 6,
CI Vat Violet 13 etc. can also be mentioned.

CI Vat as a thioindigo dye
Red 1, CI Vat Red 2, CI Va
t Red 41, CI Vat Red 47, CI
Vat Violet 2, CI Vat Viol
etc. can be mentioned.

As the fluorescent organic pigment, CI PIGME can be used.
NT GREEN 7, CI PIGMENT BLU
Examples thereof include phthalocyanine-based organic pigments such as E 15: 3 and naphthalocyanine-based organic pigments. As the light diffusing agent that can be used in the present invention, both known inorganic fine particles and polymer fine particles can be used. The shape of the light diffusing agent is not particularly limited, and various shapes such as a granular shape, a spherical shape, a plate shape, a hollow shape, a needle shape, and a spindle shape can be adopted. The average particle diameter of the light diffusing agent is preferably 0.01 to 50 μm. The average particle size is more preferably 0.1 to 10 μm, and further preferably 0.1 to 8 μm. The distribution of particle size is preferably narrow, and more preferably the average particle size ± 2μ.
The particles having m have a distribution in the range of 70% by weight or more based on the whole particles.

The light diffusing agent preferably has an absolute value of the difference in refractive index from the matrix resin of 0.02 to 0.2.
This is because when a light diffusing agent is used, it is required to achieve both a high level of light diffusivity and high light transmittance. From the viewpoint of transparency, the case where the refractive index of the light diffusing agent is lower than that of the matrix resin is more preferable. Examples of the inorganic fine particles include the following. That is, barium sulfate, calcium carbonate, silica, alumina, magnesia, mica, talc, aluminum hydroxide, titanium oxide, lithium fluoride, calcium fluoride,
Magnesium sulfate, magnesium carbonate, magnesium oxide, zinc oxide, zirconium oxide, cerium oxide, ground glass, glass milled fiber, glass beads, ultra-thin glass flakes, glass balloons, alumina balloons,
And calcium silicate. Further, these particles may have the surface of the particles coated with a compound having a composition different from the composition inside the particles.

Examples of the polymer fine particles of the present invention include organic crosslinked particles obtained by polymerizing a non-crosslinkable monomer and a crosslinkable monomer. Examples of non-crosslinkable monomers include acrylic monomers, styrene monomers, acrylonitrile monomers, and olefin monomers. These may be used alone or in combination of two or more. Furthermore, other copolymerizable monomers other than such monomers can be used. Examples of other organic crosslinked particles include silicon-based crosslinked particles.

On the other hand, particles of heat-resistant polymer such as polyether sulfone particles can also be mentioned as the polymer fine particles of the present invention. That is, those in which the morphology of the fine particles is not impaired even when the matrix resin is in the molten state by heating do not require a crosslinkable monomer. Further, as the polymer fine particles, various epoxy resin particles, urethane resin particles,
Thermosetting resins such as melamine resin particles, benzoguanamine resin particles, and phenol resin particles can also be used. As the light diffusing agent, more preferably, organic crosslinked particles can be mentioned. Such particles have high controllability of particle diameter and particle shape, and can control light diffusivity to a higher degree. Further, particularly when the matrix resin is a polycarbonate resin or the like, there is an advantage that thermal discoloration or the like does not easily occur during molding at high temperature.

Acrylic monomers used in such organic crosslinked particles include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and 2-ethylhexyl. Methacrylate, phenyl methacrylate and the like can be used alone or in combination. Of these, methyl methacrylate is particularly preferable.

As the styrene type monomer, styrene,
Alkyl styrenes such as α-methyl styrene, methyl styrene (vinyl toluene) and ethyl styrene, and halogenated styrenes such as brominated styrene can be used, and among these, styrene is particularly preferable. Acrylonitrile and methacrylonitrile can be used as the acrylonitrile-based monomer. As the olefin-based monomer, ethylene, various norbornene type compounds, etc. can be used. Still other copolymerizable other monomers include glycidyl methacrylate, N-
Examples thereof include methylmaleimide and maleic anhydride, and as a result, units such as N-methylglutarimide can be included.

On the other hand, examples of the crosslinkable monomer for the vinyl non-crosslinkable monomer include divinylbenzene, allyl methacrylate, triallyl cyanurate, and the like.
Triallyl isocyanate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane (meth) acrylate, pentaerythritol tetra ( Examples thereof include (meth) acrylate, bisphenol A di (meth) acrylate, dicyclopentanyl di (meth) acrylate, dicyclopentenyl di (meth) acrylate and N-methylol (meth) acrylamide.

As a method for producing organic crosslinked particles composed of an acrylic monomer or the like, in addition to a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate,
The seed polymerization method, the two-step swelling polymerization method, etc. can be mentioned. Also in the suspension polymerization method, the aqueous phase and the monomer phase are separately held and both are accurately supplied to a continuous disperser,
By controlling the particle size by the number of revolutions of the disperser, or by passing the monomer phase through an aqueous liquid having dispersability in a continuous production method in the same manner as a small-sized orifice of several to several tens of μm or a porous filter. A method of supplying and controlling the particle size is also possible.

The silicon-based crosslinked particles have a siloxane bond as a main skeleton and an organic substituent in a silicon atom, and have a high degree of crosslinking represented by polymethylsilsesquioxane and methylsilicon rubber particles. Some of them have a low degree of crosslinking, but those having a high degree of crosslinking represented by polymethylsilsesquioxane are preferred in the present invention. Examples of the organic group substituting the silicon atom of the silicon-based crosslinked particles include an alkane group such as a methyl group, an ethyl group, a propyl group, a butyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and a carboxyl group. A group, a carbonyl group, an ester group, an ether group or the like can be used.

As a method for producing such silicon-based crosslinked particles, a method is generally used in which trifunctional alkoxysilane or the like is hydrolyzed and condensed in water to grow siloxane bonds to form three-dimensionally crosslinked particles. The particle size can be controlled by, for example, the amount of alkali in the catalyst or the stirring process. On the other hand, as a method for producing polymer fine particles other than the organic cross-linked particles, other methods such as a spray drying method, an in-liquid curing method (coagulation method), a phase separation method (coacervation method), a solvent evaporation method, a reprecipitation method, etc. A combination of a nozzle vibration method and the like when performing these can be mentioned.

Further, as the form of the fine polymer particles, in addition to a single-phase polymer, a core-shell polymer form or an IPN structure having a structure in which two or more kinds of components are intertwined with each other is possible. . Further, composite type particles having a core of inorganic fine particles and a shell of organic crosslinked particles or a shell of organic crosslinked particles and a shell of epoxy resin, urethane resin or the like can also be used.

The above light diffusing agent may be coated with various surface treating agents. In particular, it is preferable that the inorganic fine particles are coated with a surface treatment agent because the discoloration of the material due to heat deterioration can be suppressed. Examples of the surface treatment agent include organic acid compounds such as fatty acids, resin acids, maleic acid, and sorbic acid, ester compounds of these organic acids with monohydric or polyhydric alcohols, sulfonic acid-based surfactants, and organic titanate-based agents. Examples thereof include coupling agents, organic aluminate-based coupling agents, phosphate-based coupling agents, organic silane-based coupling agents, silane compounds containing Si—H groups, and diene-based polymers such as polybutadiene and polyisoprene. ..

Titanium dioxide particles are preferably used as the light-reflecting agent. Titanium dioxide particles are manufactured by
Although not limited by the crystal structure and the particle size, titanium oxide produced by the chlorine method and having a rutile crystal structure is more preferable. Generally, the particle size of titanium oxide particles for pigment is 0.1 to 0.4 μm, but the particle size may be less than 0.1 μm. These titanium dioxide particles are generally surface-treated with an inorganic surface treatment agent (such as alumina and / or silica). It is preferable that these titanium dioxide particles are further treated with an organic surface treatment agent. Examples of the organic surface treatment agent include siloxanes such as alkylpolysiloxane, alkylarylpolysiloxane, and alkylhydrogenpolysiloxane, and organosilicones such as alkylalkoxysilane and amino silane coupling agents. Preferred treating agents include methyl hydrogen polysiloxane, methyl trimethoxysilane, trimethylmethoxysilane, N-β (aminoethyl) -γ-
Surface treatment with aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane and the like can be mentioned. In the surface treatment agent,
A stabilizer, a dispersant and the like may be contained in an amount that does not impair the object of the present invention. As the surface treatment method, titanium dioxide particles and a surface treatment agent are dispersed in water or an organic solvent to perform a wet treatment, or a dry treatment using a super mixer, a Hensyl mixer, or a surface treatment agent A method of mixing titanium particles and a thermoplastic resin at the same time with a V-type blender, and a method of simultaneously charging and extruding into an extruder are also effective.

The laminated structure of the present invention can be molded by various methods, but preferably, a method of filling a resin into the mold cavity can be mentioned. This is because the degree of freedom in shape is extremely high, and a higher degree of designability can be achieved.
Examples of such methods include injection molding, rotational molding,
Powder compression methods such as powder compression molding and ultrasonic powder molding can be mentioned. The injection molding method is more preferable. This is because such a molding method can efficiently manufacture the entire laminated structure. Powder molding has an advantage when a large-sized or low-distortion molded product is obtained.

The procedure for manufacturing the laminated structure of the present invention is as follows:
A method of molding one layer, molding the next layer in a state where the molded product is inserted in a mold of the next step, and laminating two layers can be mentioned. A laminated structure having a three-layer structure can be obtained by molding with two layers inserted in the mold. In the case of the injection molding method, a multicolor molding method in which a plurality of layers are continuously formed by one molding machine, and an insert molding method in which each layer is molded by an independent molding machine are used as the method for producing the laminated structure of the present invention. used. In particular, a laminated structure in which all layers are obtained by injection molding is suitable in the present invention.

Further, in this molding method, various molding methods in which other factors are added can be used. For example, it is possible to appropriately combine ultra-high speed injection molding, injection compression molding, heat insulation mold molding, local high temperature mold molding, in-mold molding, sandwich molding, gas assist molding and the like. That is, a combination of a plurality of these may be used. Among such molding methods, ultra-high speed injection molding is a suitable method particularly when a design is applied to the interface of the laminated structure.
In such a case, the flow of the resin tends to be extremely complicated, and an unfilled portion is likely to be finally generated in the design portion due to the way the resin wraps around. In the case of ultra-high speed injection molding, it is possible to reduce the melt viscosity of the resin, achieve uniform flow, and simplify the wraparound of the resin. The injection speed of ultra-high speed injection molding is 300 mm / sec or more, preferably 35 mm
0 mm / sec or more is included.

The combination with injection compression molding is suitable when there is a precise pattern in the interface portion. Further, it is possible to achieve a molded product with less distortion and weld. Furthermore, it improves the adhesiveness of the interface and contributes to the strength and product life of the laminated structure. Of the above-mentioned injection compression molding, so-called injection press molding is extremely suitable. What is injection press molding?
The capacity of the initial mold cavity is made larger than the capacity of the filling resin, and a small amount of the filled resin with respect to the capacity of the mold cavity is reduced until the mold cavity has a predetermined shape, and the resin inside is compressed. This is a molding method in which a resin is filled in the unfilled portion in the mold cavity to obtain a molded product.

In the case of ordinary molding, the laminated structure of the present invention, particularly the molded product of the second and subsequent layers, tends to have a low resin density on the resin surface side of the first layer and at the flow end, In addition, the resin density tends to increase near the gate. As a result, warpage is likely to occur especially in a large plate-shaped laminated structure. Such warpage can be significantly reduced by injection press molding. This is because in the case of injection press molding, pressure is applied in the thickness direction, so there is no pressure distribution in the in-plane direction of the mold, and because the distance in the thickness direction is extremely short, there is no loss of pressure applied to the resin. This is because the pressure necessary for the proper contraction of is uniformly applied. Further, even when an unfilled portion is generated in the design or the like as described above, if such a portion is small, it is possible to fill it.

As is generally known, injection press molding can be carried out at an extremely low pressure, so that the level of mold clamping pressure of the injection molding machine can be greatly reduced. This is a particularly large-sized molded product, and in the molded product having a long flow length, the quality of the product can be improved and the cost required for equipment can be reduced. For the same reason, it is preferable to combine adiabatic mold molding and local high temperature mold molding (halogen lamp irradiation, electromagnetic induction heating, high-speed switching of heat medium, ultrasonic mold, etc.). That is, in the production of the laminated structure of the present invention, ultra-high speed injection molding, injection compression molding (including injection press molding), adiabatic mold molding, and local high temperature mold molding are performed especially when there is a pattern on the interface. It is preferable to use them in appropriate combination. Furthermore, it is preferable to use a combination of ultra-high speed injection molding and injection compression molding, heat insulation mold molding or local high temperature mold molding.

When sandwich molding is combined, it is possible for either one layer or the other to have a two-layer construction. When combined with gas assisted molding, one layer,
Alternatively, by forming the other layer, or one layer and the other layer together as a hollow structure, it is possible to reduce the weight of each layer and to impart different design characteristics and optical functions. For example, filling the hollow portion with a compound having a photochromic property to prepare a photoreactive product.

In the case where the laminated structure of the present invention is required to have a high surface hardness depending on the purpose of use, it is more preferable to subject the surface to a hard coat treatment. Various hard coating agents can be used as the hard coating agent, and examples thereof include a silicone resin type hard coating agent and an organic resin type hard coating agent. Silicone resin hard coating agent
A resin having a siloxane bond, for example, a partial hydrolyzate of trialkoxysilane and tetraalkoxysilane or an alkylated product thereof, a hydrolyzed mixture of methyltrialkoxysilane and phenyltrialkoxysilane, and colloidal silica filling. Examples thereof include partial hydrolysis-condensation products of organotrialkoxysilane. Although these include alcohols and the like generated during the condensation reaction, they may be further dissolved or dispersed in any organic solvent, water, or a mixture thereof, if necessary. Examples thereof include fatty acid alcohols, polyhydric alcohols and their ethers, and esters. In addition, in order to obtain a smooth surface state, various surfactants such as siloxane-based or fluoroalkyl-based surfactants may be added to the hard coat layer.

Examples of the organic resin-based hard coating agent include melamine resin, urethane resin, alkyd resin, acrylic resin, polyfunctional acrylic resin and the like. Here, examples of the polyfunctional acrylic resin include resins such as polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate, and phosphazene acrylate. Of these hard coating agents, silicone resin-based hard coating agents that are excellent in long-term weather resistance and have a relatively high surface hardness are preferable. Particularly, after forming a primer layer composed of various resins, a silicone resin-based hard coating agent is formed on the primer layer. The thing which formed the hardened layer adjusted from the coating agent is preferable.

Examples of the resin forming the primer layer include urethane resins, acrylic resins, polyester resins, epoxy resins, melamine resins, amino resins, and polyester acrylates, urethane acrylates, epoxy acrylates, which are composed of various blocked isocyanate components and polyol components. Various polyfunctional acrylic resins such as phosphazene acrylate, melamine acrylate and amino acrylate can be mentioned, and these can be used alone or in combination of two or more kinds. Among these, particularly preferred are those containing 50% by weight, and more preferably 60% by weight or more of acrylic resin and polyfunctional acrylic resin, and those comprising acrylic resin are particularly preferred. Acrylic resin primer layers are particularly suitable for polycarbonate resins.

Further, the resin forming the primer layer of the silicone resin type hard coating agent includes a light stabilizer and an ultraviolet absorber described later, a catalyst of the silicone resin hard coating agent, a heat / photopolymerization initiator, a polymerization inhibitor, Silicone defoaming agent, leveling agent, thickening agent, anti-settling agent, anti-sagging agent, flame retardant, various additives of organic / inorganic pigments / dye and additives may be included. The acrylic resin forming the primer layer of the silicone resin-based hard coating agent is (a) a primer composition mainly composed of a monomer component, which is applied to the surface of the molded body and then heated, or ultraviolet rays, electron beams, radiation, etc. Which is cured by irradiating the active energy ray (hereinafter, may be referred to as an acrylic resin (a)), and (b) after polymerizing a polymer component in advance, a solution or melt of the polymer is used as a primer composition. Any of those applied and cured by volatilizing a solvent or the like (hereinafter sometimes referred to as acrylic resin (b)) can be used. In particular, the latter acrylic resin (b) is more preferable because it can reduce unreacted residual monomer that is likely to cause deterioration as much as possible.

As one of the preferred embodiments of the acrylic resin used as a primer for the silicone resin type hard coat agent, the molar ratio of the alkyl methacrylate monomer and the (meth) acrylate monomer having an alkoxysilyl group is 99: 1 to 1: 1. 60:40, more preferably 9
The copolymer obtained by copolymerizing in the ratio of 7: 3 to 70:30 is mentioned. Moreover, as one of the preferable embodiments of the acrylic resin used as the primer for the silicone resin-based hard coat agent, 99-60% by weight of an acrylic resin containing a hydroxy group and 1-40% by weight of a hydrolyzed condensate of an alkoxysilane compound. (However R _a R _'b -SiO
Weight converted to _{4- (a + b) / 2} . However, R and R'can also be a mixture or reaction product with a monovalent organic group).

The acrylic resin containing a hydroxy group is
A copolymer of an alkyl methacrylate monomer and a hydroxy group-containing alkyl methacrylate monomer is preferable, and 2-hydroxyethyl methacrylate is particularly preferable as the monomer. On the other hand, as the alkoxysilane compound, alkyltrialkoxysilane is preferable, and methyltrimethoxysilane and methyltriethoxysilane are particularly preferable. The alkoxysilane compounds can be used alone or in combination. The hydrolysis-condensation product of the alkoxysilane compound is obtained by subjecting it to a hydrolysis-condensation reaction under acidic conditions, and as such an acid, a volatile acid such as acetic acid or hydrochloric acid is preferable. Further, a mixture or reaction product of a hydrolysis-condensation product of an alkoxysilane and a hydroxy group-containing acrylic resin and a mixture of a melamine resin can also be mentioned. In the acrylic resin (b), the concentration of the solid content of the resin forming the primer layer in the primer composition is preferably 1 to 50% by weight,
It is more preferably 3 to 30% by weight.

Further, the above primer composition may contain a light stabilizer and an ultraviolet absorber for the purpose of improving the weather resistance of the laminated structure. Examples of the light stabilizer include hindered amine light stabilizers and nickel complex light stabilizers. These agents may be used alone or in combination of two or more, and are preferably used in an amount of 0.1 to 50 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the resin forming the primer layer. . Examples of the ultraviolet absorber include benzotriazole ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, salicylate ultraviolet absorbers, and triazine ultraviolet absorbers. These agents may be used alone or in combination of two or more, and are preferably used in an amount of 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the resin forming the primer layer. .

Further, the primer composition may contain a catalyst capable of curing the silicone resin type hard coating agent. The coating of the primer composition on the surface of the laminated structure is a bar coating method, a doctor blade method, a dip coating method, a flow coating method (shower coater, curtain flow coater), a spray coating method, a spin coating method, a roller coating method ( A method such as a gravure roll coating method or a transfer roll coating method) can be appropriately selected according to the shape of the substrate to be coated. Also,
The thickness of the primer layer is preferably 0.1 to 10 μm, more preferably 1 to 5 μm.

As the silicone resin type hard coating agent,
More preferably, an organosiloxane resin composed of a hydrolysis-condensation product of a trialkoxysilane compound and a hydrolysis-condensation product of a tetraalkoxysilane compound can be mentioned. Further, it is preferable to contain metal oxide fine particles dispersed in a colloidal form from the viewpoint of adjusting the surface hardness of the hard coat layer, the dyeability, the refractive index, the thickness of the coating film, and the like. Among such metal oxide fine particles, colloidal silica is the most typical.

A more preferable silicone resin type hard coating agent is an organosiloxane composed of colloidal silica (component x), trialkoxysilane hydrolyzed condensate (y component) and tetraalkoxysilane hydrolyzed condensate (z component). Resin can be mentioned. Particularly, in order to obtain a hard coat composition that forms a hard coat layer having excellent wear resistance, it is preferable that 70% by weight or more of the trialkoxysilane is methyltrialkoxysilane, and substantially all of the trialkoxysilane is methyltrialkoxy. More preferably, it is silane. The tetraalkoxysilane is preferably tetramethoxysilane or tetraethoxysilane. These alkoxysilanes can be used alone or in combination.

The y component and the z component are a mixture of a part or all of the alkoxysilane hydrolyzed and a condensate of a part or all of the hydrolyzate, which undergoes a sol-gel reaction. It is obtained by In particular, it is preferable to use the following process (1) and process (2) for the preparation because it is possible to obtain a coat layer having more excellent abrasion resistance without the formation of precipitates.

Process (1): A trialkoxysilane in a colloidal silica dispersion is hydrolyzed and condensed under an acidic condition. Process (2): (i) Tetraalkoxysilane is added to the reaction liquid obtained by the reaction of the process (1) to cause a hydrolysis condensation reaction, or (ii) the reaction liquid obtained by the reaction of the process (1). And a reaction solution in which the tetraalkoxysilane has been hydrolyzed and condensed beforehand. The mixing ratio of the x-component, y-component and z-component, which are the solid content of the organosiloxane resin, is preferably 5 to 45% by weight for the x component and 50 to 50 for the y component in terms of R ⁸ SiO _3/2. 80% by weight, z component is ₂ to 3 in terms of SiO ₂
It is used in an amount of 0% by weight, more preferably the x component is 15
˜35 wt%, the y component is 55 converted to R ⁸ SiO _3/2 .
~ 75 wt%, the z component is 3 to 20 in terms of SiO _2.
% By weight. Here, R ⁸ means a monovalent organic group.

The hard coat composition usually further contains a curing catalyst. As such a catalyst, sodium acetate, potassium acetate and benzyltrimethylammonium acetate are preferably used. When the basic water-dispersed colloidal silica is used as the colloidal silica and the aliphatic carboxylic acid is used as the acid during the hydrolysis of the alkoxysilane, the curing catalyst is already contained in the hard coat composition. It will be. As the coating method of the hard coat composition, various methods mentioned as the coating method of the primer composition can be appropriately selected. Further, the thickness of the silicone resin-based hard coat layer is usually 2 to 10 μm, preferably 3
~ 8 μm. The hard coat layer may also contain various light stabilizers and ultraviolet absorbers listed in the primer composition.

The laminated structure of the present invention is excellent in aesthetics and design because continuous color tone changes (gradation color) are recognized along the sheet surface. In particular when the laminated structure is transparent or translucent, it can be used as decorative organic glass and glass windows. By using the laminated structure as an organic glass and a glass window, as compared with ordinary colorless and transparent glass, it has excellent aesthetics and by using glass having various colors,
You can make a variety of products and windows. In particular, when a sheet-shaped laminated structure is provided with a character or a figure in a three-dimensional pattern at the interface where two kinds of layers contact each other, the character or figure is a three-dimensionally emphasized organic glass. be able to.

A preferred embodiment of the laminated structure of the present invention is characterized by comprising a sheet-shaped laminated structure and a light source section, and the light source section is arranged at a side end portion of the laminated structure. A high design sheet-like laminated structure can be mentioned. The light source portion can be arranged at any part of the side surface end portion of the laminated structure, but as described above, the side surface end portion is laminated from the side surface from the viewpoint that superior design and aesthetics can be obtained. It is preferably the end where the layer containing the colorant and having a monotonic change in thickness is formed in the direction of the corresponding other side of the structure. Explaining with reference to the side views shown in FIG. 3 and FIG. 4, the light source unit has a side surface end portion (FIG. 3) of the thick portion of the layer (3) or a side end portion (thickness of the layer (3) in the laminated structure. 4). The light source section may be arranged at one of the side surface end portions as shown in FIGS. 3 and 4, or may be arranged at both side surface end portions.

Further, in the case of a laminated structure having a light source at the side end portion, it is preferable that characters or figures are formed in a three-dimensional pattern, especially at the interface where two types of layers are in contact. This is because, as mentioned above, it is possible to obtain extremely excellent design and aesthetic aesthetics, in which the figure is visually or three-dimensionally observed from the surface where the color tone changes continuously due to the presence of the light source at the side edge. is there. Such excellent designability is exhibited especially when a fluorescent colorant, a light diffusing agent, or a high-reflecting agent is incorporated in one layer, and therefore it is more preferable to include these additives. is there.

In order to achieve a design in which a three-dimensional character or figure is observed by the light source at the side end, the following constitution is suitable. That is, when a resin containing a fluorescent colorant or a light-reflecting agent is used for the layer on which the three-dimensional pattern is convex and the thickness of the layer is thin (that is, when the total thickness is substantially uniform, The light source unit is arranged at the side surface end of the layer which is colorless or colored with another coloring agent (thick side). In such a configuration, when the fluorescent colorant is included, the convex portion of the three-dimensional pattern is brighter. Will be observed.

Further, the above-mentioned excellent design and aesthetic effects are more exerted in the decorative organic glass or the glass window in which the laminated structure is transparent or translucent. That is, when the light source section is arranged at the side end portion of the sheet-shaped laminated structure in the organic glass, the gradation effect of the color tone is emphasized by the irradiation of light from the light source section. Further, the sheet-shaped laminated structure provided with characters or figures in the above-described three-dimensional pattern is more transparent in its entirety by being irradiated with light from the side edges, while the characters or figures are more three-dimensionally emphasized. The effect is obtained. At that time, the side surface end portion of the sheet-shaped laminated structure in which the light source portion is arranged contains a dye, a pigment, or a light diffusing agent along the direction of the other side surface from the side surface end portion and is monotonous. It is preferable that it is an end portion where a layer having a large thickness change is formed.

In particular, one layer is formed of a transparent resin containing a fluorescent dye and has a monotonic thickness change in at least one direction of the sheet surface, and the other layer is substantially colorless and transparent. A preferred embodiment is a decorative organic glass or glass window formed of resin. The light source unit is provided with a household power source, an automobile power source, a vehicle power source, a portable power source, and an electric lamp that emits light using a battery as a power source. Further, in the case of a structure in which light is emitted to the side surface end portion of the laminated structure, the light source itself does not have to be arranged at the side surface end portion, and may be a structure in which light is guided to the side surface end portion with an optical fiber or the like. As the electric light, any of well-known electric lights which are usually used for household use, automobile use and vehicle use can be used. The shape of the electric lamp is not particularly limited, and can take various shapes such as a point shape, a spherical shape, a tubular shape, and a surface shape. A point light source emits a point light, a line light source emits a line emission, or a surface light source produces a surface. Either of the light emissions can be used.

Electric lamps include incandescent lamps, tungsten lamps,
Halogen tungsten lamp, halogen lamp, mercury lamp, sodium lamp, xenon lamp, xenon flash lamp, metal halide lamp, fluorescent lamp,
LEDs (light emitting diodes), EL (electroluminescence), semiconductor lasers, etc. can be used,
Especially cold cathode fluorescent lamps, semi-hot fluorescent lamps, hot cathode fluorescent lamps, flat fluorescent lamps, black lights, LEDs, EL, semiconductor lasers, short arc metal lamps, short arc xenon lamps, halogen lamps, super lamps used in the field of information equipment. It is preferable to use a high pressure mercury lamp, an internal electrode type rare gas fluorescent lamp, an external electrode type rare gas fluorescent lamp, or the like.

The light from the electric lamp may be directly radiated to the side end portion of the laminated structure, or may be radiated only with a specific wavelength component through an optical filter or a prism, or through a light diffusing plate or the like. The light emitted from the electric lamp may be emitted while changing the optical axis. Further, the light from the electric lamp may be continuously turned on by irradiation, or may be continuously or discontinuously blinked by repeating irradiation and non-irradiation. Further, since the laminated structure of the present invention is made of resin, it is lightweight and can be used as an automobile window. When used as an automobile window, it is preferable that each layer of the laminated structure is formed of a polycarbonate resin in terms of transparency, heat resistance and impact resistance. When it is used as an automobile window, the surface of which the surface hardness is improved by the above-mentioned surface coating is suitable.

Of the various automobile windows, the automobile window of the present invention is preferably used for other glass windows except the windshield (windshield). For example, the automobile window of the present invention can be applied to a front door window, a rear window, a quarter window, a back window or a sunroof window. FIG. 10 shows the form of the laminated structure when the laminated structure of the present invention is used as a back window of an automobile, and FIG. 11 shows a layout of windows in the automobile.
Is shown in.

As shown in FIGS. 10 and 11, when the laminated structure is arranged as an automobile window, the color tone may change from the upper part to the lower part. Further, the change in shade may be left or right. 10 and 1 for the laminated structure.
As shown in FIG. 1, a character or figure having a three-dimensional pattern may be provided at the interface where the two layers contact. At that time, as shown in FIG. 10-B, by arranging a light source part under the laminated structure (window) and irradiating light, it is possible to emphasize the change in color tone, and the character or figure can be more solid. It can also be expressed as Of course, the light source unit may be disposed not only in the lower portion but also in the upper portion, the left side, or the right side depending on the form and combination of the layers constituting the laminated structure.

Further, according to the present invention, there is provided a box-shaped container excellent in aesthetics and design using the laminated structure.
That is, a box-shaped container in which at least one surface is formed of a laminated structure is provided. It is also possible to combine structures having various colors as a laminated structure into a box-shaped container, and by using a laminated structure having a three-dimensional pattern such as letters and figures, not only colors but also three-dimensional patterns can be obtained. It can also be made into a highly designed box-shaped container. In particular, the box-shaped container is a member of a housing in various OA devices such as a computer and a mobile terminal, a member of a housing in various electric and electronic devices such as a mobile phone and a portable audio device, a housing in an optical device,
In addition, it can be advantageously used as a housing for miscellaneous goods.

At least one of the surfaces forming the box-shaped container is formed of the sheet-shaped laminated structure. The shape of the box-shaped container is not particularly limited and may be determined according to the shape of the article in which the box-shaped container is used. This shape may be a box shape having four or more surfaces formed of a flat body. In addition, taking the shape consisting of 6 planes as an example,
It may be a box type whose entire surface is surrounded by a sheet-like object, or may be a box type in which a flat body does not exist on one or two sides of the hexahedron. A box type in which a flat body does not exist on these two surfaces is surrounded by, for example, four flat surfaces and is open at the top and bottom.
It may be a face piece.

The box-shaped container does not necessarily have to be composed of only a rectangular flat body. For example, at least one flat body may be curved. Further, it may be a box type which is composed of a planar body which is entirely curved. An example thereof is a tubular box type. In the case of this curved flat body or tubular shape, the radius of curvature (R) is L / 2 or more, preferably 3 L or more, where L is the length of one side of one surface of the box-shaped structure. At least one surface of the box-shaped container is composed of the sheet-shaped laminated structure, and in order to take advantage of the high designability of the sheet-shaped laminated structure, at least the surface of the visible portion is the sheet-shaped laminated structure. Should be configured. In addition, the box-shaped container can be formed by pressure-bonding or adhering the side surface end portion of the flat body of the sheet-shaped laminated structure with an adhesive. It is also possible to bend the sheet-shaped laminated structure at one place or several places by heating or the like to form a flat body having two or more surfaces.

Further, the box-shaped container can be prepared by insert molding as described in (a) to (c) below. These are merely for the purpose of illustration, modifications of these may be used, and other molding methods may be used. (A) One or a plurality of the sheet-shaped materials prepared in advance by injection molding, etc., by previously forming a sheet-shaped material including the A layer having a monotonous thickness change (which may further include three-dimensional characters or figures). After inserting into the mold,
A method of molding a box-shaped container by filling a resin to be the layer B by injection molding and stacking. (B) A sheet-like material composed of the layer A having a monotonous thickness change (which may further include three-dimensional characters or figures) is prepared in advance by injection molding or the like, and the obtained sheet-like material is heated or the like. A method of bending to form a flat body, then inserting the flat body into a mold, filling a resin to be layer B by injection molding, and stacking the resin to form a box-shaped container. (C) In the two-color molding, the thickness of the first mold is monotonous (three-dimensional characters or figures may be included).
A sheet-like article comprising the layer A having the above is prepared by injection molding in advance, and then the sheet-like article obtained by rotating or sliding the die or the molded article is set in the second die, and the second die A method for forming a box-shaped container by filling a resin to be layer B by injection molding and stacking the layers.

At least one surface of the box-shaped container of the present invention may be composed of the above-mentioned highly-designed sheet-like laminated structure, and the other surface may be composed of another sheet-shaped material such as a metal plate or a resin plate. It may be configured. The box-shaped container is excellent in design and aesthetics because continuous color tone changes are formed in various forms along the sheet surface. Therefore, it can be used for various devices, members of devices, and housings of daily necessities. For example, housings for office automation equipment such as computers and associated components; housings for communication or electronic and electrical equipment such as mobile phones and portable audio equipment; household items such as storage boxes for tape and disk cases and containers for various items. Can be used for the housing.

When the sheet-like laminated structure constituting the surface is transparent or semi-transparent, it can be used as a box-shaped container having a light source inside, and can be further used for lighting equipment, optical display boards, and other optical equipment. Also available for housing. A schematic diagram in which the box-shaped container is used for the housing of the OA device is shown in FIG. 15-A. In the case of the box-shaped container shown in FIG. 15-A, an OA device (CD player) is housed in the box-shaped container, and four side surfaces thereof are constituted by a sheet-shaped laminated structure. A cross section of the sheet-shaped laminated structure forming one side surface of FIG. 15-A is shown in 15-B. Figure 15-B
As shown in FIG. 5, the sheet-like laminated structure is composed of a layer 94 made of a resin containing a colorant and a layer 96 made of a resin not containing the colorant, and a pattern 9 is formed at the interface between the two layers.
1 is formed.

Further, a light source section 92 is arranged at the side end portion of the sheet-like laminated structure. O shown in FIG. 15-A
The device A has a side surface composed of the sheet-like laminated structure, and the laminated structure is provided with a design so that light can be emitted from the light source section below. Thus, a container in which the design is three-dimensionally displayed is formed with high designability due to color change (gradation). The light from the light source unit may be continuously emitted or may be blinking. As described above, the sheet-shaped laminated structure of the present invention can have a semi-spherical shape, a semi-cylindrical shape or the like. Further, it may have a spherical shape in which hemispherical structures are superposed or a cylindrical shape in which semi-cylindrical shapes are superposed. In these forms, the thickness of the colored layer can be changed in various ways, but from the viewpoint of designability, a change with high symmetry is preferable. Therefore, in the case of a hemispherical shape, it is preferable that the thickness changes symmetrically with respect to the normal line passing through the center of the sphere among the normal lines of the surface formed from the end of the molded product.

Further, the above-mentioned form does not need to be a perfect hemispherical shape or the like, and may be a form in which a part is missing. For example, in the case of a hemispherical shape, a shape in which the shape projected in the normal direction is a double circle can be mentioned. In such a case, the side end of the molded product can be selected from the end face corresponding to the outer circle and the end face corresponding to the inner circle. Such a hemispherical laminated structure is particularly suitable for use in lighting gloves. Conventionally, it was either completely uniform illumination or non-uniform illumination with poor design, but by using the laminated structure of the present invention as an illumination glove, it is possible to provide illumination with a light distribution excellent in design. Becomes A further advantage is that when a slight amount of light is required such as at bedtime, a light source at the end of the side surface can be used to produce a comfortable light.

That is, according to the present invention, the sheet-like laminated structure has a hemispherical shape, and the light source section can be arranged inside the hemispherical shape, and A decorative lighting globe is provided in which two hemispherical structures are stacked to form a sphere and a light source can be placed inside the sphere. Further, similarly, there is provided a decorative lighting glove which is changed to the semi-spherical shape and is made into a semi-cylindrical shape, and a decorative lighting globe which is changed to a spherical shape and made into a cylindrical shape. Furthermore, it is preferable that these decorative lighting gloves have a three-dimensional pattern of characters or figures at the interface where the two layers come into contact with each other, and that a light source is separately installed at the side end portion thereof. . The light amount of the light source at the side end may have any relative intensity with respect to the light amount of the internal light source, but a more preferable embodiment is when the light amount of the light source at the side end is lower.

Such a concrete example is shown in FIGS. Such an illumination globe has a configuration in which two hemispheres (71 and 75) are combined to form a sphere.
In normal lighting, the internal light source (81) is turned on, and when slight brightness is required, the light source (8
Turn on 2). In the case of the internal light source (81), the pattern (73) formed by the three-dimensional pattern attached to the interface portion achieves excellent designability by producing a difference in shade, and the light source (8) at the side end portion
In the case of 2), the outline is slightly raised and the whole exhibits a fantastic light.

[0127]

The present invention will be further described with reference to the following examples. Molded product manufactured by the method shown below (structural laminate)
On the other hand, the design source emitted from the laminated structure was evaluated by shining light with the following light source and arrangement. (Light Source and Arrangement) (i) Backlight Method: As shown in FIG. 2, the following light source was installed on the back side of the laminated structure, and the design of the laminated structure was evaluated from the front side. (Light source a): When a 40 W white fluorescent lamp (rated 100 V) is installed on the back surface of the laminated structure (2 m thick on the fluorescent lamp).
m light diffusing plate was installed and observed with the laminated structure placed on the light diffusing plate for illuminating uniformly in the photographic light box) (Light source b): 100 W halogen lamp on the back surface of the laminated structure ( When rated 12V, total luminous flux 3,000lm is installed (distance between laminated structure and halogen lamp is about 5cm)
(Ii) Edge light method: As shown in FIG. 3 and FIG. 4, the following electric lights are installed on the side edge of the laminated structure (the side edge of the thick portion or the side edge of the thin portion) from the front side. The designability of the laminated structure was evaluated. (Light source c): a straight tube type cold cathode fluorescent lamp having a diameter of 2.5 mm and a length of 220 mm (NEC long-life type, central brightness 35, so as to be almost in contact with the side surface end of the B layer thick part of the laminated structure). 000 cd / m ² , lamp current 6 mA) (light source d): high brightness type white LEDs are arranged in a line at regular intervals so as to be almost in contact with the side edge of the thin layer B layer of the laminated structure. When installed by the above method (ii) -1. Thick part side end: When an electric lamp is installed at the B layer thick part side end of the laminated structure (ii) -2. Thin-walled portion side end: When an electric lamp is installed at the B-layer thin-walled portion side end of the laminated structure (1) Designability The overall designability of the laminated structure was visually evaluated from the surface side of the laminated structure. The evaluation was performed on the hue from the thick portion side to the thin portion side of the laminated structure layer (B) and the shade (gradation) thereof. (2) Designability The designability of the characters expressed inside the laminated structure was visually evaluated from the surface side of the laminated structure. The evaluation was performed based on the following criteria. (2) -1. Shape: (i) Planar: The characters expressed inside the laminated structure look planar. (Ii) Three-dimensional: The characters expressed inside the laminated structure look three-dimensional (that is, the characters are shaded and the characters appear to float inside the laminated structure). (2) -2. Decoration: (i) Emphasis: The characters expressed inside the laminated structure appear to be emphasized. (Ii) Color removal: The characters expressed inside the laminated structure appear to be colored. (Iii) Fantastic ... The characters expressed inside the laminated structure look illusionary due to the outline blurring in the diffused light. The thermoplastic resin composition used in the examples was prepared as follows. (I) <When part of the layer is composed of a material containing a dye>

Reference Examples 1 to 6 After dry-blending the components shown in Table 2 at the compositional proportions shown in Table 2 (units are parts by weight), a uniaxial shaft with a vent equipped with a Dalmage 2-stage screw having a diameter of 30 mmφ Using an extruder [VSK-30 manufactured by Nakatani Machinery Co., Ltd.], a strand was extruded under the conditions of a cylinder temperature and a die temperature of 290 ° C. and a vent suction degree of 3,000 Pa, cooled in a water bath, and then cut with a pelletizer. It was made into pellets. After drying the pellets with a hot air drier, the molding shown in the following examples was performed. However, with respect to the sample code "PMMA", the above-mentioned melt-kneading was not performed, and the raw material was directly subjected to drying and molding.

[0129]

[Table 2]

The symbols showing the components shown in the raw material name column of Table 2 are as follows. (Thermoplastic resin) PC : 99.77 parts by weight of a polycarbonate resin powder having a viscosity average molecular weight of 18,500 made from bisphenol A and phosgene by a conventional method, Sandstab P
A mixture of 0.03 parts by weight of EPQ (manufactured by Sandoz) and 0.2 parts by weight of pentaerythritol tetrastearate (these stabilizer release agents, and optionally the colorant are uniformly premixed and melted) Extruded to obtain pellets). For PC and the resin composition comprising PC, the drying conditions during molding were 120 ° C. for 5 hours, the cylinder temperature was 300 ° C., and the mold temperature was 100 ° C. PMMA : Polymethylmethacrylate resin (Delpet 80N manufactured by Asahi Kasei Corporation). Regarding the PMMA and the resin composition comprising PMMA, the drying conditions during molding were 100 ° C. for 5 hours, the cylinder temperature was 280 ° C., and the mold temperature was 80 ° C. PO : cyclic polyolefin resin (manufactured by Nippon Zeon Co., Ltd.)
Zeonex E48R). For PO and the resin composition composed of PO, the drying condition during molding is 120 ° C.
5 hours, cylinder temperature is 300 ℃, mold temperature is 10
It was set to 0 ° C. (Colorant) R: Perinone red dye (Pl manufactured by Arimoto Chemical Co., Ltd.)
ast Red 8315) Y: quinoline yellow dye (Pl manufactured by Arimoto Chemical Industry Co., Ltd.)
ast Yellow8050) G: Anthraquinone type green dye (Ori Green5602 manufactured by Arimoto Chemical Co., Ltd.) B: Anthraquinone type blue dye (manufactured by Bayer MAC)
ROLEX BlueRR) A molded product was prepared by the following method.

Example 1 The above-mentioned polycarbonate resin (PC (R)) and polycarbonate resin (PC) were each dried at 120 ° C. for 5 hours with a hot air dryer, and then a multi-injection device having two cylinder inner diameters of 50 mmφ was provided. Molding was performed using an injection molding machine capable of color molding (FN-8000-36ATN manufactured by Nissei Plastic Co., Ltd.). Using one of the two cylinders, a molded product for forming the layer (A) shown in FIG. 5 was used, the cylinder temperature was 300 ° C., the mold temperature was 100 ° C., and the injection speed was 150 m.
Molded at m / sec. The molded product forming the layer (A) has a thickness on the gate side of 4.2 mm and a thickness on the flow end side of 0.8 mm, and is a surface formed by a straight line connecting the both ends (layer (A) surface). It has a shape that draws a convex surface on. On the other hand, characters (TCL) are attached to the central part as a three-dimensional pattern, and the character part has a shape having a thickness of +1 mm convex with respect to the surface of the layer (A). After performing such molding, the plate on the core side of the molding machine was replaced to mold the layer (B). The layer (B) was molded by inserting the molded product forming the layer (A) into the mold (fixed side). The layer (B) is molded by using the remaining one of the two cylinders and injecting the resin forming the layer (B) at a cylinder temperature of 300 ° C., a mold temperature of 100 ° C., and an injection speed of 300 mm / sec. 6 and 9
An integrally molded product (laminated structure) shown in was obtained.

In forming the layer (B), after closing the mold, a vacuum pump (ULVAC PM manufactured by Nippon Vacuum Technology Co., Ltd.) was used.
(A combination of B006CM mechanical booster and EC803 rotary pump) was used, and after evacuation for 10 seconds, molding was performed. Exhaust was performed through a gas vent clearance provided around the mold cavity. In addition, the same main mold was used as the mold, and only the plate was replaced (one channel is omitted in FIGS. 7 and 8). Both the layer (A) and the layer (B) were formed by a hot runner (external heating method manufactured by Mold Masters) at a temperature of 310 ° C. The hot runner had a gate diameter of 3.5 mmφ.

Examples 2 to 4 As the materials shown in Table 3, molding was carried out in the same manner as in Example 1 except that the drying conditions, the cylinder temperature and the mold temperature were changed according to the material to be molded, and an integrally molded product was obtained. (Layered structure) was obtained.

[0134]

[Table 3]

As is apparent from Table 3, for example, in the case of Example 1, a color having a gradation from pale red to dark red from the molded product layer (B) thick part side to the layer (B) thin part side. At the same time, it is possible to obtain excellent designability in which the characters expressed inside the molded product are emphasized two-dimensionally with respect to the entire molded product. (II) <When part of the layer is composed of a material containing a fluorescent dye>

Reference Examples 1, 2, and 7 to 10 After dry-blending the components shown in Table 4 at the composition ratios shown in Table 4, a single-screw extruder with a vent having a diameter of 30 mmφ and two stages of Dalmage screw [ Nakatani Machine Co., Ltd.
Manufactured by VSK-30], the strands were extruded under the conditions of a cylinder temperature and a die temperature of 290 ° C., and a vent suction degree of 3,000 Pa, cooled in a water bath, and then cut with a pelletizer to form pellets. After drying the pellets with a hot air drier, the molding shown in the following examples was performed. However, the sample symbol "PMM
Regarding “A” and “PO”, the above-mentioned melt-kneading was not performed, and the raw materials were directly subjected to drying and molding.

[0137]

[Table 4]

The symbols showing the components shown in the raw material name column of Table 4 are as follows. (Colorant (fluorescent dye)) FR: Perylene fluorescent red dye (BASF LUM)
OGEN F Red300) FY: Perylene fluorescent red dye (BASF LUM)
OGEN F Yellow083 FO: Perylene fluorescent red dye (BASF LUM)
OGEN F Orange 240) A molded product was prepared by the method described below.

Examples 5 to 7 As a material shown in Table 5, molding was performed in the same manner as in Example 1 except that the drying conditions, the cylinder temperature and the mold temperature were changed according to the material to be molded, and an integrally molded product was obtained. (Layered structure) was obtained.

[0140]

[Table 5]

As is clear from Table 5, in the case of Example 7, for example, a gradation from a light fluorescent red to a dark fluorescent red from the thick part side of the molded article layer (B) to the thin part side of the layer (B). The color it has is obtained. Further, when a white fluorescent lamp (light source a) is applied from the back side of the molded product, excellent designability is obtained in which the characters expressed inside the molded product are emphasized in a plane with respect to the entire molded product. Further, when a cold cathode fluorescent lamp (light source c) is applied from the end face of the thick part of the layer (B) of the molded product, the characters expressed inside the molded product emit light and a shadow is provided. Thereby, excellent designability in which characters are three-dimensionally emphasized can be obtained for the entire molded product. (III) <When part of the layer is made of a material having high light reflectivity>

Reference Examples 3, 4, 11 and 12 After dry-blending the components shown in Table 6 in the composition ratios shown in Table 5, a vented single-screw extruder equipped with a Dalmage 2-stage screw having a diameter of 30 mmφ [ Nakatani Machine Co., Ltd.
Manufactured by VSK-30], the strands were extruded under the conditions of a cylinder temperature and a die temperature of 290 ° C., and a vent suction degree of 3,000 Pa, cooled in a water bath, and then cut with a pelletizer to form pellets. After drying the pellets with a hot air drier, the molding shown in the following examples was performed.

[0143]

[Table 6]

The symbols showing the components shown in the raw material name column of Table 6 are as follows. (Light-reflecting agent) Ti: Titanium oxide (PC-3 manufactured by Ishihara Sangyo Co., Ltd.) A molded product was prepared by the method described below.

Examples 8 to 10 [0145] Molding was carried out in the same manner as in Example 1 except that the materials shown in Table 7 were used, and the drying conditions, cylinder temperature, and mold temperature were changed according to the material to be molded, and an integrally molded product was obtained. (Layered structure) was obtained.

[0146]

[Table 7]

As is clear from Table 7, for example, in the case of Example 8, when the cold cathode fluorescent lamp (light source c) is applied from the end face of the thick part of the layer (B) of the molded product, it is expressed inside the molded product. In the character portion, the reflection of light different from other portions occurs. Thereby, excellent designability in which characters are three-dimensionally emphasized can be obtained for the entire molded product. (IV) <When a part of the layer is composed of a material having light diffusivity>

Reference Examples 3, 10, and 13 to 15 After dry-blending the components shown in Table 8 at the composition ratios shown in Table 8, a vented single-screw extruder equipped with a Dalmage 2-stage screw having a diameter of 30 mmφ [ Nakatani Machine Co., Ltd.
Manufactured by VSK-30], the strands were extruded under the conditions of a cylinder temperature and a die temperature of 290 ° C., and a vent suction degree of 3,000 Pa, cooled in a water bath, and then cut with a pelletizer to form pellets. After drying the pellets with a hot air drier, the molding shown in the following examples was performed.

[0149]

[Table 8]

The symbols showing the components shown in the raw material name column of Table 8 are as follows. (Light diffusing agent) S: Silicon-based crosslinked particles (TOE Pearl 120 manufactured by GE Toshiba Silicone Co., Ltd.) A: Acrylic crosslinked particles (Techpolymer MBX-5 manufactured by Sekisui Plastics Co., Ltd.) M: Inorganic fine particles (Nitto) Spinning Co., Ltd. glass fiber PF
E-301S) A molded product was prepared by the method described below.

Examples 11 to 14 As the materials shown in Table 9, molding was carried out in the same manner as in Example 1 except that the drying conditions, the cylinder temperature and the mold temperature were changed according to the material to be molded, and an integrally molded product was obtained. (Layered structure) was obtained.

[0152]

[Table 9]

As is clear from Table 9, in the case of Example 11, for example, when a halogen lamp (light source b) was applied, the molded product layer (B) was moved from the thick part side to the layer (B) thin part side. A color having a gradation from red to orange to yellow is obtained. Further, excellent characters can be obtained in which the characters expressed inside the molded product are planarly colored with respect to the entire molded product. When a high-intensity type white LED (light source d) is applied from the end face of the thick part of the layer (B) of the molded product, the character outline expressed in the molded product is slightly dusty in the diffused light. It is observed in the state. Further, since the characters are in a color-depleted state, excellent designability that gives a fantastic feeling can be obtained.

Further, as seen in Example 14, a white LED of a high brightness type is obtained from the end surface of the molded product on the side of the thin portion (B) (the end surface on the side of the thick portion of the layer (A) made of a light diffusing material).
When the (light source d) is applied, the surface shines in uniform shades of color. That is, when a part of the layer is composed of the light diffusing material, completely different design properties can be obtained in the direction of shining light.

Reference Examples 16 to 22 Each component shown in Table 10 was dry blended in a composition ratio (unit is parts by weight) shown in Table 10 with a tumbler, and then diameter 30 mmφ, L / D = 33.2, kneading zone. Using a twin-screw extruder with vents equipped with two screws (KTX30, manufactured by Kobe Steel, Ltd.), cylinder temperature and die temperature 290 ° C, and vent suction degree 3,000P
The strand was extruded under the condition a, cooled in a water bath, and then strand-cut with a pelletizer to pelletize.
After drying the pellets with a hot air drier, the molding shown in the following examples was performed. In the dry blending, less than 1 part by weight of the additive is used in the release agent with respect to 100 parts by weight of the PC (polycarbonate resin).
The fluorescent dye, the ordinary dye, the light diffusing agent, and the ultraviolet absorber were mixed in a weight ratio of 1% by weight with a master agent uniformly mixed with PC in a super mixer. Furthermore, for additives less than 0.01 parts by weight per 100 parts by weight of PC, 1% by weight of the master agent was used as a further 1% by weight of the master agent.

[0156]

[Table 10]

The symbols showing the components shown in the raw material name column of Table 10 are as follows. (Thermoplastic resin) PC: Polycarbonate resin powder having a viscosity average molecular weight of 19,700 (Panlite L-12 manufactured by Teijin Chemicals Ltd.)
25WX) (Phosphorus stabilizer) PQ: Tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene-diphosphonite as a main component stabilizer (Clariant Japan KK Sandstub P-EPQ) PLUS) M: Trimethyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd.)
TMP) IR: Tris (2,4-di-tert-butylphenyl) phosphite (Irg, manufactured by Nippon Ciba-Geigy Co., Ltd.)
afos168) (Release agent) SA: Monoester of stearic acid and glycerin (Rikemar S-100A manufactured by Riken Vitamin Co., Ltd.) SL: Saturated fatty acid triester of glycerin, and mixture of ester of higher alcohol and saturated fatty acid (RIKEN) Vitamin Co., Ltd. Rikemar SL900) PT: Pentaerythritol tetrastearate (fluorescent dye) FR: Perylene red fluorescent dye (BASF Lumo)
gen F Red 300) FO: Perylene-based orange fluorescent dye (BASF Lumo)
gen F Orange240) HP: Coumarin-based optical brightener (Hakkor PSR manufactured by Hakkor Chemical Co., Ltd.) (dye) B: Anthraquinone-based blue dye (Bayer MAC)
ROLEX BlueRR) Y: quinoline yellow dye (Pl manufactured by Arimoto Chemical Industry Co., Ltd.)
as Yellow 8050) (light diffusing agent) A: Acrylic cross-linked particles (Techpolymer MBX-5 manufactured by Sekisui Plastics Co., Ltd.) S: Silicon cross-linked particles (Tospearl 120 manufactured by GE Toshiba Silicones Co., Ltd.) (UV absorber) ) TN: Triazine-based ultraviolet absorber (2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-
[(Hexyl) oxy] -phenol, TINUVIN1577 manufactured by Ciba-Geigy Co., Ltd. CS: Benzotriazole-based UV absorber (2- (2 ′)
-Hydroxy-5'-t-octylphenyl) benzotriazole, Chemisorb 79)

Example 15 (Preparation of windows for automobiles) Polycarbonate resin of Reference Examples 16 and 17 (PC
(A)) and a polycarbonate resin (PC (B)) are dried at 120 ° C. for 5 hours by a hot air dryer, respectively, and then an injection molding machine capable of multicolor molding equipped with two injection devices each having a cylinder inner diameter of 50 mmφ (Nissei Resin Industrial Co., Ltd. FN-800
0-36 ATN) was used to mold a model molded article assuming a rear window of an automobile shown in FIG. FIG. 11 shows a schematic diagram of the state of being attached to a car. As shown in FIG. 12, the model molded article was molded by a two-color molding method using a slide-type mold, and a molding method of performing injection press molding in molding the second layer. In addition, the molding is performed by primary injection (first layer: PC (B)) and secondary injection (2
Layer: PC (A)) uses a valve gate type hot runner, and the temperature of the hot runner is 310 ° C.

The main shape of the molded product is as follows. The upper edge has a lateral length of about 250 mm and the upper edge has a curvature of about R.
1,880 mm, the lateral length of the lower edge is about 300 mm, the curvature of the lower edge is about R2,050 mm, and the length in the height direction is about 210 mm. The thickness of the first layer was 5.9 mm on the gate side and 0.5 mm on the flow end side, and the second layer was 5.9 mm on the gate side (flow end side of the first layer) and 0.5 mm on the flow end side. is there. The thickness of the entire molded product is 6.4 mm, which is a uniform thickness. The gate has a width of about 200 mm and a thickness of 2.0 mm for both the first and second layers.
It is a film gate of. The change in thickness is made up of a surface formed by a straight line connecting both ends, and a three-dimensional pattern is given by making the thickness of the layer composed of PC (B) from the surface to be +1 mm convex.

The molding procedure was as follows. First, as shown in FIG. 12-A, the PC is used in the primary injection process.
(B), cylinder temperature 300 ℃, mold temperature 100
It was molded at a temperature of 50 ° C. and an injection speed of 50 mm / sec. Holding pressure is 30
Molding was performed at MPa and cooling for 30 seconds. The primary injection process is
The pellets of PC (B) dried with hot air at 120 ° C. for 5 hours are supplied to the hopper (43) of the primary injection unit (42),
Resin (4) melted and plasticized by the screw (44)
The mold cavity (55) for primary injection was filled with 1) by the forward movement operation (45) of the screw. The valve on the primary injection side of the hot runner (40) was closed after the pressure holding process.
In the secondary injection unit, the pellets of PC (A) dried with hot air at 120 ° C. for 5 hours were supplied to the hopper (46) of the secondary injection unit (48) and the screw (4
It is in a state of being melted and plasticized by 7).

Next, as shown in FIG. 12-B, after cooling the resin inside the mold cavity, the mold is retracted (56).
Then, a molded product (57) of the first layer was obtained while being left on the mold fixing side. After the start of cooling, the resin was measured for the next molding. Next, as shown in FIG. 12-C, the mold was slid upward (58), and the mold cavity was changed from the one for primary injection to the one for secondary injection. Then [12-
As shown in D], the mold was closed (59) to obtain a resin filling space including a mold cavity for secondary injection and a molded product of the first layer. Here, the core plate (51) was opened by 2 mm more than the predetermined thickness of the molded product. Then, as shown in FIG. 12-E, in the secondary injection step, the screw (47) is moved forward (61), the PC (A) is moved to a cylinder temperature of 300 ° C., a mold temperature of 100 ° C., and an injection speed of 5%.
It was filled at 0 mm / sec. The filling time was about 3.5 seconds. As shown in the figure, the filling of the resin (PC (A)) (60) is insufficient with respect to the mold cavity capacity.

As shown in FIG. 12-F, the core plate (51) was advanced to press the resin (62) in the mold cavity. The advance of the core plate starts 0.5 seconds before the end of the filling (that is, the overlap time is 0.5 seconds), and the moving speed of the core plate is 1 mm / se.
c, pressing was performed at a pressing pressure of 20 MPa. The breathing was performed for about 37 seconds from the start of pressing. Then, the pressure of the press was set to 0 MPa, cooling was performed for 45 seconds, and after cooling, the molded product was taken out. (Ii) Surface Coat Treatment Further, the obtained laminated structure was subjected to a hard coat treatment on the surface side corresponding to the vehicle outer side (the side of the layer made of injection-press-molded PC (A)) by the following procedure. That is, the coating composition (i-1) shown below was applied to one surface of the laminated structure by a flow coater, left standing at 25 ° C. for 20 minutes, and then 12
It heat-cured at 0 degreeC for 30 minutes, and formed the 1st layer. Then, the coating composition (ii-1) shown below was further applied with a flow coater and allowed to stand at 25 ° C. for 20 minutes, and then 1
The second layer was formed by heat curing at 20 ° C. for 2 hours. The film thickness of the first layer was about 2 μm, and the film thickness of the second layer was about 5 μm. The obtained laminated structure was a molded product having no distortion and having a good coating, and could be sufficiently put into practical use when placed in an automobile as shown in FIG. Further, this laminated structure has a peculiar design property as an automobile glass window having a gradation color tone. Further, such a laminated body has a function of stereoscopically displaying the characters in the central portion by shining light from the side surface on the lower side (the side where the thickness of the PC (B) is thicker), and has a peculiar design property that has never been seen before. It was a highly valuable glass window for automobiles.

Coating Composition (i-1) Methyl methacrylate (hereinafter abbreviated as MMA ) was placed in a flask equipped with a reflux condenser and a stirrer and purged with nitrogen.
70 parts, 2-hydroxyethyl methacrylate (hereinafter H
EMA) 39 parts, azobisisobutyronitrile (hereinafter abbreviated as AIBN) 0.18 parts and 1,2
-200 parts of dimethoxyethane was added and mixed and dissolved. Then, the mixture was reacted in a nitrogen stream at 70 ° C. for 6 hours with stirring. The obtained reaction solution was added to n-hexane for reprecipitation purification, and the composition ratio of MMA / HEMA was 70/30 (molar ratio).
90 parts of a copolymer of (acrylic resin (I)) was obtained. The weight average molecular weight of the copolymer was measured by GPC (column;
From Shodex GPCA-804, eluent: THF), it was 80,000 in terms of polystyrene.

In addition, methyltrimethoxysilane 142
Parts, 72 parts of distilled water, 20 parts of acetic acid are mixed with ice water while cooling,
This mixed solution was stirred at 25 ° C. for 1 hour and diluted with 116 parts of isopropanol to obtain 350 parts of a methyltrimethoxysilane hydrolysis-condensation solution (X). On the other hand, 208 parts of tetraethoxysilane and 81 parts of 0.01N hydrochloric acid were mixed under cooling with ice water, and this mixed solution was stirred at 25 ° C. for 3 hours and diluted with 11 parts of isopropanol to obtain a tetraethoxysilane hydrolysis condensate solution ( Y) 300 parts were obtained. Next, as a composition for the first layer of hard coat, a mixture of 8 parts of the acrylic resin (I), 40 parts of methyl ethyl ketone, 20 parts of methyl isobutyl ketone, 5.2 parts of ethanol, 14 parts of isopropanol and 10 parts of 2-ethoxyethanol. Dissolve in a solvent, and then add 10 parts of methyltrimethoxysilane hydrolysis-condensation solution (X) to this solution, and add 5 parts at 25 ° C.
After stirring for 1 minute, 1 part of melamine resin (Cymel 303 manufactured by Mitsui Cytec Co., Ltd.) was added to the solution to give 25
The mixture was stirred at 0 ° C for 5 minutes to prepare a coating composition (i-1).

Coating composition (ii-1) Further, as a composition for the second layer of the hard coat, 100 parts of a water-dispersed colloidal silica dispersion (manufactured by Nissan Chemical Industries, Ltd., Snowtex 30, solid content concentration: 30% by weight). Distilled water (12 parts) and acetic acid (20 parts) were added and stirred, and to this dispersion was added methyltrimethoxysilane (134 parts) while cooling with an ice-water bath. The mixture solution was stirred at 25 ° C. for 1 hour, and the obtained reaction solution was added with tetraethoxysilane hydrolysis-condensation solution (Y).
20 parts and 1 part of sodium acetate as a curing catalyst were added and diluted with 200 parts of isopropanol to prepare a coating composition (ii-1).

Example 16 (Production of Lighting Globe) A spherical lighting globe (bulb cover molded product) obtained by combining the hemispherical laminated structures shown in FIG. 13 and FIG. Molded at molding temperature and injection speed. As shown in the schematic cross-sectional view of FIG. 14, in such a molded article, the upper surface layer is composed of PC (D) having a light diffusing property, and the upper back layer is composed of PC (C). The molded product has a diameter of about 10 cm and a thickness of 6 mm. P
After molding the portion composed of C (D) first, the molded product was insert-molded to form a laminated structure. Injection press molding was performed in insert molding. The obtained laminated structure was used as a cover for a light bulb as shown in FIG. 13, and had an atmosphere with a gentle color change.

Example 17 (Creation of Dome Type Fluorescent Lamp Cover) A hemispherical dome type fluorescent lamp cover was molded by the same molding machine and substantially the same molding temperature and injection speed as in Example 1.
Such a molded product is a PC (C) whose surface layer is almost transparent.
And the back layer is composed of PC (D). Diameter is about 200 mm, height is about 50 mm, thickness is 6 m
It consists of m. In this molded product, after the part composed of PC (D) is molded first (2 points of side gate from the outer periphery), insert molding is performed (1 point of direct gate from the back of the tower top) to form a laminated structure. did. Injection press molding was performed in insert molding. This laminate was configured such that the PC (C) layer was thick at the dome-shaped top portion and the PC (D) layer was thick at the dome-shaped peripheral portion. The obtained laminated structure was used as a cover for a fluorescent lamp and had a good design with a change in brightness.

Example 18 (Preparation of Light Bulb Cover) A hemispherical laminated structure was obtained in the same manner as in Example 17, and then cut in half along the axis of symmetry to prepare a bulb cover. Further, a light source formed by arranging white LEDs was installed at the end portion of the cut side surface. The molded product is composed of PC (F) with a light diffusing agent in the surface layer and PC in the back layer.
(E), and both layers had a change in thickness. The obtained laminated structure emits a gentle light because the portion near the light source has low transparency, and the entire cover emits an appropriate light by the LED light source provided at the end of the cut side surface. This moderate light was suitable for sleeping, etc., and the color tone with gradation produced comfort.

Example 19 (Preparation of Box-shaped Container) Four flat plate-like laminated structures were pasted together to form FIG.
A box-shaped container having a gradation color tone shown in was prepared. The flat laminated structure used was molded using the same molding machine and substantially the same molding temperature and injection speed as in Example 1.
Such a plate-shaped laminated structure has a fluorescent dye-containing PC (B) and PC as shown in the schematic cross-sectional view of FIG. 15-B.
It is composed of a back layer portion composed of (G) and a surface layer portion composed of PC (C). The flat laminated structure has a height and a width of 150 mm, and a thickness of 5 mm.
The thickness of each layer is 4 mm on the gate side and 1 mm on the flow end side. Each gate was a film gate having a thickness of 1 mm. The change in thickness consists of a plane consisting of a straight line connecting both ends. From such a plane, PC (B) and PC
A three-dimensional pattern is provided by making the layer formed by (G) have a convex thickness of +1 mm. First layer (PC
(B) and PC (G) are separately molded, and then the molded product is inserted into the second layer (PC (C)).
Was formed by injection press molding. After laminating the four plate-shaped laminated structures, as shown in FIG. 15-B, a light source unit in which white LEDs are arranged is installed on the side surface on the lower side (the side where the layer made of PC (C) has a large thickness). Then, a box-shaped laminated structure was obtained. A design was achieved in which a three-dimensional pattern provided by such a light source emerges as a three-dimensional pattern. FIG. 15-A shows that it is possible to insert a CD reproducing device into such a box-shaped laminated structure to produce a CD reproducing device having a high design. It is possible to achieve high designability by changing the intensity and color of the light source according to the change of the audio information.

Example 20 (Preparation of Water Tank) A water tank of high design was prepared in which the plate-shaped laminated structure was formed as one of four side surfaces. In the plate-shaped laminated structure, a layer made of PC (E) was separately molded as the first layer, and in a state where this was inserted, a layer made of PC (F) was molded as the second layer by injection press molding. The three-dimensional pattern of the pattern is given by making the thickness of the layer composed of PC (E) convex by +1 mm in the same manner as in Example 19. Further, a light source section in which white LEDs are arranged is installed on the side surface on the upper side (the side where the layer made of PC (F) has a large thickness), and almost the entire surface shines uniformly in blue. The aquarium having such a laminated structure on the inner side of the inner surface had its ornamental power further enhanced.

Example 21 (Preparation of Ruler) A ruler composed of a laminated structure was prepared. PC on the top side
It is composed of a layer of (C), the lower side is composed of a layer of PC (E), a pattern with a convex three-dimensional pattern is attached to the lower side, and molding is performed first, and then it is inserted into a mold. It was molded by injection press molding. The obtained ruler has a thickness change of two layers, a change in color tone and a pattern,
It had a high design quality.

[0172]

EFFECTS OF THE INVENTION According to the present invention, there is provided a laminated structure having a high degree of freedom and continuous color tone change (gradation color) and capable of three-dimensionally adding characters, pictures and patterns capable of various internal expressions. it can. Since the sheet-like laminated structure of the present invention is excellent in the characteristics of the change in color tone and the three-dimensional expression of characters and figures, various uses can be expected. For example, in addition to automobile windows, showcases, lighting fixtures, box-shaped containers, illuminated panels (vending machines, game machines such as slot machines, and signboards), vehicle windshields, helmets and their windshields, glasses, protection It can also be used as a shield, furniture, sundries (stationery, tableware, cleaning supplies, cooking utensils, accessory cases, toys, etc.).

[Brief description of drawings]

FIG. 1 is a schematic view showing a shape of a right-angled cross section of a sheet surface of an example of a sheet-shaped laminated structure of the present invention.

FIG. 2 is a side view showing a schematic diagram when a light source (L) is arranged on the back surface of the laminated structure of the present invention by a backlight method and the designability thereof is observed.

FIG. 3 is a side view showing a schematic diagram when a light source (L) is arranged on the end face of the layer (B) of the laminated structure of the present invention on the side of the thick portion by the edge light method and the design is observed.

FIG. 4 is a side view showing a schematic view when arranging a light source (L) on an end surface of a layer (B) of a laminated structure of the present invention on the side of a thin portion by an edge light method and observing its design.

FIG. 5 is a layer (A) of a laminated structure used in Examples.
It is a perspective view which represents typically the outline of the molded product shape which forms.

FIG. 6 is a side view schematically showing an outline of a laminated structure used in Examples.

FIG. 7 is a side view showing a schematic view of a molding die when the layer (A) is molded. Regarding the hot runner flow path of the fixed mold, the one for the layer (B) is omitted.

FIG. 8 is a side view showing a schematic view of a molding die when a layer (A) molded article is inserted and the layer (B) is molded. Regarding the hot runner channel of the stationary die, the one for the layer (A) is omitted.

FIG. 9 is a front view schematically showing the outline of a laminated structure used in Examples. FIG. 9 shows a mode in which the color tone changes from dark to light from the lower part to the upper part of the figure, but this change is omitted in the drawing.

FIG. 10-A is a perspective view schematically showing an example of an automobile glass window created in the example. 10-B: It is a figure which shows the cross section of this glass window typically. The dark part is made of PC (B), the white part is made of PC
(A).

FIG. 11 is a perspective view schematically showing a state in which the automobile glass window created in the example is used as a back window of an automobile.

FIG. 12 shows a two-color molding and injection press molding process for making an automobile glass window. 12-A: shows the step of primary injection. P in the primary injection process
C (B) is filled in the mold. 12-B: A step of opening the mold after cooling the molded product made of PC (B). 12-C: Shows a step of replacing the mold cavity by sliding the mold. 12-D: Shows the step of closing the mold in the state of 12-C. The core plate is retracted, and the mold is closed with the capacity of the mold cavity being larger than the molding capacity of the second layer. 12-E: shows a secondary injection step, and a predetermined amount of resin (PC (A)) is filled in the mold cavity in the state of 12-D. 12-F: a step in which the core plate is moved forward by the movement of the core plate cylinder into the mold cavity to compress the resin to a predetermined amount. Note that the compression is started before the filling of the resin (PC (A)) is completed.

FIG. 13 is a front view schematically showing a spherical lighting globe created in an example.

14-A: A diagram schematically showing a cross section of an upper hemispherical portion of the lighting globe of FIG. 13. The dark part is a PC
(D) and the white portion is PC (C). 14-B: It is the figure which showed typically the cross section of the lower hemisphere part of the globe for illumination of FIG. The dark portion is composed of PC (D), and the white portion is composed of PC (C).

FIG. 15-A is a perspective view schematically showing a box-shaped container created in Example. 15-B: A diagram schematically showing a cross section in the vertical length direction of a plate-shaped laminated structure that constitutes the box-shaped container. The dark part is composed of PC (B) and PC (G), and the white part is P (P)
It is composed of C (C).

[Explanation of symbols]

1 Laminated structure body 2 Laminated structure layer (A) 3 Laminated structure layer (B) 4 Three-dimensional pattern of the pattern in the laminated structure layer (A) (thickness of such part is +1 mm with respect to the layer (A) face) X observation direction (arrow) L light source 5 vertical length of laminated structure body 6 thickness of laminated structure body 7 thickness of laminated structure body layer (B) at gate portion 8 laminated structure Lower end (flow end) of body layer (A)
In thickness 9 Length of the three-dimensional pattern portion of the design 10 Thickness of the three-dimensional pattern portion of the design (+1 mm with respect to the layer (A) surface) 11 Both the layer (A) and the layer (B) of the laminated structure have the same thickness. Position of the portion having the same thickness 12 Thickness of layer (A) in the above 11 13 Fixed side mold 14 Layer (A) core side mold 15 Layer (A) hot runner tip valve 16 Layer (A) hot Runner channel 17 Layer (A) cylinder 18 Layer (A) resin flow 19 Movable mold 20 Layer (B) hot runner tip valve 21 Layer (B) hot runner channel 22 Layer (B) Cylinder 23 Flow of resin for layer (B) 24 Core-side mold for layer (B) 30 Glass window body for automobile 31 Three-dimensional pattern provided on glass window body (convex in colored layer (34)) 32 Side of glass window body Light source unit 33 installed on the surface of the glass window layer forming the front side of the glass window (outside of the automobile) (there is a hard coat treatment on the surface) 34 Layer of colored resin forming the back side of the glass window (inside of the automobile) 35 Inside the light source unit LED 40 Hot-runner unit for molding (valve gate type) 41 Resin (PC (B)) filled in the mold cavity in the primary injection process 42 Primary injection unit (injection unit for the primary injection process ) 43 hopper of primary injection unit 44 screw of primary injection unit 45 arrow indicating forward movement of screw of primary injection unit 46 hopper of secondary injection unit 47 screw of secondary injection unit 48 secondary injection unit (secondary injection unit (Injection unit for injection process) 49 Resin (PC (A)) filled in the mold cavity in the secondary injection process 50 Mold Cavity for Secondary Injection Process 51 Core Plate 52 for Compression Operation of Injection Press Molding Hydraulic Cylinder 53 for Moving Entire Die Hydraulic Cylinder 54 for Moving Core Plate 2 Color with Slide Mechanism Molding die 55 A mold cavity for the primary injection process (see [12-
In [A], a state in which the resin PC (B) is filled in the cavity is shown. 56 An arrow 57 showing the operation of retracting the mold (the mold is opened) 57 A molded product obtained in the molding of the first layer 58 A mold The arrow 59 indicating the movement of the mold upwards The arrow indicating the movement of the mold forward (the mold is closed) 60 The resin (PC (A)) 61 2 filled in the mold cavity for the secondary injection process 61 2 An arrow 62 indicating the movement of the cylinder in the next injection step. In the molding of the second layer, the core plate (51) moves forward while pressing the resin in the cavity by the movement of the cylinder (53) to reach a predetermined thickness. The arrow 70 indicates an illumination glove main body 71 an illumination glove upper hemisphere 72 a broken line representing the inner wall surface of the molded product 73 a three-dimensional pattern 74 attached to the laminated body interface portion of the upper glove hemisphere Fitting part between the upper and lower hemispheres of the bulb 75 Lower globe hemisphere for illumination 76 Ribs for installing a light source for illumination 77 Layer on the front side of the upper hemisphere for illumination 78 Layer on the rear side of the upper hemisphere for illumination 79 Layer on the front side of the lower hemisphere of the illumination globe 80 Layer on the back side of the lower hemisphere of the illumination globe 81 Light bulb 82 for illumination LED 83 installed at the side end of the molded product 90 Frame for holding the LED (82) 90 Box-shaped laminated structure body 91 Three-dimensional pattern attached to the interface portion of the laminated structure 92 Light source unit 93 installed at the side end of the molded product Electronic equipment enclosed in a box-shaped container (internal optical recording medium Can be seen through from the front) 94 Layers on the back side of the laminated structure (PC (B) and PC
(Layer consisting of (G)) 95 Arrow indicating the observation direction of the molded product 96 Layer on the surface side of the laminated structure (layer consisting of PC (C)) 97 White LED installed on the side end of the molded product

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) F21S 2/00 F21V 3/04 G F21V 3/04 G09F 7/16 Z G09F 7/16 13/18 N 13 / 18 13/20 D 13/20 21/04 Q 21/04 F21Y 101: 00 // F21Y 101: 00 101: 02 101: 02 F21S 1/00 F (72) Inventor Ikko Furukawa Uchisaiwaicho, Chiyoda-ku, Tokyo 1-2-2 Teijin Kasei Co., Ltd. F-term (reference) 3E067 AA11 AB31 AB60 AB61 AB62 AB91 AC01 AC03 BA05A BB14A BB25A CA11 EE09 FA01 FC01 GD09 3E086 AB01 AD02 BA04 BA15 BA35 BB22 BB61 BB63 CA33 LB0309A05 ALB01 LC01 LC03 LC05 LC06 LC07 LD01 LD06 LD09 LE01 LE11 LE16 LE17 MD06 MD07 4F100 AK01A AK01C AK01D AK25A AK25B AK25C AK25D AK43A AK43B AK43C AK43D AK45A BA80A80A80B80A80A80A80A80A80A80A80AAK80D BA10C BA10D BA41A BA41B CA13B CA13C CA30B DD40B EH36 EH36A EH36B EH36C EH36D GB07 GB16 GB32 GB90 HB00 JA12A JA12B JA12C JA12D JL10 JN01A JN01C JN01 CD36 CD02 CA03 CD02 CA03 CD02 CA03 CD02 CA03 CD02 CA02 CA02 CA02 CA02 CD02 CA02 CA03 FA02

Claims (41)

[Claims] 1. A sheet-like laminated structure comprising (1) at least two types of layers formed of a thermoplastic resin, and (2) an outer layer on at least one surface of the laminated structure, A layer (B) formed of a transparent resin,
(3) At least one layer constituting the laminated structure is
A dye, a pigment, or a light diffusing agent, and having a monotonic thickness change in at least one direction of the sheet surface of the laminated structure, and (4) the laminated structure is formed of a transparent resin. A highly designable sheet-like laminated structure, wherein continuous color tone changes are observed along the sheet surface when visually observed from the outer surface of the layer (B). 2. The sheet-like laminated structure according to claim 1, wherein characters or figures having a three-dimensional pattern are formed at an interface where the two kinds of layers are in contact with each other. 3. The average thickness is 1 to 50 mm.
The sheet-shaped laminated structure described. 4. The laminated structure, wherein one layer is formed of a transparent resin containing a dye or a pigment and has a monotonous thickness change in at least one direction of a sheet surface,
The sheet-like laminated structure according to claim 1, wherein the other layer is formed of a substantially colorless transparent resin. 5. The laminated structure, wherein one layer is formed of a transparent resin containing a fluorescent dye and has a monotonous change in thickness in at least one direction of the sheet surface, and the other layer is The sheet-shaped laminated structure according to claim 1, which is formed of a substantially colorless transparent resin. 6. The laminated structure, wherein one layer is formed of a transparent resin containing a dye or a pigment and has a monotonous change in thickness in at least one direction of the sheet surface, and the other layer. 2. The sheet-like laminated structure according to claim 1, wherein is formed of a transparent resin containing a dye or a pigment having a color different from that of the layer. 7. The laminated structure, wherein one layer is formed of a transparent resin containing a fluorescent dye and has a monotonous thickness change in at least one direction of a sheet surface, and the other layer is The sheet-shaped laminated structure according to claim 1, which is formed of a transparent resin containing a dye or a pigment having a color different from that of the layer. 8. The laminated structure, wherein one layer is formed of a transparent resin containing a dye or a pigment and has a monotonous change in thickness in at least one direction of the sheet surface, and the other layer. The sheet-shaped laminated structure according to claim 1, wherein the sheet-shaped laminated structure is formed of a transparent resin containing a light diffusing agent. 9. The laminated structure, wherein one layer is formed of a transparent resin containing a dye or a pigment and has a monotonous change in thickness in at least one direction of the sheet surface, and the other layer. 2. The sheet-shaped laminated structure according to claim 1, wherein the sheet-shaped laminated structure is formed of a transparent resin containing a high-reflecting agent. 10. The sheet-like laminated structure according to claim 1, wherein the transparent resin is a polycarbonate resin, a polyalkylmethacrylate resin, a cyclic polyolefin resin or an amorphous polyarylate resin. 11. The sheet-shaped laminated structure according to claim 1, wherein the transparent resin is a polycarbonate resin. 12. All the constructed layers are formed from the same type of resin and the resin is selected from the group consisting of polycarbonate resin, polyalkylmethacrylate resin, cyclic polyolefin resin or amorphous polyarylate resin. The sheet-shaped laminated structure described. 13. The sheet-like laminated structure according to claim 1, wherein all the constituted layers are formed of a polycarbonate resin. 14. The sheet-like laminated structure according to claim 1, wherein at least one layer is formed by injection molding. 15. The sheet-like laminated structure according to claim 1, wherein all layers are formed by injection molding. 16. The sheet-shaped laminated structure according to claim 1, which has a flat plate shape. 17. The sheet-like laminated structure according to claim 1, which has a semi-spherical shape. 18. The sheet-like laminated structure according to claim 1, which has a semi-cylindrical shape. 19. A decorative organic glass or glass window comprising the sheet-like laminated structure according to claim 1. 20. The decorative organic glass or glass window according to claim 19, wherein the sheet-like laminated structure is provided with characters or figures in a three-dimensional pattern at an interface where two kinds of layers are in contact with each other. 21. A sheet having a high design property, comprising the sheet-like laminated structure according to claim 1 and a light source section, and the light source section is arranged at a side end portion of the laminated structure. Laminated structure. 22. A side end of the sheet-like laminated structure on which the light source part is arranged contains a dye, a pigment or a light diffusing agent along a direction from the side end to the other side corresponding to the side end. The highly designable sheet-like laminated structure according to claim 21, which is an end portion where a layer having a monotonous change in thickness is formed. 23. The highly designable sheet-like laminated structure according to claim 21, wherein the sheet-like laminated structure is provided with characters or figures in a three-dimensional pattern at an interface where two kinds of layers are in contact with each other. 24. A decorative organic glass window comprising the sheet-like laminated structure according to claim 21, 22 or 23. 25. The sheet-shaped laminated structure, wherein one layer is formed of a transparent resin containing a fluorescent dye and has a monotonous thickness change in at least one direction of the sheet surface, and the other layer. The decorative organic glass or glass window according to claim 24, wherein the decorative organic glass or glass window is formed of a substantially colorless transparent resin. 26. A highly-designed automobile window comprising the sheet-like laminated structure according to claim 1. 27. The automobile window according to claim 26, wherein the window is a front door window, a rear door window, a back window, a quarter window or a sunroof window. 28. The automobile window according to claim 26, wherein the sheet-shaped laminated structure is provided with characters or figures in a three-dimensional pattern at an interface where two kinds of layers are in contact with each other. 29. The automobile window according to claim 26, wherein the sheet-like laminated structure has a light source portion arranged at an end portion of a side surface thereof. 30. A highly-designable box-shaped container having at least one surface formed of the sheet-like laminated structure according to claim 1. 31. The box-shaped container according to claim 30, wherein at least the surface of the visible portion is formed of the sheet-shaped laminated structure according to claim 1. 32. The box-shaped container according to claim 30, wherein the sheet-shaped laminated structure is provided with characters or figures in a three-dimensional pattern at an interface where two kinds of layers contact each other. 33. The box-shaped container according to claim 30, wherein the sheet-like laminated structure has a light source section arranged at an end portion of a side surface thereof. 34. A highly-designable electric device contained in the box-shaped container according to claim 30. 35. A highly-designable electronic device contained in the box-shaped container according to claim 30. 36. A highly-designable optical device contained in the box-shaped container according to claim 30. 37. A highly-designable lighting fixture in which a light source is contained in the box-shaped container according to claim 30. 38. The sheet-like laminated structure according to claim 1, wherein the structure has a hemispherical shape, and a light source unit can be disposed inside the hemispherical shape. Decorative lighting gloves. 39. The sheet-like laminated structure according to claim 1, wherein the structure has a hemispherical shape, and two of the hemispherical structures form a spherical body. A decorative lighting glove that is capable of being stacked on top of one another and arranging a light source section in the spherical body. 40. The sheet-like laminated structure according to claim 1, wherein the structure has a semi-cylindrical shape, and the light source part can be arranged inside the semi-cylindrical shape. Decorative lighting glove made. 41. The lighting glove according to claim 38, 39 or 40, wherein the sheet-like laminated structure is provided with characters or figures in a three-dimensional pattern at an interface where two kinds of layers are in contact with each other.