JP2003225973A - High design sheet-like laminated structure and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sheet-like laminated structure having excellent aesthetic properties and design properties and having a plurality of layers formed of a thermoplastic resin having a change of a continued color tone. <P>SOLUTION: The sheet-like laminated structure comprises (1) at least two types of layers formed of the thermoplastic resin, (2) the laminated structure formed of a transparent resin containing a dye or a pigment in one layer, having a simple change of a thickness in at least one direction of the sheet surface, and other layer formed of a substantially colorless transparent resin or a transparent resin containing the dye or the pigment having a color different from that of the layer, (3) the entire laminated structure having a transparency, (4) the laminated structure recognized in a change of the continued color tone along the sheet surface when visually observed from an outside surface of the layer (B) formed of the transparent resin, and a character or a graphical form of a stereoscopic pattern in a boundary brought into contact with two types of the layers so that all the layers are formed of injection molding. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, there has been a demand for product design for increasing the added value of products. Above all, there is the highest demand for high-quality products. 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 preliminarily mounted in a mold and injection molding is used. However, these molding methods are used for sheet making, printing,
In addition to requiring many steps such as trimming, it is hard to say that the design is attractive enough.

On the other hand, in Patent Document 1 and Patent Document 2, the thickness of the outer layer and the inner layer is changed, the outer layer is composed of a resin containing a colorant, and a container with gradation color in the vertical direction and its molding. A method has 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]

[Patent Document 1] JP-A-53-83884

[Patent Document 2] Japanese Unexamined Patent Publication No. 56-123235

[0005]

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 intended 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 semitransparent sheet-like laminated structure having a continuous shape change, having a thickness having sufficient shape retention.

Still another object of the present invention is to provide decorative glass windows, interior members, showcase glass windows, partitions, doors, vehicle window glass, vehicle outer panels, lamp covers, ornaments, vehicle instrumental panels and centers. Panels, interior / exterior moldings and garnishes for vehicles, display devices, display boards, light guide plates, sign boards, windshields, roofing materials, furniture, housing parts of various office automation equipment such as computers and mobile terminals, mobile phones and portable acoustics. To provide a sheet-like laminated structure having a practical strength that can be advantageously used as a member of a housing in various electric devices such as devices, an electric decoration panel such as a pachinko machine and a slot machine, and a material such as miscellaneous goods. It is in.

[0007]

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) In the laminated structure, 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, and Layer is formed of a substantially colorless transparent resin or a transparent resin containing a dye or pigment having a color different from that of the layer, and (3) the entire laminated structure has transparency, ) In the laminated structure, a continuous change in color tone is recognized along the sheet surface when visually observed from the outer surface of the layer (B) formed of a transparent resin, and the interface between the two layers is in contact. In three-dimensional pattern with letters or figures Are subjected, all layers have been found to be achieved by a high design quality sheet-like laminate structure characterized by comprising formed by injection molding.
Hereinafter, the laminated structure of the present invention will be described in more detail.

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 / absence of coloring of each layer, the color of coloring, and the like. The aesthetics and design change depending on the direction of the eye 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 4 are included.

Aspect 1 Layer 2 (layer (A)) is formed of a resin containing a dye or a pigment (hereinafter, these may be abbreviated as “colorant”), and the colorant has a certain concentration in the resin. It is contained almost uniformly. On the other hand, the layer 3 (layer (B)) is formed of a 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. In reference numeral 4 indicating a character or a figure (hereinafter, these may be abbreviated as "design"), since the thickness of the layer 2 is locally increased, the design is recognized in a relatively dark color tone.

Aspect 2 In contrast to Aspect 1, the resins forming layers 2 and 3 are reversed. 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 locally contain the colorant is increased, the pattern is recognized in a relatively pale color tone (white state).

Aspect 3 The resins forming the layers 2 and 3 each contain a coloring agent, but the coloring agents of different colors from those of the layers 2 and 3 are contained. 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.

[0013]

[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 thickness change in at least one direction of the sheet surface, and the other layer is A sheet-like 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 made of a resin containing light diffusing particles (light diffusing agent), and the layer 3 is made 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.

As will be described later, in Embodiments 1 (in the case of fluorescent colorant) and Embodiment 4, the position of the light source, the type of the colorant (especially the fluorescent colorant), the action of the light diffusing particles, and the like cause the three-dimensional pattern The image becomes more prominent and makes you feel a fantastic image. 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 three-dimensional or fantastic 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 color tone along the sheet surface is observed. A change is recognized. Therefore, it is desirable that the change in thickness is not stepwise but is gentle or linear. However, fine irregularities are locally formed in the pattern portion such as characters and figures, but the surface irregularities for forming this pattern are excluded from the category of monotonous thickness change.

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 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, from one side toward the other side (for example, from side AB to side C-
Towards D), with a monotonic change in thickness. (Ii) It has a monotonic change in thickness in the diagonal direction from the corner A to the corner C. (Iii) Side A-B, side B-C, side C-D, and side D-A from the center of the rectangle (the portion where two diagonal lines intersect).
Has a monotonic change in thickness (quadrangular pyramid or inverted quadrangular pyramid). (Iv) A monotonous change in thickness is made 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
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-mentioned examples (i) to (v) are for 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.

The laminated structure of the present invention is in the form of a flat plate and does not necessarily need to have a uniform thickness.
It is practical and preferable that the thicknesses are substantially the same. A suitable thickness is 2 to 20 mm, preferably 3 to 15 mm. The laminated structure is in the form of a flat plate, and is a plate-like member that forms straight lines in which both surfaces are substantially parallel in a cross section perpendicular to the surface, or is a curved flat plate or has a radius of curvature of 5 cm or more, preferably 15 cm. As described above, a flat plate having a curved surface of 30 cm or more is particularly preferable. Further, it may be a flat plate having a slight change in thickness. Further, in addition to the case where the surface is smooth, minute unevenness may be provided on any one of the surfaces 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. Since the laminated structure of the present invention is formed by forming each layer with a transparent resin and is transparent as a whole, it is effective for further developing the aesthetic appearance and the design due to continuous color tone change. In addition, a design with letters or figures is applied, and the design is observed in a fantastic or three-dimensional manner 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. In particular, when a fluorescent colorant or a light diffusing agent is mixed in one layer, the stereoscopic effect is more remarkable when the light source is located on the side surface of the laminated structure (the surface perpendicular to the end of the sheet surface). Will be things.

Particularly in the first to fourth aspects, when a fluorescent colorant or a light diffusing agent (particularly a fluorescent dye) is blended, the sheet-like laminated structure of the present invention makes the light source position a backlight with respect to the visual direction. 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. Utilizing this, for example, 2
By switching the two light sources (backlight and edge light), the pattern can be displayed alternately in a planar or three-dimensional manner or in a planar or fantasy manner.

The laminated structure of the present invention is excellent in design because the entire laminated structure has transparency.
The total light transmittance of the entire laminated structure is preferably 10 to 90%, preferably 20 to 70%, and the haze is 0.1 to 15%, preferably 0.15 to 10%. Is advantageous. Next, the thermoplastic resin used to form the laminated structure of the present invention will be described. As described above, in the laminated structure of the present invention, as long as the colored layer is formed of at least a 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 0.001 to 2 parts by weight, more preferably 0.005 to 1 part by weight per 100 parts by weight of the thermoplastic resin.
Parts by weight, more preferably 0.005 to 0.5 parts by weight.

Similarly, in the case of a transparent resin containing a fluorescent colorant exhibiting high designability, the composition ratio is
Per 100 parts by weight of the thermoplastic resin, preferably 0.00
1-2 parts by weight, more preferably 0.005-1 parts by weight,
It is more preferably 0.005 to 0.5 part by weight. As a transparent resin containing a light diffusing agent, JISK7
It is preferable that the plate-like molded product having a smooth surface and a thickness of 2 mm measured according to 105 has a total light transmittance of 10 to 93% and a haze of 20 to 90%. More preferable total light transmittance is 30 to 90%, particularly 50 to 90%, and more preferable haze is 30 to 90%.

In the present invention, the layer needs to be transparent, and therefore the resin forming the layer is a transparent thermoplastic resin. As the transparent thermoplastic resin, polystyrene resin, high impact polystyrene resin, hydrogenated polystyrene resin, polyacrylic styrene resin, ABS resin, AS
Resin, AES resin, ASA resin, SMA resin, polyalkylmethacrylate resin, polyphenyl ether resin,
Polycarbonate resin, amorphous polyalkylene terephthalate resin, amorphous polyamide resin, poly-4-methylpentene-1, cyclic polyolefin resin, amorphous polyarylate resin, polyether sulfone, styrene thermoplastic elastomer, olefin Examples thereof include thermoplastic elastomers such as thermoplastic elastomers, polyamide thermoplastic elastomers, polyester thermoplastic elastomers and polyurethane 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 of the present invention 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.

The cyclic polyolefin resin of the present invention includes APO resin manufactured by Mitsui Chemicals, Inc., Arton manufactured by JSR Co., Zeonex manufactured by Nippon Zeon Co., Ltd., and hydrogenated-α-olefin-dicyclopentadiene. Examples thereof include copolymers. Particularly, it is preferable that at least one layer is a polycarbonate resin from the viewpoint of mechanical strength, heat resistance and the like of the laminated structure. Most preferred is a laminated structure in which all layers are composed 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.

Carbonyl halide, carbonate ester or haloformate is used as the carbonate precursor, and specific examples thereof include phosgene, diphenyl carbonate or dihaloformate of dihydric phenol. In producing a polycarbonate resin by reacting the dihydric phenol and the carbonate precursor by an interfacial polymerization method or a melt polymerization method, a catalyst, an end terminating agent, for preventing the oxidation of the dihydric phenol, if necessary. Antioxidants and the like may be used. 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 the trifunctional or higher polyfunctional aromatic compound 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.
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 gives 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%. In particular, in the case of the melt transesterification 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 5 mol% in the total amount of the aromatic polycarbonate.
0.5 mol%, particularly preferably 0.01 to 0.3 mol%
Are preferred. The ratio is ¹
It can be calculated by H-NMR 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 stopper 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).

[0039]

[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 above 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.

[0043]

[Chemical 2]

[0044]

[Chemical 3]

(In the formula, X is -R-O-, -R-CO-O.
-Or-RO-CO-, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5, and n represents an integer of 10 to 50. Show. )

The substituted phenols of the general formula (2) are preferably those in which n is 10 to 30, particularly 10 to 26. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, Octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like can be mentioned.

Suitable substituted phenols of the general formula (3) are compounds in which X is —R—CO—O— and R is a single bond, 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 at the end of at least 5 mol%, preferably at least 10 mol% based on all the ends of the obtained polycarbonate resin. More preferably, 80 mol% or more of the terminal terminator is introduced into all terminals, that is, it is more preferable that the hydroxyl group (OH group) at the terminal derived from the dihydric phenol is 20 mol% or less, and particularly preferably. This is the case where 90 mol% or more of the terminal terminator is introduced to all the terminals, that is, the OH 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 under 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.

Also, a polymerization catalyst is used to accelerate the polymerization rate.
As the polymerization catalyst, for example, water can be used.
Sodium oxide, potassium hydroxide, dihydric phenol
Alkali metal compounds such as thorium salt and potassium salt, water
Calcium oxide, barium hydroxide, magnesium hydroxide
Alkaline earth metal compounds such as tetramethylammonium
Um hydroxide, tetraethylammonium hydroxide
Nitrogen-containing substances such as side, trimethylamine, and triethylamine
For basic compounds, alkali metals and alkaline earth metals
Lucoxides, alkali metal and alkaline earth metal organics
Acid salts, zinc compounds, boron compounds, aluminum
Compounds, silicon compounds, germanium compounds, organic
Tin compounds, Lead compounds, Osmium compounds, Anne
Timon compounds Manganese compounds, Titanium compounds, Di
Usual esterification of ruconium compounds, ester
The catalyst used for the le exchange reaction can be used. Touch
The medium may be used alone or in combination of two or more.
May be used. The amount of these polymerization catalysts used depends on the amount of raw materials.
Preferably 1 × 10 1 mol of dihydric phenol ^-8~
1 x 10^-3Equivalent, more preferably 1 × 10^-7~ 5 x 10
^-FourIt is selected within the equivalent range.

In the polymerization reaction, in order to reduce the number of phenolic terminal 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, the phosphonium salt or ammonium salt type is preferred. 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, if the molecular weight is less than 10,000, the high temperature characteristics are deteriorated, and if it exceeds 40,000, the moldability is deteriorated. Therefore, it is represented by the viscosity average molecular weight. 10,0
It is preferably from 00 to 40,000, and from 14,000 to
Those of 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 the drawdown performance which is important for blow molding, the drip prevention performance for improving flame retardancy, and the 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 the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

A releasing agent can be added to the thermoplastic resin of the present invention, and this gives preferable results in that distortion at the time of releasing can be suppressed. The release agent is generally a saturated fatty acid ester, for example, monoglycerides such as stearic acid monoglyceride, triglycerides such as stearic acid triglyceride, polyglycerin fatty acid esters such as decaglycerin decasterate and decaglycerin tetrastearate, 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. The release agent is a thermoplastic resin 10.
0.01 to 1 part by weight is used per 0 part by weight.

If necessary, a phosphorus-based heat stabilizer may 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 2
You may use it in combination of 2 or more types. Phosphorus heat stabilizer is
0.0001 to 0 .. per 100 parts by weight of the thermoplastic resin.
It is suitable to use 5 parts by weight, preferably 0.001 to 0.05 parts by weight.

To the thermoplastic resin, an antioxidant which is generally known for the purpose of preventing oxidation can be added. 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 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 preferred range of addition of these ultraviolet absorbers and light stabilizers is 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin.

Further, the transparent thermoplastic resin of the present invention may be blended with a bluing agent for canceling 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 "Macrolex Violet B" manufactured by Bayer, "Dialesin Blue G" manufactured by Mitsubishi Chemical Co., Ltd., "Sumiplast Violet B" manufactured by Sumitomo Chemical Co., Ltd.], and generic name Solvent Violet31.
[CA. No68210; Trade name "Mitsubishi Resin Co., Ltd." Dialesin Violet D "], general name Solve
nt Violet33 [CA. No. 60725; Trade name "Mitsubishi Resin Co., Ltd." Dialesin Blue J "], general name Solvent Blue 94 [CA. No615
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 [Trade name Bayer "Macrolex Blue RR"] and generic name Solvent Blue45
[CA. No61110; trade name "Terrazol Blue RLS" manufactured by Sand Co., Ltd., Macrolex Violet, Terrazol Blue RLS and the like manufactured by Ciba Specialty Chemicals, and the like, and Macrolex Violet and Terrazol Blue RLS are particularly preferable.

In the thermoplastic resin, other conventional additives within the range of transparency, for example, reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass beads, glass balloon, milled) are used. Fiber, glass flake, carbon fiber, carbon flake, carbon beads, carbon milled fiber, metal flake,
Metal fibers, metal-coated glass fibers, metal-coated carbon fibers, metal-coated glass flakes, silica, ceramic particles, ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, graphite, conductive carbon black, various whiskers, etc.), flame retardants (Halogen type, phosphate type, metal salt type, red phosphorus, silicon type, fluorine type, metal hydrate type, etc.), heat-resistant agent, fluorescent brightening agent, antistatic agent, flow modifier, inorganic and An organic antibacterial agent, a photocatalytic antifouling agent (fine particle titanium oxide, fine particle zinc oxide, etc.), an impact modifier typified by graft rubber, an infrared absorber, and a photochromic agent can be added.

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, it is possible to selectively remove the information recording layer, the reflection layer and the protective coating layer from the optical information recording medium from the resin substrate, and collect and use the resin itself. The method described can be used.

Next, the colorant contained in at least one layer constituting the laminated structure of the present invention will be described. Colorants include dyes, pigments, or light diffusers. These are what are known per se as resin colorants,
The desired color can be determined by selecting from the type of resin, dispersibility in resin, processing temperature, and the like. Two or more kinds of colorants may 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 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 dyes 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 Violet 1
3, CI Solvent Violet 14, CI
Disperse Violet 28, CI So
lvent Green 3, CI Solvent
Anthraquinone dyes and quinoline dyes known as Green 28 include CI Solvent.
Yellow 33, CI Solvent Yell
ow 157, CI Disperse Yellow
54, CI Disperse Yellow 16
0 can be mentioned. Examples of perinone dyes include CI Solvent Red 135 and CI S
solvent Red 179, CI Solvent
Orange 60 and the like can be mentioned. These can be used alone or in combination of two or more, and a fluorescent colorant capable of performing coloring according to the purpose can also be used, and examples thereof include fluorescent dyes, and phthalocyanine complexes and naphthalocyanine complexes. Fluorescent organic pigments can be used.

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 thereof include xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes.

Among these, from the viewpoint of fluorescence durability (weather resistance), the perylene fluorescent dye, the coumarin fluorescent dye, and the benzopyran fluorescent dye are 100% by weight of the fluorescent dye.
It is preferable to contain 5% by weight or more.

Various types 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. Specific examples are as follows.
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 So
Lvent Green 5 and BASF LUM
As the OGEN series F Orange240, F
Red300, F Yellow083, F Red
339, F Violet 570 and the like.

Among the above, those containing 5% by weight or more of the perylene fluorescent dye in 100% by weight of the total amount of the fluorescent dye can be preferably used. Specific examples of the fluorescent dyes other than the perylene-based fluorescent dye, the coumarin-based fluorescent dye, and the benzopyran-based fluorescent dye include the following.

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. Fluorescent organic pigments include CI PIGMENT GREEN 7, CIP
Examples thereof include phthalocyanine organic pigments such as IGMENT BLUE 15: 3, and naphthalocyanine organic pigments.

As the light diffusing agent that can be used in the present invention, 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. More preferably 0.1-10
The average particle size is μm, more preferably 0.1 to 8
It has an average particle diameter of μm. The particle size distribution is preferably narrow, and more preferably the particle size distribution is such that the particles having an average particle size of ± 2 μm are 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 refractive index difference 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 silicone-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, the crosslinkable monomer is not required if the shape of the fine particles is not impaired even when the matrix resin is heated and melted. Further, as the polymer particles, various thermosetting resins such as epoxy resin particles, urethane resin particles, melamine resin particles, benzoguanamine resin particles, and phenol resin particles can 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-based 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 made 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 silicone-based crosslinked particles have a siloxane bond as a main skeleton and have an organic substituent on a silicon atom, and have a high degree of crosslinking represented by polymethylsilsesquioxane and methylsilicone 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 silicone-based crosslinked particles include an alkane group such as a methyl group, an ethyl group, a propyl group, and 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 silicone-based crosslinked particles, a trifunctional alkoxysilane or the like is hydrolyzed and condensed in water to grow a siloxane bond by 3
A method of forming dimensionally crosslinked particles is generally used, and the particle size can be controlled by, for example, the amount of alkali in the catalyst or the stirring step. On the other hand, as a method for producing polymer fine particles other than the organic cross-linked particles, there are a spray drying method, a liquid curing method (coagulation method), a phase separation method (coacervation method), a solvent evaporation method, a reprecipitation method, and the like. 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 can be adopted. . 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. ..

The titanium dioxide particles are not limited by the production method, crystal structure and particle size, but are titanium oxide produced by the chlorine method, and those having a rutile type crystal structure are 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-aminopropyltrimethoxysilane, N-β (aminoethyl).
Surface treatment with -γ-aminopropylmethyldimethoxysilane and the like can be mentioned. The surface treatment agent may contain a stabilizer, a dispersant and the like 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 Titanium particles and thermoplastic resin at the same time V
A method of mixing with a mold blender and a method of simultaneously charging into an extruder and extruding are also effective.

The method for molding the laminated structure of the present invention is an injection molding method. This is because such a molding method can efficiently manufacture the entire laminated structure.

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 into 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.

Ultra-high speed injection molding is a suitable method for a laminated structure having a pattern on the interface. 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. 300m as the injection speed for ultra high speed injection molding
m / sec or more, preferably 350 mm / sec or more.

In combination with injection compression molding, it is suitable when the interface portion has a precise pattern. 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. 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 a laminated structure having a pattern on the interface of the present invention, it is preferable to use an ultrahigh-speed injection molding, an injection compression molding, an adiabatic mold molding, and a local high temperature mold molding in an appropriate combination. . Further, 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, 1
It is possible for either one layer or the other to be a two-layer structure. When combined with gas assist molding, 1
By forming one layer, another layer, or both one layer and another layer as a hollow structure, it is possible to reduce the weight of each layer and to impart different design characteristics and optical functions. is there. For example, filling the hollow portion with a compound having a photochromic property to prepare a photoreactive product.

[0102]

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, a fluorescent lamp was installed on the back side of the laminated structure, and the design of the laminated structure was evaluated from the front side. (Ii) Edge light method: As shown in FIGS. 3 and 4, a cold cathode tube having a diameter of 2.6 mm and a length of 220 mm is installed on the end face of the laminated structure (the end face of the thick portion or the end of the thin portion),
The design of the laminated structure was evaluated from the front side. (Ii) -1. Thick part end face: When a cold cathode tube is installed on the end face of the laminated structure on the B layer thick part side (ii) -2. Thin-walled end face: When a cold cathode tube is installed on the end face of the laminated structure on the B-layer thin-walled part

(1) Designability The designability of the entire 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 from the surface side of the laminated structure was visually evaluated. 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) Colored text: 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 blurred outline of the characters in the diffused light.

The thermoplastic resin composition used in the examples was prepared as follows.

(I) <When a part of the layer is composed of a material containing a dye> [Reference Examples 1 to 6] Composition ratios shown in Table 2 for each component shown in Table 2 (units are parts by weight). ), Dry blended, and then a single screw extruder with a vent equipped with a Dalmage 2-stage screw having a diameter of 30 mm [NSKATANI MACHINERY: VSK-
30] using a cylinder temperature and a die temperature of 290
The strand was extruded under the conditions of ℃ and vent suction degree of 3000 Pa, 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. 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.

[0110]

[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, SandstabP-
A mixture of 0.03 parts by weight of EPQ (manufactured by Sandoz) and 0.2 parts by weight of pentaerythritol tetrastearate (these stabilizer releasing agents, and optionally a coloring agent are uniformly premixed and melt 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 multiple injection units each having a cylinder inner diameter of 50 mmφ were 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 form 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) was molded by using the remaining one of the two cylinders at a cylinder temperature of 300 ° C., a mold temperature of 100 ° C., and an injection speed of 30.
The resin for forming the layer (B) was injected at 0 mm / sec to perform the integral molding (laminated structure) shown in FIGS. 6 and 9. In forming the layer (B), a vacuum pump (ULVAC PMB00 manufactured by Nippon Vacuum Technology Co., Ltd.) was used after closing the mold.
6CM mechanical booster and EC803 rotary pump were used together), and after evacuation for 10 seconds, molding was performed. Exhaust was performed through a gas vent clearance provided around the mold cavity.

The same main mold is used as the mold, and only the plates are replaced (see FIGS. 7 and 8).
Then, one channel is omitted). 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 The materials shown in Table 3 were used, and molding was carried out in the same manner as in Example 1 except that 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.

[0118]

[Table 3]

As is clear 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 in the composition ratios shown in Table 4, 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 3000 Pa, cooled in a water bath, and then cut into pellets by a pelletizer. After drying the pellets with a hot air drier, the molding shown in the following examples was performed. However, for the sample symbols "PMMA" and "PO", the above-mentioned melt-kneading was not performed, and the raw materials were directly subjected to drying and molding.

[0121]

[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 (LUM manufactured by BASF)
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 the materials shown in Table 5, 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.

[0125]

[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 molded product layer (B) thick part side to the layer (B) thin part side. The color it has is obtained. Further, by shining light from the back surface of the molded product, it is possible to obtain excellent designability in which the characters expressed inside the molded product are emphasized in a plane with respect to the entire molded product. Further, when light 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 Layer is Composed of Material Having Light Diffusivity> Reference Examples 3, 10 and 11 to 13 Each component shown in Table 6 was dried at the composition ratio shown in Table 6. After blending, vented single-screw extruder equipped with a Dalmage 2-stage screw with a diameter of 30 mmφ [Nakatani Machinery 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 3000 Pa, cooled in a water bath, and then cut into pellets by a pelletizer. After drying the pellets with a hot air drier, the molding shown in the following examples was performed.

[0128]

[Table 6]

The symbols showing the components shown in the raw material name column of Table 6 are as follows.

(Light Diffusing Agent) S: Silicone cross-linked particles (TO Toshiba Pearl 120 manufactured by GE Toshiba Silicone Co., Ltd.) A: Acrylic cross-linked particles (Techpolymer MBX-5 manufactured by Sekisui Plastics Co., Ltd.) M: Inorganic Fine particles (Nitto Boseki Co., Ltd. glass fiber PF
E-301S) A molded product was prepared by the method described below.

Examples 8 to 11 The materials shown in Table 7 were used, and 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.

[0132]

[Table 7]

As is clear from Table 7, for example, in the case of Example 8, a color having a gradation from red to orange and yellow from the molded product layer (B) thick part side to the layer (B) thin part side. Is obtained. Further, by shining light from the back surface of the molded product, it is possible to obtain an excellent design property in which the characters expressed inside the molded product are flatly colored with respect to the entire molded product. When light 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 are observed with the contour of the character slightly blurred in the diffused light. 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 11, when light is applied from the layer (B) thin portion side end surface of the molded article (the thick portion side end surface of the layer (A) made of a light diffusing material), the surface has a uniform color. Shines in the shade of. 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.

[0134]

EFFECTS OF THE INVENTION The present invention is a laminated structure having a high degree of freedom and continuous color tone change (gradation color) and capable of providing characters, pictures, and patterns capable of a variety of internal expressions. The industrial effect is extremely large.

[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 view when a light source is arranged on the back surface of the laminated structure of the present invention by a backlight system and the designability thereof is observed.

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

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.

[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 laminated structure layer (A) X observation direction (arrow) L light source 5 vertical length of laminated structure body (200 mm) 6 thickness of laminated structure body (5 mm) 7 gate of laminated structure body layer (B) (0.8 mm) 8 in lower part of the laminated structure body layer (A) at the lower end (flow end)
Thickness (0.8 mm) 9 Length of three-dimensional pattern portion of pattern (75 mm) 10 Thickness of three-dimensional pattern portion of pattern (+1 mm relative to layer (A) plane) 11 Layer (A) of laminated structure and Position of a part where both thicknesses of layer (B) are 2.5 mm (50 mm from the lower end) 12 Thickness of layer (A) in the above 11 (2.5 mm) 13 Fixed-side mold 14 Core side for layer (A) Mold 15 layers (A) hot runner tip valve 16 layers (A) hot runner flow path 17 layers (A) cylinder 18 layers (A) resin flow 19 movable mold 20 layers (B) hot Runner tip valve 21 Layer (B) hot runner channel 22 Layer (B) cylinder 23 Layer (B) resin flow 24 Layer (B) core side mold

Continued front page    F-term (reference) 4F100 AK01A AK01B AK02A AK02B                       AK25A AK25B AK43A AK43B                       AK45A AK45B BA02 BA07                       CA13A CA13B GB08 GB33                       GB41 HB00A HB00B JA12A                       JA12B JB16A JL10 JN01A                       JN01B                 4F206 AA12 AA21 AA27 AA28 AB14                       AF00 AG01 AG03 AH26 AH42                       AH48 AR12 JA07 JB22 JB28                       JL02 JQ06 JQ81

Claims (7)

[Claims] 1. A sheet-like laminated structure comprising (1) at least two layers of layers formed of a thermoplastic resin, and (2) the laminated structure wherein one layer is a dye or a pigment. Is formed of a transparent resin containing and has a monotonous thickness change in at least one direction of the sheet surface,
The other layer is formed of a substantially colorless transparent resin or a transparent resin containing a dye or pigment having a color different from that of the layer, and (3) the entire laminated structure has transparency, 4) In the laminated structure, continuous color tone change is observed along the sheet surface when visually observed from the outer surface of the layer (B) formed of a transparent resin, and the two layers are in contact with each other. A highly-designable sheet-like laminated structure characterized in that all layers are formed by injection molding, in which characters or figures are formed by a three-dimensional pattern at the interface. 2. The sheet-like laminated structure according to claim 1, which has a flat plate shape having an average thickness of 2 to 20 mm. 3. 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. 4. The sheet-shaped laminated structure according to claim 3, wherein the transparent resin is a polycarbonate resin. 5. All the constructed layers are formed from the same kind of resin and the resin is selected from polycarbonate resin, polyalkylmethacrylate resin, cyclic polyolefin resin or amorphous polyarylate resin.
The sheet-shaped laminated structure described. 6. The sheet-like laminated structure according to claim 3, wherein all the constituted layers are formed of a polycarbonate resin. 7. A decorative organic glass comprising the laminated structure according to any one of claims 1 to 6.