JP2001232663A - Method for producing multilayer molded article and molded article - Google Patents

Abstract

(57) [Summary] [Problems] To obtain a multilayered molded article having more excellent interlayer adhesion than conventional sheet insert molding methods,
A molding method for obtaining a molded article having a multilayer structure capable of coping with such a problem in appearance, and such a product are provided. A molding method for obtaining a molded article having a multilayer structure by a sandwich molding method of a thermoplastic resin, wherein (1) a thermoplastic resin sheet in which a sheet layer is previously formed on a surface of a mold cavity and / or a surface of a mold core. (2)
The injection speed at the time of filling the thermoplastic resin forming the skin layer and the thermoplastic resin forming the core layer into the mold cavity in which the sheet is mounted is 300 mm / sec or more when filling the thermoplastic resin forming the core layer. A molding method for obtaining a multilayer molded article having a sheet layer, a skin layer and a core layer by filling under the following conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article having a multilayer structure excellent in adhesion between layers. Specifically, by combining the sheet insert molding method and the sandwich molding method and performing injection molding that satisfies specific conditions, the adhesion between the layers is more excellent than the conventional sheet insert molding method and the multilayer structure molded product The present invention relates to a method for obtaining a multilayered molded article having good mechanical properties and good appearance, and a molded article comprising the same, particularly a large product.

[0002]

2. Description of the Related Art Conventionally, products having a multilayer structure have been mainly manufactured by sandwich molding, multicolor molding, in-mold molding,
It was manufactured by an insert molding method or the like. In recent years, there has been a demand for a product design that imparts different functions to each layer of a product in order to increase the value of the product, such as enhancing the functionality and design of the product, saving resources and environmental measures through recycling and painting less. I have. In particular, there is the highest demand for adding a specific function to the product surface to increase added value.

[0003] In response to such demands, conventionally, printing or hard coating is applied to the surface of a thermoplastic resin sheet, the sheet is inserted into the surface of a mold cavity or the surface of a core, and a thermoplastic resin is placed in the mold cavity. There has been proposed a method in which a sheet and a molded product are integrated by filling by an injection molding method, and value is added to a surface portion. In such a case, in order to strengthen the adhesiveness between the sheet portion and the thermoplastic resin, the thermoplastic resin forming the sheet is made of the same type as the thermoplastic resin injected and filled into the mold forming the molded article body. (Japanese Patent Application Laid-Open Nos. 60-92586 and 60-19551).
No. 5 publication).

[0004] However, there are cases where such normal sheet insert molding cannot sufficiently cope. For example,
This is the case where it is required to use a material different from the molded article body for the sheet and to impart various functions. In such a case, sufficient adhesion may not be obtained in some cases. Also, when an inorganic filler is blended in the thermoplastic resin forming the molded article main body, for example, when printing or the like is performed on the interface side surface of the sheet, such an inorganic filler may damage the printed surface. There is a case where the appearance of the molded product becomes insufficient due to scratches on the sheet interface even without printing. That is, there is a demand for a molding method that can cope with these problems.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a molded article having a multi-layered structure having better adhesion between layers than the conventional sheet insert molding method, and to cope with such problems in appearance. An object of the present invention is to provide a molding method for obtaining a molded article having a multilayer structure, and to provide such a product. The present inventor has conducted intensive studies to solve the above problems, and as a result, combines the sheet insert molding and the sandwich molding, and fills the resin which forms the core layer in the sandwich molding at a high speed higher than a specific injection speed. As a result, the present inventors have found that a desired good product can be obtained, and have reached the present invention.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a molding method for obtaining a molded article having a multilayer structure by a sandwich molding method of a thermoplastic resin, wherein (1) a mold cavity surface and / or a mold core surface are previously formed. A thermoplastic resin sheet forming a sheet layer is mounted, and (2) a thermoplastic resin forming a skin layer and a thermoplastic resin forming a core layer are formed in a mold cavity in which the sheet is mounted, and a core layer is formed. Injection speed of 300mm / s when filling thermoplastic resin
a molding method for obtaining a multilayered molded article having a sheet layer, a skin layer, and a core layer by filling under a condition of not less than ec,
And its products.

The present invention is a molding method using a sandwich molding method as a basic element. Here, the sandwich molding refers to a thermoplastic resin forming a skin layer in a mold (hereinafter sometimes simply referred to as a “skin layer resin”) and a thermoplastic resin forming a core layer (hereinafter simply referred to as a “core layer resin”). "May be referred to as"") to form a layer structure composed of a skin layer and a core layer.

As a method for injecting the resin for the skin layer and the resin for the core layer, sequential injection, simultaneous injection, or a combination of sequential injection and simultaneous injection can be used as appropriate. In particular, a method in which the skin layer is slightly preferentially injected simultaneously is preferable.

In the sandwich molding of the present invention, a method using one or more injection cylinders can be used in addition to a method using two or more injection cylinders independently for each resin for each resin.

In the case of using a single injection cylinder, the resin of the skin layer and the resin of the core layer are separated and accumulated in a front chamber and a rear chamber by a movable mandrel, and the resin of the skin layer is injected into the mold by injection. After filling, a movable mandrel method in which the resin of the core layer is filled through a hole at the tip of the movable mandrel. In addition, the resin of the skin layer is extruded from the auxiliary device, and the resin in the core layer is plasticized by the injection device after the accumulation in the injection device is enabled by the switching valve in the hot runner. After accumulating the resin in the injection device, a mono-sandwich method of allowing and filling the mold with a switching valve or the like in a hot runner can be used, and any method can be used in the present invention. it can.

In the case of using a plurality of cylinders, a method in which the resin of the skin layer and the resin of the core layer are formed into a layered structure by using a merging nozzle, or a method in which the resin is merged at a gate portion or the like in a mold can be used.

When a merge nozzle is used, both a parallel nozzle and a V-type nozzle can be used, and it is preferable to use a concentric double tube type as the internal structure of the nozzle. Further, the number of resin layers in the nozzle is basically a two-channel type, but a three-channel type or more capable of further increasing the number of layers can also be used.

In the case of merging at a gate portion or the like in a mold, the configuration is such that resins injected from a plurality of cylinders are multi-layered by a concentric double tube type gate system through independent hot runner manifolds. In addition to the method, a method of forming a multilayer at a gate portion through a cold runner can also be used.

As the gate system using the hot runner, any of an internal heating system and an external heating system may be used. In the case of the external heating system, any of an open gate system and a valve gate system may be used. You may.

In the present invention, preferably, the cylinder has two independent cylinders and has a concentric double tube type nozzle structure. Cylinders are made independent, and conditions such as cylinder temperature and injection speed can be selected for each cylinder. It becomes possible. That is, the optimum resin temperature (cylinder temperature), injection speed and its pattern, injection start timing, injection capacity, and the like for each device are determined.

One of the requirements of the present invention for sandwich molding is to attach and mold a thermoplastic resin sheet to the surface of the mold cavity and / or the surface of the mold core (hereinafter referred to as “Requirement (1)”). "). According to such requirements, it is possible to impart a specific function to the surface of the molded article by utilizing the properties of the thermoplastic resin sheet itself. By applying various functions such as oiliness and printing, it is possible to efficiently impart the surface of a molded article with these functions and high design properties comparable to painting.

In the present invention, the surface of the mold cavity refers to the surface of the mold cavity in the fixed mold.
The mold core surface refers to the surface of the mold cavity in the movable mold. The mold cavity refers to a portion of the mold that is filled with resin to obtain a molded article main body (excluding runners and sprues).

Examples of the thermoplastic resin (hereinafter, may be simply referred to as “sheet layer resin”) used in the thermoplastic resin sheet include, for example, polyethylene resin, polypropylene resin, ethylene-propylene copolymer, polystyrene resin, diene resin, and the like. A thermoplastic graft polymer obtained by grafting a vinyl cyanide compound and an aromatic vinyl compound onto rubber (so-called ABS resin), and a thermoplastic graft polymer obtained by grafting a vinyl cyanide compound and an aromatic vinyl compound onto an ethylene-propylene copolymer (so-called AES) Resin), a thermoplastic graft polymer obtained by grafting a vinyl cyanide compound and an aromatic vinyl compound onto an acrylic elastic body (so-called ASA resin), and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound (so-called A resin).
S resin), acrylic resin such as polymethyl methacrylate, polymethyl pentene resin, polyamide resin, aromatic polyester resin, wholly aromatic polyester resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polysulfone resin, polyarylene sulfide resin, poly Various thermoplastic elastomers such as ether sulfone resin, polyisobutylene, styrene, olefin, urethane, polyester, polyamide, etc., polyisobutylene, cyclic polyolefin resin, or copolymers, mixtures, and modified products of these polymers Is raised. It is also possible to use a combination of two or more of these thermoplastic resins, and these thermoplastic resins may contain various additives. Further, it may be a thermoplastic resin sheet in which different or same thermoplastic resins or their compositions are laminated.

The thermoplastic resin sheet used in the present invention comprises:
In addition to a general melt extrusion method, an inflation method, a continuous casting method, a cell casting method, a method such as a solution casting method and a powder molding method can be used. Further, in these methods, a method of directly melt-extruding from a molten state such as a melt transesterification reaction in a production process of a raw material resin,
Alternatively, a sheet having a small heat history can be obtained by directly performing the solution casting from the solution state after the polymerization.

The thickness of such a sheet is 10 to 200
0 μm is preferable, and more preferably 100 to 1000 μm
m, particularly preferably 200 to 700 μm. 10
In the range of 2000 μm, the sheet itself has sufficient strength,
It is possible to effectively balance the mechanical strength of the entire molded article. That is, if the thickness is too thin, the strength of the entire sheet is insufficient, and the flow of the resin causes deformation of the sheet itself.

In the present invention, such a thermoplastic resin sheet can be mounted on either the mold cavity surface or the mold core surface, or on both surface sides. In particular, mounting the sheets on both surfaces is a preferable method because the heat histories at the time of molding on both surface sides can be made equal, which is advantageous against warpage of the molded product.

In order to predict the effect of the sheet on the heat history, the temperature, specific heat, thermal conductivity, density, and the like of the thermoplastic resin filled by sandwich molding, the main mold and the thermoplastic resin sheet during molding. By calculating from the crystallization latent heat or the like, it is also possible to analyze such heat history and confirm the influence on the shape of the molded article. In particular, using the temperature of the surface of the thermoplastic resin of the skin layer in contact with the thermoplastic resin sheet as an index, at least the temperature at which the temperature is higher than the glass transition temperature of the thermoplastic resin of the skin layer (the highest temperature in the case of a plurality of layers). It is preferable to design the sheet so that the sheet can be maintained for 0.1 second, and it is more preferable to design the sheet thickness, the molding conditions, and the apparatus environment that can be maintained within a range of 1 second or more, and as an upper limit within 60 seconds. For example,
Using ADINA and ADINA-T (name of software developed at the Massachusetts Institute of Technology) and the like,
It can be calculated by transient heat conduction analysis by the nonlinear finite element method.

When the stretching ratio of the thermoplastic resin sheet locally increases depending on the shape of the product, the thermoplastic resin sheet is formed by a straight molding method, a drape molding method, a plug assist molding method, an air blow molding method, or the like. It is also possible to use a preformed shape by a conventionally known method such as a method of heating vacuum molding, a method of heating press molding, or a method of heating and pressure forming. Further, the preforming step of giving a shape to the thermoplastic resin sheet in advance may be performed in an injection molding die from the viewpoint of improving the efficiency of the step.

Further, as the thermoplastic resin sheet used in the present invention, a sheet which has been subjected to a treatment such as hard coating or printing in advance can be used.

In the present invention, a known hard coat agent can be used as a compound for forming a crosslinked film as a hard coat film on a thermoplastic resin sheet. As a hard coating agent, a resin having a high surface hardness, for example, an acrylic resin,
Melamine-based, urethane-based, epoxy-based, and other well-known silicone-based hard coat agents such as those capable of having a hard coat property equivalent to that of glass by a siloxane bond in an organosiloxane resin can be used.

In addition, a known curing method such as ultraviolet curing, heat curing, electron beam curing, infrared irradiation and hot air drying may be used alone or in combination according to the type of the hard coat agent. Can also. In such a case, particularly when the stretching ratio of the thermoplastic resin sheet locally increases as described above, after hardening the hard coat agent to such an extent that the hard coat agent is not completely hardened, without shaping, or After shaping and shaping to obtain a multilayer structure molded article, a method in which the hard coat agent is completely cured can be adopted. In addition, a hard coat agent is applied as a gel or sol having a partially cross-linked structure, and then molded without shaping or by shaping to form a multilayer structure molded article. Can be completely cured.

When the resin material is a polycarbonate or a heat-resistant acrylic resin, it is particularly preferable to provide a primer layer having good adhesion between the hard coat agent and the resin, and it is not particularly limited. For example, an acrylic resin containing an ultraviolet absorber can be used.

Known methods such as a bar coating method, a spray coating method, and a roll coating method can be used as a method for applying the hard coat film forming raw material. The thickness of the lamination sheet thus obtained is determined by the appearance of a molded product, impact resistance, abrasion resistance, weather resistance and the like. The thickness is preferably 1 to 50 μm, and more preferably 2 to 30 μm
It is. When the thickness of the hard coat film is in the range of 1 to 50 μm, the sheet has both sufficient damage resistance and flexibility of the sheet, and can be applied to various molded product shapes as a sheet having resistance to bending and the like. .

At the time of coating, an organic solvent can be added as a diluent to the raw material for forming a hard coat film. Organic solvents that can be used include butyl acetate, ethyl acetate, toluene, isopropanol and the like. The amount used is such that the solid content concentration of the primer layer is 1-5.
0% by weight, and the solid content concentration of the hard coat film forming raw material is 1 to 70% by weight.
More preferably, the content is 3 to 30% by weight.
If necessary, a leveling agent, an antistatic agent, a release agent, a matting agent, an inorganic filler and the like can be added to the raw material for forming a hard coat film.

Further, in the present invention, characters and patterns can be formed by printing on a part of the thermoplastic resin sheet for use.

As a printing method, a conventionally known printing method such as gravure printing, lithographic printing, flexographic printing, dry offset printing, pad printing, screen printing and the like can be used according to the product shape and printing application.

The composition of the printing ink used in printing may be a resin or oil as a main component, and may be a natural resin such as rosin, gilsonite, shellac, copearl, or phenol. System and its derivatives, amino resin, butylated urea, melamine resin, polyester alkyd resin, styrene resin, acrylic resin, phenol resin, epoxy resin, polyamide resin, polycarbonate resin, saturated polyester resin, amorphous polyarylate resin, Amorphous polyolefin resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride
Synthetic resins such as vinyl acetate copolymers, butyral resins, methylcellulose resins, ethylcellulose resins, and urethane resins can be used. In particular, when printing is performed on the surface on the interface side with the skin layer, an ink component having high heat resistance is required. As such a resin, a polycarbonate resin, an amorphous polyarylate resin, and the like are preferable. In addition, a desired color can be adjusted by using a pigment or a dye in the printing ink.

On the other hand, as other surface treatments, a fluorine-based or water-repellent / oil-repellent coat, or a water immersion coat using a photocatalyst or the like can be used.

The method for mounting the thermoplastic resin sheet on the surface of the mold cavity and / or the surface of the mold core includes the following. For example, a method of applying static electricity to a thermoplastic resin sheet and mounting the same on the cavity surface and / or the core surface of the mold, or by suctioning the thermoplastic resin sheet from a suction groove provided in the mold by vacuum or the like. A method of mounting on a cavity surface and / or a core surface of a mold, a hole is previously formed in a gate portion or a tab portion of a thermoplastic resin sheet, and then mounted using pins provided on a mold cavity surface or a core surface. And a method in which an iron piece or the like is attached to a tab portion or the like of a thermoplastic resin sheet, and a magnet is embedded in a mold cavity surface or a core surface in advance and mounted. Other conventionally known methods can be used.

Examples of the thermoplastic resin sheet include an acrylic resin having excellent surface hardness, an aromatic polyester resin, a wholly aromatic polyester resin, and a polyamide resin having excellent chemical resistance, gas barrier properties, and sheet formability with high appearance. Preferable examples include resins and polyarylene sulfide resins. Above all, preferable examples include aromatic polyester resins.

According to the present invention, the injection speed at the time of filling the resin of the skin layer and the resin of the core layer into the mold cavity in which the thermoplastic resin sheet is mounted according to the above requirement (1) is determined. The second requirement is that filling is performed under a condition of 300 mm / sec or more (hereinafter, may be referred to as “requirement (2)”). Filling is performed under such conditions using a sandwich molding method to obtain a molded article having a multilayer structure having a sheet layer, a skin layer, and a core layer.

By performing the filling that satisfies the requirement (2), the melt viscosity of the resin forming the core layer can be reduced, and the resin of the skin layer can be filled while being strongly stretched in the flow direction. As a result, it is possible to form a sandwich with a thin skin layer without causing a break phenomenon. This makes it possible to freely select a sheet layer corresponding to the required surface properties and a core layer in consideration of the strength of the entire molded product without considering the adhesion between the core layer and the sheet layer. It becomes possible.
This is because the skin layer serving as the adhesive layer can be made thinner, so that the influence of the skin layer on the strength and the like of the whole molded article is reduced.

The requirement (2) is based on the condition that the resin of the core layer has an injection speed of 300 mm / sec or more, preferably 350 mm / sec or more, particularly preferably 400 mm / sec or more. The upper limit of the speed is about 800 mm / sec. 300 ~
In the range of 800 mm / sec, it is possible to achieve the object of the present invention and to obtain a good multilayer-structured molded product with little burnt generated on the molded product due to high speed. Here, the injection speed refers to an average speed from the start to the end of filling into the mold cavity, and does not necessarily have to be a constant speed, and molding can be performed at multiple injection speeds.

In order to achieve an injection speed of 300 mm / sec or more, it is fundamental to increase the injection horsepower by increasing the capacity of the accumulator or increasing the horsepower of the motor. It is also necessary to optimize the structure of the injection cylinder, hydraulic control system, motor control system, and the like in order to achieve control and response of the screw speed and position at extremely high speed and short time. As such a system, various currently known methods can be used.

The power source may be a system using a hydraulic pump or a system using an electric motor (including a linear motor), but a system using a hydraulic pump is more preferable for large molded products. In addition, the injection device
Even if it is an in-line system by advancing a general plasticizing screw, any of a so-called pre-plaster system in which a plasticizing screw and a plunger for filling are separated can be used.

On the other hand, on the surface of the mold, a mold having a sufficient gas vent groove so that the gas inside the mold proceeds smoothly, a porous sintered metal, a vacuum pump through a vent hole, etc. A pressure-reducing device is preferably used.

Incidentally, in the present invention, the injection speed of the resin for the skin layer can be set to various conditions which enable the formation of a sandwich molded product. For example, when the resins join in a molten state, such as when using a joining nozzle, the resin of the skin layer is injected slightly before or almost simultaneously with the resin of the core layer, and the resin of the core layer is defined in the present invention. During the injection at the required injection speed, the resin of the skin layer is continuously filled, and the filling of the resin of the core layer and the resin of the skin layer is completed almost at the same time, or the filling of the resin of the skin layer is completed with a slight delay. Molding under conditions is preferred. The injection speed and the like of the resin of the skin layer may be determined so as to enable such filling.

On the other hand, when the resin of the skin layer and the resin of the core layer are joined at a portion where the resin solidifies, unlike the case of joining in a joining nozzle or a hot runner, for example, the layered resin is formed in a mold cavity. In the case of the sequential injection molding method in which the above-mentioned merging occurs, or in the case of multi-layering at the gate portion through a cold runner, it is preferable to fill the skin layer with a resin at an injection speed of 300 mm / sec or more. More preferably, it is 350 mm / sec or more. Under such conditions, the first skin layer
The solidification of the resin is further suppressed, and the resin is easily drawn in by the flow of the resin in the core layer, so that a thin skin layer can be stably formed. More preferable in the present invention is a simultaneous injection method.

As a result, in the present invention, it is possible to manufacture a molded article having a thin layer structure of the skin layer, which was not sufficiently obtained by the conventional sandwich molding method. Even if sheet insert molding is performed, it is possible to improve the adhesion to the sheet without greatly affecting the overall mechanical properties.

Therefore, according to the present invention, when the total average thickness of the skin layer and the core layer in the molded article having a multilayer structure is 1, the ratio of the average thickness of the skin layer is 0.01 to 0.3.
0 is provided, and provides a method of molding the same. In addition, as a stable lower limit in various thermoplastic resins, the ratio of the average thickness of the skin layer is 0.05, and a more stable lower limit is a value of 0.10, and the distance from the gate to the flow end is 200 mm. Such a thin skin layer can be formed even in a large-sized multilayer structure molded product as described above. Here, the average thickness is represented by a value obtained by dividing a cross-sectional area in the flow path by a flow length (a distance from a gate portion to a flow end portion).

As a molding method for obtaining the product of the present invention, it is possible to use a combination of the molding method of the present invention and injection compression molding, in-mold molding, gas-assist molding and the like.

The thermoplastic resin used as the resin for the skin layer and the resin for the core layer in the present invention includes, for example, polyethylene resin, polypropylene resin, polystyrene resin, polyacrylstyrene resin, ABS resin, AS resin, AES resin, ASA Resin, SMA resin, general-purpose plastics represented by polyalkyl methacrylate resin, polyphenylene ether resin, polyacetal resin, polycarbonate resin, aromatic polyester resin,
Engineering plastics represented by polyamide resin, cyclic polyolefin resin, polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate), etc.
What is called super engineering plastics such as polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, and polyphenylenesulfide can also be used. Further, thermoplastic elastomers such as styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and polyurethane-based thermoplastic elastomer can also be used. Any of these thermoplastic resins can be used as a skin layer and a core layer. The use of a mixture of these thermoplastic resins can be appropriately selected according to the intended use of the composition. Among them, a polycarbonate resin is preferably used because it has excellent heat resistance, mechanical strength, and transparency.

According to the present invention, by improving the affinity between the resin of the sheet layer and the resin of the skin layer, it is possible to obtain a molded article having a good multilayered structure even in a combination having poor adhesion by the conventional sheet insert molding. It is possible to obtain.
Here, as a method of increasing the affinity, (1) a thermoplastic resin of the same type as the resin of the sheet layer is used as the resin of the skin layer, and (2) a thermoplastic resin having a high affinity with the resin of the sheet layer is used. (3) A resin composition comprising a resin for the sheet layer and a resin for the core layer is used. (4) A thermoplastic resin having a high affinity for the sheet layer (or the core layer) and the same type of the core layer (or the sheet layer). Use of a resin composition composed of a thermoplastic resin, and (5) a resin composed of a thermoplastic resin having a high affinity for a sheet layer (or a core layer) and a thermoplastic resin having a high affinity for a core layer (or a sheet layer). It is possible to select from using a composition and the like. For example, solubility parameters can be used as a guide for the quality of the affinity. However, since the present invention is particularly directed to a combination having a low affinity, it is more preferable to use a resin composition. In this case, it is desirable that the compatibility be increased by devising the viscosity ratio of the resins, the reaction between the resins, and the addition of a compatibilizer.

In the present invention, as the core layer, a polycarbonate resin excellent in mechanical strength, heat resistance and the like can be particularly preferably mentioned. On the other hand, the sheet layer forming the surface is excellent in chemical resistance and surface hardness. Resins can be preferably used. Among them, an aromatic polyester resin can be mentioned as one of the preferable resin of the sheet layer. Therefore, according to the present invention, there is provided a multilayered molded article in which the thermoplastic resin forming the core layer in the multilayered molded article is a polycarbonate resin, and the resin forming the sheet layer is an aromatic polyester resin, and such a molding method. Is done.

Here, the skin layer is preferably made of at least one resin selected from an aromatic polyester resin, an aliphatic polyester resin and a thermoplastic polyester elastomer or a resin composition thereof, a polycarbonate resin and / or an acrylic resin. Examples thereof include a resin composition comprising at least one resin selected from an aromatic polyester resin, an aliphatic polyester resin, and a thermoplastic polyester elastomer.

The polycarbonate resin in the present invention is usually obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or a carbonate prepolymer obtained by a solid phase transesterification method. It is a polymerized product or a product obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.

Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4
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 known as bisphenol A), 2,2-bis} (4-hydroxy-3-methyl)
Phenyl {propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dibromo) 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
α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy Diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester and the like, and these may be used alone or in combination of two or more. Can be mixed and used.

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
A homopolymer obtained from at least one bisphenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, or Copolymers are preferred. In particular, bisphenol A homopolymer and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis {(4-hydroxy- Copolymers with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used.

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

In producing the polycarbonate resin by reacting the above-mentioned dihydric phenol with the carbonate precursor by the interfacial polycondensation method or the melt transesterification method, if necessary, a catalyst, a terminal stopper and the oxidation of the dihydric phenol may be used. An inhibitor or 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 bifunctional carboxylic acid, Further, a mixture of two or more of the obtained polycarbonate resins may be used.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-
Dimethyl-2,4,6-tris (4-hydroxydiphenyl) 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) )
Examples thereof include ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, among which 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Ethane is preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

When a polyfunctional compound which produces such a branched polycarbonate resin is contained, the proportion is 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.001 to 1 mol%, based on the total amount of the aromatic polycarbonate. 0.01
~ 0.3 mol%. In addition, particularly in the case of the melt transesterification method, a branched structure may be generated as a side reaction, and the amount of such a branched structure is also 0.001 to 1 mol%, preferably 0.005 to 5 mol%, of the total amount of the aromatic polycarbonate.
0.5 mol%, particularly preferably 0.01 to 0.3 mol%
Is preferred. The ratio is ¹ H
-It can be calculated by NMR measurement.

The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and 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, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, for promoting the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, and the resulting polycarbonate resins are capped by groups based on monofunctional phenols, so that Excellent heat stability. Such a monofunctional phenol is generally a phenol or a lower alkyl-substituted phenol, and may be a monofunctional phenol represented by the following general formula (1).

[0060]

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(Wherein A is a hydrogen atom or a carbon number of 1 to 9)
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, for example, phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

Further, other monofunctional phenols include:
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 used. Among these, phenols having a long-chain alkyl group represented by the following general formulas (2) and (3) as a substituent are preferably used.

[0063]

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[0064]

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

As such substituted phenols of the general formula (2), those having n of 10 to 30, especially 10 to 26, are preferred. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol and Octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol and the like can be mentioned.

As the substituted phenols of the general formula (3), a compound in which X is -R-CO-O- and R is a single bond is suitable, and n is 10 to 30, especially 10 to 26.
Are preferred, and specific examples thereof include, for example, decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Examples include tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate.

The terminal terminator is desirably introduced at least 5 mol%, preferably at least 10 mol%, based on all terminals of the obtained polycarbonate resin. More preferably, the terminal terminator is introduced in an amount of 80 mol% or more with respect to all terminals, that is, the terminal hydroxyl group (OH group) derived from dihydric phenol is more preferably 20 mol% or less, and particularly preferably. This is the case when 90 mol% or more of the terminal terminator is introduced to all the terminals, that is, when the OH group is 10 mol% or less. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol with the carbonate ester while heating in the presence of an inert gas. It is performed by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C. In the late stage of the reaction, the system was adjusted to 1.33 × 10 ³ -1.
The alcohol or phenol produced by reducing the pressure to about 3.3 Pa is easily distilled. Reaction time is usually 1-4
About an hour.

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

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium and potassium salts of dihydric phenol, 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 Manganese, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds 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. The amount of the polymerization catalyst used is preferably 1 × 10 ⁻⁸ to 1 ×, based on 1 mol of the dihydric phenol used as the raw material.
It is selected in the range of 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents.

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 is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
It is preferable to add compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate, and ethoxycarbonylphenylphenyl carbonate. Of these, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred, and 2-methoxycarbonylphenylphenyl carbonate is particularly preferred.

Further, in the melt transesterification method, it is desirable to neutralize the activity of the catalyst remaining after polymerization by using a deactivator. Examples of such a deactivator include benzenesulfonic acid, p-toluenesulfonic acid, methylbenzenebenzenesulfonate, ethylbenzenebenzenesulfonate, butylbenzenesulfonate, octylbenzenesulfonate, phenylbenzenesulfonate, methyl p-toluenesulfonate, p-toluenesulfonate -Sulfonic esters such as ethyl toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate;
Trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene, methyl acrylate-sulfonated styrene copolymer, 2-phenyl-2-propyl dodecylbenzenesulfonic acid, 2-phenyl-2-butyl dodecylbenzenesulfonic acid, Tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, Dodecylbenzenesulfonic acid tetraoctyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, Silammonium methyl sulfate, 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, Examples include compounds such as tetraethylammonium dodecylbenzyl sulfate and tetramethylammonium dodecylbenzyl sulfate, but are not limited thereto, and two or more of these compounds may be used in combination.

Among them, phosphonium salts or ammonium salts are preferred. The amount of such a catalyst is preferably 0.5 to 50 mol per 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 to 500 ppm, based on the polycarbonate resin after polymerization. 0.01 to 300 ppm, particularly preferably 0.01 to 300 ppm
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 properties and the like will be reduced. 10,00
0-40,000 is preferable, and 14,000-3
Particularly preferred are those having a molecular weight of 0000. Also, two or more polycarbonate resins may be mixed. The viscosity average molecular weight in the present invention is determined by inserting the specific viscosity (η _SP ) obtained from a solution of 0.7 g of a polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C. into the following equation. η _SP /c=[η]+0.45×[η] ² c (where [η]
Is the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

The aromatic polyester resin of the present invention is a polymer or copolymer obtained by a condensation reaction comprising an aromatic dicarboxylic acid or a reactive inducer thereof and a diol or an ester derivative thereof as main components. .

The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-
Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-
Biphenyl ether dicarboxylic acid, 4,4'-biphenylmethane dicarboxylic acid, 4,4'-biphenyl sulfone dicarboxylic acid, 4,4'-biphenyl isopropylidene dicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4′-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4 ′
Aromatic dicarboxylic acids such as -p-terphenylenedicarboxylic acid and 2,5-pyridinedicarboxylic acid are preferably used, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferably used.

Two or more aromatic dicarboxylic acids may be used as a mixture. In addition, if it is a small amount, it is also possible to use one or more kinds of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecane diacid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid together with the dicarboxylic acid. .

The diol which is a component of the aromatic polyester of the present invention includes ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, 2-methyl -1,3-propanediol, aliphatic diols such as diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and fragrances such as 2,2-bis (β-hydroxyethoxyphenyl) propane Ring-containing diols and the like, and mixtures thereof, and the like. If the amount is further small, one or more long-chain diols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, or the like may be copolymerized.

The aromatic polyester of the present invention can be branched by introducing a small amount of a branching agent.
The type of the branching agent is not limited, and examples thereof include trimesic acid, trimellitic acid, trimethylolethane, trimethylolpropane, and pentaerythritol.

Specific aromatic polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene -1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, and the like,
Copolymerized polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate and the like can be mentioned. Among them, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and a mixture thereof having a good balance of mechanical properties and the like are preferable, and polybutylene terephthalate: polyethylene terephthalate is more preferably 9: 9 by weight. 1 to
1: 9, particularly preferably 8: 2-
The mixture was mixed at a ratio of 2: 8.

The structure of the terminal group of the obtained aromatic polyester resin is not particularly limited, except that the ratio of the hydroxyl group and the carboxyl group in the terminal group is almost the same, and that one of the ratios is large. You may. Further, the terminal groups may be blocked by reacting a compound having reactivity with such terminal groups.

According to a method for producing such an aromatic polyester resin, a dicarboxylic acid component and the diol component are polymerized while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony and the like according to a conventional method.
It is performed by discharging water or lower alcohol produced as a by-product outside the system. For example, examples of the germanium-based polymerization catalyst include oxides, hydroxides, halides, alcoholates, and phenolates of germanium, and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, and the like. Can be exemplified.

In the present invention, compounds such as manganese, zinc, calcium, and magnesium used in a transesterification reaction which is a prior stage of a conventionally known polycondensation can be used in combination, and phosphoric acid is added after the transesterification reaction is completed. Alternatively, it is also possible to deactivate such a catalyst with a phosphorous acid compound or the like to perform polycondensation.

The molecular weight of the aromatic polyester resin is not particularly limited, but the intrinsic viscosity measured at 25 ° C. using o-chlorophenol as a solvent is 0.4 to 1.
2, preferably 0.65 to 1.15.

A release agent can be added to the thermoplastic resin of the present invention (including any of the sheet layer, skin layer and core layer). As the release agent, a saturated fatty acid ester is generally used. Esters, higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used. The release agent is 0.01 to 100 parts by weight of the thermoplastic resin.
1 part by weight is used.

The thermoplastic resin of the present invention (sheet layer,
If necessary, a phosphorus-based heat stabilizer can be added to the skin layer and the core layer. As the phosphorus-based heat stabilizer, a phosphite compound and a phosphate compound are preferably used. Examples of the phosphite compound include triphenyl phosphite, trisnonylphenyl phosphite, and tris (2,4-di-ter
(t-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl Diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-te
rt-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-
Examples thereof include phosphite compounds such as di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite. Of these, tris (2,4-di-tert-butylphenyl) phosphite, distearylpentaerythritol diphosphite, and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite are preferred.

On the other hand, examples of the phosphate compound used as a heat stabilizer include tributyl phosphate,
Trimethyl phosphate, tricresyl phosphate,
Triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like, among which triphenyl phosphate, trimethyl phosphate preferable.

Further, other phosphorus-based heat stabilizers include tetrakis (2,4-di-tert-butylphenyl)-
4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3 '
-Biphenylenediphosphonite, tetrakis (2,4-
Phosphonite compounds such as di-tert-butylphenyl) -3,3′-biphenylenediphosphonite and bis (2,4-di-tert-butylphenyl) -4-biphenylenediphosphonite can also be preferably used.

The phosphorus-based heat stabilizers may be used alone or in combination of two or more. The phosphorus-based heat stabilizer is used in an amount of 0.0001 to 1.0 part by weight, preferably 0.001 part by weight, based on 100 parts by weight of the thermoplastic resin of the present invention.
1 to 0.5 part by weight, more preferably 0.005 to 0.1 part
It is appropriate to use in the range of parts by weight.

The thermoplastic resin of the present invention (including any of the sheet layer, the skin layer and the core layer) may contain an antioxidant generally known 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-t
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-hexamethylenebis (3,5-di-t
tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-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. The preferable range of the addition amount of these antioxidants is 0.0001 to 5 parts by weight, preferably 0.001 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin.
0.5 parts by weight.

For the purpose of improving weather resistance and cutting harmful ultraviolet rays, the thermoplastic resin of the present invention (including any of the sheet layer, skin layer and core layer) is further blended with an ultraviolet absorber and a light stabilizer. can do. Examples of such an ultraviolet absorber include a benzophenone-based ultraviolet absorber represented by, for example, 2,2′-dihydroxy-4-methoxybenzophenone, and, for example, 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-benzo Triazole and 2- (3,
5-di-tert-amyl-2-hydroxyphenyl)
A benzotriazole-based ultraviolet absorber represented by benzotriazole is exemplified. Further screws (2, 2, 6, 6
Hindered amine light stabilizers such as -tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate can also be used. These may be used alone or in combination of two or more. The preferable range of the addition amount of these ultraviolet absorbers and light stabilizers is 0.0001 to 10 parts by weight, preferably 0.010 parts by weight, per 100 parts by weight of the thermoplastic resin.
It is 01 to 5 parts by weight.

The thermoplastic resin of the present invention (sheet layer,
A bluing agent can be blended into the skin layer and the core layer (including both layers) in order to cancel a yellowish color due to an ultraviolet absorber or the like. It is particularly useful for polycarbonate resins. As a specific bluing agent, for example, a common name Solvent Violet 13
[CA. No (color index No) 60725;
Brand name “Macrolex Violet B” manufactured by Bayer, “Diaresin Blue G” manufactured by Mitsubishi Chemical Corporation, “Sumiplast Violet B” manufactured by Sumitomo Chemical Co., Ltd.], Solvent Violet 31 [C]
A. No. 68210; Trade name “Diaresin Violet D” manufactured by Mitsubishi Chemical Corporation], generic name Solvent
Violet 33 [CA. No. 60725; Trade name “Diaresin Blue J” manufactured by Mitsubishi Chemical Corporation], generic name S
solvent Blue 94 [CA. No61500;
Trade name: Mitsubishi Chemical Corporation "Diaresin Blue N"], Generic name: Solvent Violet 36 [C
A. No. 68210; brand name “Macrolex Violet 3R” manufactured by Bayer AG], generic name Solvent
Blue97 [trade name “Macrolex Blue RR” manufactured by Bayer AG] and generic name Solvent Blue
45 [CA. No. 61110; Trade name “Tetrazol Blue RLS” manufactured by Sando Co., Ltd.], Ciba Specialty
Examples include Macrolex Violet and Triazole Blue RLS of Chemicals.

The thermoplastic resin (including any of the sheet layer, the skin layer and the core layer) of the present invention may further contain other conventional additives such as reinforcing agents (talc, mica, clay,
Wollastonite, calcium carbonate, glass fiber, glass beads, glass balloon, milled fiber, glass flake, carbon fiber, carbon flake, carbon beads, carbon milled fiber, metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber , 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, phosphate, metal salt) , Red phosphorus, silicon-based, fluorine-based, metal hydrate-based, etc., heat-resistant agents, coloring agents (pigments and dyes such as carbon black and titanium oxide), light diffusing agents (acrylic cross-linked particles, silicon cross-linked particles, ultra-thin) Glass flakes, calcium carbonate particles, etc.) For fluorescent whitening agent, luminous pigment, fluorescent dye, antistatic agent, flow modifier, crystal nucleating agent, inorganic and organic antibacterial agent, photocatalytic antifouling agent (fine particle titanium oxide, fine particle zinc oxide, etc.), graft rubber Representative impact modifiers, infrared absorbers, and photochromic agents can be blended. Particularly when it is necessary to contain a large amount of inorganic filler, it is preferable to include the inorganic filler in the resin of the core layer.

In the present invention, among the above-mentioned reinforcing agents, in combination with a polycarbonate resin, a glass filler having a difference in refractive index from the polycarbonate resin of 0.015 or less can be preferably mentioned. Such a glass-based filler has a glass composition different from that of a conventional glass, does not contain boron oxide and fluorine which are glass fluxes, contains titanium oxide and zirconium oxide, and raises the refractive index of the glass. This is a glass with improved properties. As the glass shape, fibers, beads, flakes, various shapes such as milled fiber can be used,
In particular, fibers and flakes are preferred.

As the reinforcing agent, those which have been surface-treated with various coupling agents such as a silane coupling agent and a titanate coupling agent can be used. Particularly, a glass filler can be preferably used.

According to the present invention, defects such as the occurrence of defects in the printed layer and the lack of uniformity due to the damage of the interface are caused by sheet insert molding of a thermoplastic resin containing a reinforcing agent such as an inorganic filler. It also makes it possible to solve problems. That is, by using a thermoplastic resin containing a reinforcing agent such as an inorganic filler for the core layer, it is possible to prevent the reinforcing agent from directly damaging the printed layer on the sheet surface or the sheet itself. In particular, it is effective in combination with an amorphous thermoplastic resin requiring transparency and a glass-based filler having a small refractive index difference between such a resin and a polycarbonate resin, more preferably a refractive index difference between the polycarbonate resin and the polycarbonate resin. In a combination with a glass filler having a particle size of 0.015 or less, the production method of the present invention can be said to be effective, and to obtain a molded article having a better appearance and excellent transparency and rigidity than can be obtained conventionally. Becomes possible.

That is, according to the present invention, there is provided a multilayer-structured molded article having a good appearance, in which the thermoplastic resin forming the core layer in the multilayer-structured molded article contains an inorganic filler. Provided is a resin composition comprising a glass-based filler having a refractive index difference of 0.015 or less from a polycarbonate resin, and provides a multilayer molded article having good appearance, excellent transparency and rigidity.

Further, as the thermoplastic resin (including any layers) of the present invention, a resin already formed as a product or a component, that is, a so-called recycled material can be used. In particular, it is preferable to use a recycled material as the core layer. Such a recycled material often has a coating film for coloring, abrasion resistance, antistatic properties, various functional coatings such as heat ray absorption, and a laminated film such as a metal film formed by vapor deposition, sputtering, plating or the like. These can be used either with the laminated film attached or with the laminated film removed.

For example, when an optical information recording medium having a polycarbonate resin as a substrate is used as a recycle material, these may be used as they are after being subjected to a pulverizing treatment or the like. And / or can be used by mixing with recycled materials of other thermoplastic resin materials.

On the other hand, it is also possible to selectively remove the information recording layer, the reflective layer and the protective coating layer from the optical information recording medium from the resin substrate and recover and use the resin itself. Several suggested methods shown can be used.

(I) JP-A-4-305414 (European Patent No. 476,475, US Pat. No. 5,151,4)
52), JP-A-5-200379 (European Patent No. 537,567, U.S. Patent No. 5,214,072)
And JP-A-6-223416 (European Patent No. 60
1,719, U.S. Pat. No. 5,306,349): These methods involve chemically treating the coated resin plate with, for example, an aqueous acid or alkali solution.

(Ii) JP-A-5-345321:
This method is a method of immersing the coated resin plate in hot water for a long time.

(Iii) JP-A-5-210873 and US Pat. No. 5,203,067: These methods mechanically cut the surface of a coating layer of a coated resin plate using a blade or an abrasive. It is a method of removing by polishing.

(Iv) JP-A-10-52823 and JP-A-10-58450: Such a method removes a substrate resin by contacting a rolled recording medium with heated water to remove and remove a coating film. It is a method of collecting. Such a method is particularly low cost, and is a good method in terms of quality and recovery rate.

Other examples include a method of blasting the surface of the optical information recording medium and a method of irradiating the optical information recording medium with ultrasonic waves (JP-A-11-34057).

[0107]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. The evaluation was performed by the following method. (1) Appearance The appearance of the whole molded article was evaluated by visual observation. ：: Uniform and good appearance without both bright spots and printing scratches of × below ×: Bright spots or scratches on the printed surface are observed at the interface when the angle is changed by seeing through the light source of a fluorescent lamp .

(2) Measurement of Skin Layer Thickness and Core Layer Thickness The obtained molded product was cut along the center line (see FIG. 1) in the flow direction. The thickness of the skin layer and the core layer at the section 3 cm from the flow end and 3 cm from the gate of the molded article main body in such a cross section was measured from a 10-fold enlarged photograph.

(3) Evaluation of Interface Adhesion A sample (13 cm in length and 1 cm in width) for evaluating interface adhesion was cut out from the portion shown in FIG. And the sample layer is fixed to the lower jig, and the load (N) in the steady state when the sheet layer is peeled off at 20 mm / min in the vertical direction is measured. Thereby, the adhesion between the sheet layer and the molded article main body was evaluated. UCT-1T manufactured by Orientec Co., Ltd. was used for the measurement. In addition, the sample in which the sample was broken regardless of the peeling was not recorded (indicated by “表” in Table 1).

(4) Surface Impact Strength 23 ° C., 50%
Under a RH atmosphere, a high-speed surface impact tester is used at a punching speed of 7 m / sec using a punch for punching with a semicircular tip and a radius of 1/4 inch, and a circular cradle with a radius of 1/2 inch. (Hydroshot HT manufactured by Shimadzu Corporation)
Using M-1), the punch was made to collide with the center part of the substantially plate-shaped molded product, and the energy (J) required to break through the sample was measured.

The thermoplastic resin sheets and thermoplastic resins used in the examples are as follows, and will be described below according to their symbols. (Thermoplastic resin (first resin) sheet forming the sheet layer) (i) PET-S: Using polyethylene terephthalate of [η] = 0.80, 3.6 times in the vertical direction, and then 105 times in the horizontal direction. A 100-μm-thick polyethylene terephthalate sheet obtained by stretching 3.7 times at ℃ and heat setting at 235 ° C.

(Ii) PC-S: a polycarbonate resin sheet obtained by the following production method. That is, 0.02 parts by weight of Irgafos 168 (manufactured by Nippon Ciba Geigy) and 0.02 parts by weight of pentaerythritol tetrastearate were added to 100 parts by weight of a polycarbonate resin having a viscosity average molecular weight of 25,000, which was prepared from bisphenol A and phosgene by an ordinary method. 2 parts by weight, 1 part by weight of Chemisorb 79 (manufactured by Chemipro Kasei Co., Ltd.) as a UV absorber, Macrolex Violet B (manufactured by Bayer)
0.0003 parts by weight, under a reduced pressure of 1330 Pa,
The resin was melt-extruded at 280 ° C. by a T-die extruder having a gear pump to obtain a polycarbonate resin sheet having a thickness of 0.5 mm. After silicon hard coat treatment on one surface. The printing of the pattern shown in FIG. 1 on the other surface is made uniform by mixing the ink [Natsuda 70-9132: color 136D smoke] and the solvent [isophorone / cyclohexane / isobutanol = 40/40/20 (wt%)]. , Printing on silk screen printing machine,
Dry at 100 ° C. for 60 minutes. The hard coat treatment was performed as described in the following Reference Examples.

(Thermoplastic resin forming the skin layer and the core layer) (i) PC: 100 parts by weight of a polycarbonate resin having a viscosity average molecular weight of 18,500 prepared from bisphenol A and phosgene by a conventional method, and Sandstab P-EP
Q (manufactured by Sandoz) 0.03 parts by weight,
And 0.2 parts by weight of glycerin monostearate were blended and melt-extruded at 280 ° C. under a reduced pressure of 1330 Pa using a vented 30φ single screw extruder (VSK-30 manufactured by Freesia Macross Co., Ltd.). Polycarbonate resin.

(Ii) PC-G: a viscosity-average molecular weight of 18, prepared from bisphenol A and phosgene by a conventional method.
100 parts by weight of 500 polycarbonate resin at 120 ° C.
After drying with a hot air drier for 5 hours, Sandst
ab P-EPQ (manufactured by Sandoz)
0.03 parts by weight, 2.5 parts by weight of polycaprolactone (Placcel H1P manufactured by Daicel Chemical Co., Ltd.), a bluing agent (Macrolex Violet B (manufactured by Bayer)) and glass flakes having a refractive index nd of 1.590 ( A thickness of 5 μm, an average particle diameter of 200 μm calculated as a median diameter by a standard sieve method, and an average particle diameter / thickness of 40, 20 parts by weight of Nippon Sheet Glass Co., Ltd.
Single screw extruder (VSK-3 manufactured by Freesia Macross, Inc.)
0) A pellet-shaped polycarbonate resin obtained by melt-extrusion under a reduced pressure of 1330 Pa at a cylinder temperature of 280 ° C.

(Iii) RecPC: Recycled polycarbonate resin obtained by the following steps. Polycarbonate resin substrate of bisphenol A with a viscosity average molecular weight of 15,100, water absorption of 0.20% by weight and dihydric phenol component (1.2 mm) / aluminum deposition layer (0.1 μm) / UV
Coating layer (5-10 μm) / label printing layer (20 μm
The resin substrate A (diameter: 12 cm) having the configuration of m) was rolled by a two-roll machine manufactured by Otake Machine Industry Co., Ltd., having a roll gap of 0.4 mm and a surface temperature of 130 ° C. The rolling conditions at this time were as follows: roll rotation speed = high-speed side 16 rpm;
Low-speed side 14 rpm, roll diameter = 12 inches, roll width =
24 inches. Next, it was immersed in heated water of 95 ° C. for 45 minutes as a hot water treatment and stirred while swelling. At this time, the ratio of the resin substrate was 3% by weight based on the total of the resin substrate and the heated water, and the coating component was removed. Next, the substrate was washed with water to recover the transparent polycarbonate resin substrate from which the coating components had been removed. The obtained polycarbonate resin substrate was pulverized, and the pulverized material was melt-extruded using a vented 30φ single screw extruder (VSK-30 manufactured by Freesia Macross Co., Ltd.) to obtain pellets.

(Iv) PC-PET: 30 parts by weight of polyethylene terephthalate resin (TR-8580, manufactured by Teijin Limited, intrinsic viscosity 0.8) and 70 parts by weight of polycarbonate resin (Panlite L-1225, manufactured by Teijin Chemicals Ltd.) The part was dried using a hot air drier at 120 ° C. for 5 hours, and then titanium oxide (Taipeku PC-3, manufactured by Ishihara Sangyo Co., Ltd.) was added to 0.1 part.
05 parts by weight and 0.2 parts by weight of Irgafos 168 (manufactured by Nippon Ciba Geigy Co., Ltd.)
φ single screw extruder (VSK-3 manufactured by Freesia Macross, Inc.)
A thermoplastic resin composition obtained by melt-extrusion using 0) at a cylinder temperature of 280 ° C. under a reduced pressure of 1330 Pa.

(V) PC-PCL: 15 parts by weight of polycaprolactone (Placcel H1P manufactured by Daicel Chemical Co., Ltd.), 85 parts by weight of polycarbonate resin (Panlite L-1225 manufactured by Teijin Chemicals Limited), and Irgafos
168 (manufactured by Nippon Ciba Geigy Co., Ltd.), and a cylinder temperature of 260 ° C. under reduced pressure of 1330 Pa using a 30φ single screw extruder (VSK-30 manufactured by Freesia Macross Co., Ltd.) with a vent. The thermoplastic resin composition obtained by melt extrusion. (Vi) PMMA: 100 parts by weight of polymethyl methacrylate resin (Delpet 80N manufactured by Asahi Kasei Corporation)
1 part by weight of SANOL LS770 (manufactured by Sankyo) and
2 parts by weight of Chemisorb 79 (manufactured by Chemipro Kasei Co., Ltd.) were blended, and using a vented 30φ single screw extruder (VSK-30 manufactured by Freesia Macross Co., Ltd.) under a reduced pressure of 1330 Pa and a cylinder temperature of 260 ° C. A thermoplastic resin composition obtained by melt extrusion.

REFERENCE EXAMPLE (Hard coat treatment method) 70 parts of methyl methacrylate (hereinafter abbreviated as MMA) and 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA) were provided in a nitrogen-purged flask equipped with a reflux condenser and a stirrer. Do) 39 copies,
0.18 parts of azobisisobutyronitrile (hereinafter abbreviated as AIBN) and 200 parts of 1,2-dimethoxyethane were added, mixed and dissolved. Next, 70 ° C. in a nitrogen stream
For 6 hours with stirring. The obtained reaction solution was added to n-hexane and purified by reprecipitation to obtain 90 parts of a copolymer (acrylic resin (I)) having a composition ratio of MMA / HEMA of 70/30 (molar ratio). The weight average molecular weight of the copolymer was measured by GPC (column; Shodex GPCA-8).
04, eluent; THF) from polystyrene equivalent 80,
000.

Further, methyltrimethoxysilane 142
Parts, 72 parts of distilled water and 20 parts of acetic acid were mixed under cooling with ice water,
The mixture was stirred at 25 ° C. for 1 hour and diluted with 116 parts of isopropanol to obtain 350 parts of a solution (X) of a hydrolyzed condensate of methyltrimethoxysilane. On the other hand, 208 parts of tetraethoxysilane and 81 parts of 0.01 N hydrochloric acid are mixed under cooling with ice water, the mixture is stirred at 25 ° C. for 3 hours, diluted with 11 parts of isopropanol, and a solution of the hydrolyzed condensate of tetraethoxysilane ( Y) 300 parts were obtained.

Next, as the composition for the first layer of the hard coat,
8 parts of the acrylic resin (I) is methyl ethyl ketone 40
Parts, methyl isobutyl ketone 20 parts, ethanol 5.2
, 14 parts of isopropanol and 10 parts of 2-ethoxyethanol, and then dissolved in a solution of the hydrolyzed condensate of methyltrimethoxysilane (X).
10 parts were added and stirred at 25 ° C. for 5 minutes, and the solution was further added to a melamine resin (Cymel 3 manufactured by Mitsui Cytec Co., Ltd.).
03) 1 part was added and the mixture was stirred at 25 ° C for 5 minutes to prepare a coating composition (i).

Further, as the composition for the second layer of the hard coat,
Water-dispersed colloidal silica dispersion (Nissan Chemical Industries, Ltd.)
Made Snowtex 30 solid content concentration 30% by weight) 10
To 12 parts of distilled water and 20 parts of acetic acid were added and stirred.
4 parts were added. This mixture was stirred at 25 ° C. for 1 hour. To the reaction mixture obtained, 20 parts of a tetraethoxysilane hydrolyzed condensate solution (Y) and 1 part of sodium acetate as a curing catalyst were added, diluted with 200 parts of isopropanol, and coated. Composition (ii) was prepared.

The coating composition (i) was applied to one surface of a 0.5 mm thick polycarbonate resin sheet with a wire bar, allowed to stand at 25 ° C. for 20 minutes, and then thermally cured at 120 ° C. for 30 minutes. The thickness of the first layer was 2.5 μm. Then, the coating composition (i
i) was further applied with a wire bar, left standing at 25 ° C. for 20 minutes, and thermally cured at 120 ° C. for 2 hours. The thickness of the second layer was 5.0 μm.

Example 1 The above-mentioned PC-PET was used as a resin for a skin layer and PC was used as a resin for a core layer.
After drying at 20 ° C. for 5 hours, two ultra-high-speed injection devices having a cylinder inner diameter of 50 mm φ capable of achieving an injection speed of 600 mm / sec, and an ultra-high-speed injection device having a concentric double-tube V-shaped merging nozzle Sandwich molding was performed using a sandwich molding machine (FN-8000-36ATN manufactured by Nissei Plastic Industry Co., Ltd.).

At the position shown in FIG. 1, PET-S having a 50 μm-thick household aluminum foil stuck thereto (three places) using a double-sided tape for stationery was charged on the surface and mounted on the mold core surface. After closing the mold, vacuum pump (Nihon Vacuum Technology Co., Ltd.)
ULVAC PMB006CM mechanical booster and EC803 rotary pump)
, And after evacuation for 10 seconds, molding was performed. The evacuation was performed through a gas vent clearance provided around the mold cavity.

The molding conditions are as follows: the cylinder temperature of the injection device 1 for the skin layer is 290 ° C .;
The injection device 1 measures at a back pressure of 19.6 MPa, the injection device 2 measures at a back pressure of 9.8 MPa, the injection speed of the injection device 2 is 350 mm / sec under a constant injection speed, The injection speed of the injection device 1 is 65 mm
/ Sec, the injection device 1 is injected in advance, the filling of the injection device 2 is started at about 40% of the total metering, and the filling is completed almost at the same time (simultaneous injection condition). Was molded. The molded product body is a plate-shaped molded product having a length of 210 mm, a width of 180 mm, and a thickness of 5 mm, and has a film gate (a thickness of the gate portion of 1.5 mm).
mm) (see FIG. 2). The mold temperature was maintained at 70 ° C. using a mold temperature controller. Table 1 shows the evaluation results.

[Comparative Example 1] Molding was performed under the same conditions as in Example 1 except that the conditions of the injection speed were changed to the following conditions.
That is, the injection speed of the injection device 2 is set to 50 under the condition that the injection speed is constant.
The molding was performed with the injection speed of the injection device 1 set to 10 mm / sec so as to satisfy the conditions for simultaneous injection.
In the obtained molded product, a so-called break phenomenon occurs in which the core resin breaks through the skin resin and appears on the surface of the molded product, and a sufficient sandwich molded product was not obtained. Table 1 shows the evaluation results.

[Comparative Example 2] The injection speed of injection speed 2 was set to 50.
The molding conditions were adjusted so that the break phenomenon did not occur at mm / sec. That is, the injection speed is set to 50 mm / sec together with the injection device 1 and the injection device 2, the injection device 1 is injected in advance, and the charging of the injection device 2 is started at about 20% of the total metering, and the charging is performed almost simultaneously. Molding was performed under the complete molding conditions (simultaneous injection conditions). The weighing was changed in accordance with the filling amount and the filling was performed, but other conditions were substantially the same as in Example 1. In this case, no break phenomenon occurred. Table 1 shows the evaluation results.

[Comparative Example 3] Without sandwich molding,
Molding was performed under substantially the same conditions as in Example 1 except that only the injection device 2 was used and only PC was filled. The weighing was changed according to the filling amount. Table 1 shows the evaluation results.

[Examples 2 and 3] Molding was performed in the same manner as in Example 1 except that PC-G or RecPC was used as the resin for the core layer, and PC-PCL was used as the resin for the skin layer. . The PC-PCL was dried at 80 ° C. for 8 hours. Table 2 shows the evaluation results.

[Examples 4 and 5] Molding was carried out in the same manner as in Example 1 except that PC-G or RecPC was used as the resin for the core layer and PC was used as the resin for the skin layer. Table 2 shows the evaluation results.

[Comparative Example 4] No sandwich molding was performed.
Molding was performed under substantially the same conditions as in Example 4, except that only the injection device 2 was used to fill only PC-G. The weighing was changed according to the filling amount. Table 2 shows the evaluation results.

Example 6 As a resin for the core layer, PC-
G, and PMMA as a resin for the skin layer.
0 mm / sec, the injection speed of the injection device 1 is 75 mm / s
The molding was performed in the same manner as in Example 1 except that molding was performed as ec. Table 2 shows the evaluation results.

[0133]

[Table 1]

[0134]

[Table 2]

As is clear from Table 1, when the injection speed of the resin forming the core layer is insufficient, it is difficult to form a thin skin layer, and a good laminate cannot be obtained. In such a case, both the adhesion and the strength become insufficient. On the other hand, it can be seen that if the layer configuration is made possible at a normal injection speed, a molded article having a multilayer structure having properties such as sufficient strength cannot be obtained. Further, when the sandwich molding method is used, a multilayer structure molded product having good adhesion can be obtained even when the adhesion of the sheet layer to the interface side resin is weak, and the molded product is filled in the mold cavity. It can be seen that even when the resin contains an inorganic filler, a molded article having a good appearance with a multilayer structure can be obtained.

[0136]

According to the present invention, it is possible to impart a specific function or design to the surface and to produce a multilayer-structured molded product satisfying the mechanical characteristics and the like according to the purpose with a high degree of freedom. At the same time, it is possible to obtain a molded article having a multilayer structure excellent in the adhesion between the layers and also excellent in appearance. Products obtained by such a manufacturing method are required to be functional in a surface such as an optical field such as an automobile glazing product, an optical lens, and an optical filter, and are required to be entirely transparent. Design and strength, such as boards, interior materials, exterior materials for various electric, electronic, and OA equipment, etc.
It is extremely suitable for the field where compatibility with flame retardancy is required, the field of resin recycling material, and the like, and the industrial effect achieved is extremely large.

[Brief description of the drawings]

FIG. 1 is a front view schematically showing an outline of a plate-like molded product.

FIG. 2 is a side view schematically illustrating an outline of a gate portion of a plate-shaped molded product.

FIG. 3 is a schematic view of a mold structure as viewed from the side.

[Description of Signs] 1 Plate-shaped molded product main body 2 Plate-shaped molded product gate portion (width: 180 mm) 3 Plate-shaped molded product runner portion (width: 195 mm) 4 Plate-shaped molded product width (180 mm) 5 Plate-shaped molded product Length (210 mm) 6 sprue part 7 length of discarded cab part (25 mm) 8 length of thin (2 mm) part of discarded cabine part (5 mm) 9 sample cutout part for adhesion test -1 (plate shape) A portion surrounded by a dotted line with the right end and the upper portion as end surfaces when the molded product is viewed from the front: a length of 130 mm and a width of 10 mm) 10 A portion of the sample cut-out portion for adhesion test 1 where an aluminum foil is stretched (length) 11 Sample cut-out part-2 for adhesion test (corresponding to the center when the plate-like molded product is viewed from the front, a portion surrounded by a dotted line having the upper end as an end face: length 130 mm, width 10 mm) 12 adhesion 13 Sample cut-out part-2 (length: 5 cm) of test sample cut-out part-2 13 Sample cut-out part-3 for adhesion test (dotted line with the left end and the upper end as viewed from the front of the plate-like molded product, respectively) (Enclosed part: length 130 mm, width 10 mm) 14 The part where the aluminum foil of the sample cutout part 3 for adhesion test was stretched (length 5 cm) 15 Printing on the back surface of the thermoplastic resin sheet 16 Plate-shaped molded product runner part Thickness (5 mm) 17 Plate-shaped molded product runner part height (14 mm) 18 Plate-shaped molded product sprue diameter at runner (8 m)
m) 19 Length of sprue (100 mm) 20 Gate length of plate-shaped molded product (7 mm) 21 Gate thickness of plate-shaped molded product (1.5 mm) 22 Gate thickness of plate-shaped molded product (1.5 mm) 23 Thickness of molded product body (5mm) 24 Mold part disposal mold part length -1 (thin side: 1
0 mm) 25 Mold part disposal mold part length -2 (thick side: 2
0 mm) 26 Mold part disposal mold part thickness -1 (thin side: 2
mm) 27 Mold part disposal mold part thickness -2 (thick side: 5)
28) 28 Fixed side mold for plate-shaped molded product 29 Upper block of movable mold for plate-shaped molded product 30 Lower block of movable mold for plate-shaped molded product 31 Hole for exhaust / decompression by vacuum pump 32 Mold core block 33 Resin sheet 34 Skin layer of plate-shaped product 35 Core layer of plate-shaped product

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) B29L 9:00 B29L 9:00

Claims (5)

[Claims] 1. A molding method for obtaining a molded article having a multilayer structure by a sandwich molding method of a thermoplastic resin, wherein (1) a thermoplastic resin in which a sheet layer is previously formed on a surface of a mold cavity and / or a surface of a mold core. Attach the seat and (2)
The injection speed at the time of filling the thermoplastic resin forming the skin layer and the thermoplastic resin forming the core layer into the mold cavity in which the sheet is mounted is 300 mm / sec or more when filling the thermoplastic resin forming the core layer. A molding method for obtaining a multilayer molded article having a sheet layer, a skin layer and a core layer by filling under the following conditions. 2. The multilayer molded article according to claim 1, wherein the ratio of the average thickness of the skin layer is 0.01 to 0.30 when the total average thickness of the skin layer and the core layer is 1. A molding method for obtaining a multilayer molded article. 3. The multi-layer structure molded article according to claim 1, wherein the thermoplastic resin forming the core layer is a polycarbonate resin, and the resin forming the sheet layer is an aromatic polyester resin. Molding method for obtaining a multilayer molded article of the above. 4. The molding method according to claim 1, wherein the thermoplastic resin forming the core layer in the multilayer structure molded article contains an inorganic filler. 5. A molded article having a multilayer structure obtained by the molding method according to claim 1. Description: