JPH0985903A - Thermal resin laminate and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin laminate improved in appearance inferiority caused by the disturbance of a lamination interface. SOLUTION: In a thermoplastic resin laminate wherein a thermoplastic resin 2 (B) is laminated on at least the single surface of a thermoplastic resin 1 (A) through a bonding layer, the thickness of the bonding layer is 0.1-2μm and the max. difference of undulation thereof is 10μm or less per a width of 5mm and the bonding layer 3 is the thermoplastic resin laminate being the mixed layer of the thermoplastic resin 1 (A) and the thermoplastic resin 2 (B). Further, the thermoplastic resin laminate has the bonding layer formed by simultaneously molding the thermoplastic resin (A) and the thermoplastic resin (B) of which the melt flow rate is 0.5-2 times that of the thermoplastic resin (A). Further, the thermoplastic resin laminate consists of the thermoplastic resin (A) composed of a polycarbonate resin and the thermoplastic resin (B) composed of an acrylic resin and a laminated sheet consists of thermoplastic resins (A), (B) wherein the thickness of the layer of the thermoplastic resin (B) is 3-500μm.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin laminate excellent in appearance and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, the demands on plastics for adding new functions such as weather resistance, antistatic property, flame retardancy and for cost reduction have become more severe. To meet these requirements, improvement of a single resin has hitherto been addressed, but the requirements have been increasing year by year, and it is difficult to satisfy all of these requirements, and improvement by lamination is being studied. By stacking layers, it is possible to achieve the function that meets the purpose by effectively combining the properties of multiple resins, and to create high value-added products at low cost. Film lamination, coextrusion molding, multi-layer blow molding, multi-layer injection molding, and the like have been reported as lamination methods. The methods of stacking these can be roughly divided into two.

One is a lamination by post-processing which has been generally performed in the past. First, a substrate layer, a coating layer, or both of them are formed into respective molded bodies, and, for example, a film is attached later or heat is applied. Laminating is performed by methods such as press bonding, compression molding bonding, vacuum molding bonding, and injection molding bonding. In all of these methods, it is an important point to smooth the lamination interface, which causes problems in appearance. I often did.

The other is a laminating method by simultaneous molding such as co-extrusion, multi-layer blow and multi-layer injection molding, which have been actively researched in recent years. Simultaneous molding is a method of introducing several kinds of molten resin into the mold at the same time or with a slight time delay, and laminating and molding in the mold or outside the mold in a molten state. It is not necessary and can be laminated inexpensively and continuously.

However, in this simultaneous molding, which has been attracting attention in recent years, since the molten resins of each layer come into confluent contact with different complicated flow velocity and pressure distribution, the mutual flow and pressure balance are liable to be disturbed immediately after the confluence of the laminated layers, and the laminated layers An appearance defect phenomenon such as disordered interface or non-uniform mixing occurs. In order to control such disorder at the laminated interface, for example, a partition plate is provided in the mold in Japanese Patent Publication No. 53-4070 and Japanese Patent Publication No. 51-25390, or a confluence point in Japanese Patent Publication No. 52-60853. Various investigations have been made, such as adjusting the inflow angle of the resin with a flow rate adjusting bar to make the thickness of each resin layer uniform, but it is still in the stage of various development.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin laminate in which the appearance defect due to the disorder of the laminate interface is improved.

[0007]

[Means for Solving the Problems] In order to solve the above problems, as a result of intensive studies by the present inventors, a bonding layer having a specific thickness and shape is formed at the interface between the coating layer thermoplastic resin and the substrate layer thermoplastic resin. As a result, they have found that the above problems can be solved, and completed the present invention. That is, the present invention relates to a thermoplastic resin laminate obtained by laminating a thermoplastic resin (B) on at least one surface of a thermoplastic resin (A) via a bonding layer, wherein the thickness of the bonding layer is 0.1 to 2 μm. And a maximum amplitude of waviness is 10 μm or less per width of 5 mm, and the joining layer is a mixed layer of the thermoplastic resin (A) and the thermoplastic resin (B). Regarding

In addition, the thermoplastic resin (A) and the thermoplastic resin (B) having a melt flow rate of 0.5 to 2 times the melt flow rate of the thermoplastic resin (A) are simultaneously molded. The present invention relates to a method for manufacturing a thermoplastic resin laminate having a bonding layer. Further, the thermoplastic resin (A) is a polycarbonate resin and the thermoplastic resin (B) is an acrylic resin. The thermoplastic resin laminate and the thermoplastic resin (B) layer have a thickness of 0.3 to 500 μm. Plastic resin (A)
The present invention relates to a laminated sheet comprising (B), a laminated body thereof, and a method for producing the laminated sheet.

Hereinafter, the present invention will be described in detail. The thermoplastic resins (A) and (B) used in the present invention are not particularly limited, but for example, polycarbonate resin, acrylic resin, styrene resin, polyolefin resin, polyphenylene ether resin, vinyl chloride resin. , Vinylidene chloride resin, fluorine resin, polyester resin, polyurethane resin, polyacetal resin, silicone resin, polybutadiene resin, polyisoprene resin, polyimide resin, polyamideimide resin, polyetherester resin sheet, corrugated sheet, film ( Casting, inflation, etc.), injection moldings, hollow moldings (blow molding, gas injection, pipes, etc.), deformed shapes, compression moldings, vacuum moldings, thermoplastic resins or thermoplastic elastomers used for stampable molding, etc. Yes, what Kano laminated structure by a molding method as long as it can be molded.

The polycarbonate resin is a polymer derived from a divalent phenolic compound represented by bisphenol A, and may be produced by any of the phosgene method, the transesterification method and the solid phase polymerization method. In addition to these conventional polycarbonate resins, there is a special polycarbonate resin polymerized by the transesterification method, which is obtained by a transesterification reaction between an aromatic dihydroxy compound and a carbonic acid diester. The aromatic dihydroxy compound is a compound represented by HO-Ar-OH. In the formula, Ar represents a divalent aromatic group, for example, an organic group represented by the following general formula.

[0011]

Embedded image (In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 ring-constituting carbon atoms, or A phenyl group, m and n are integers of 1 to 4, and when m is 2 to 4, each R ¹ may be the same or different, and when n is 2 to 4 Is each R
^{The two} may be the same or different. )

The aromatic group Ar is, for example, --Ar _1-
A divalent aromatic group represented by Y—Ar ₂ — (in the formula,
Ar ₁ and Ar ₂ each independently have 5 to 7 carbon atoms.
Represents a divalent carbocyclic or heterocyclic aromatic group having 0, and Y represents a divalent alkane group having 1 to 30 carbon atoms. ). In the divalent aromatic groups Ar ₁ and Ar ₂ , one or more hydrogen atoms are other substituents that do not adversely affect the reaction, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. It may be substituted with 10 alkoxy groups, phenyl groups, phenoxy groups, vinyl groups, cyano groups, ester groups, amide groups, nitro groups and the like.

Preferred specific examples of the heterocyclic aromatic group include aromatic groups having one to a plurality of ring-forming nitrogen atoms, oxygen atoms or sulfur atoms. The divalent aromatic groups Ar ₁ and Ar ₂ represent groups such as substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, and substituted or unsubstituted pyridylene. The substituent here is as described above. The divalent alkane group Y is, for example,
An organic group represented by the following general formula.

[0014]

Embedded image (In the formula, R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen,
Alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, cycloalkyl group having 5 to 10 ring carbon atoms, carbocyclic aromatic group having 5 to 10 ring carbon atoms, and 6 to 1 carbon atoms
Represents a carbocyclic aralkyl group of 0. k represents an integer of 3 to 11, R ⁷ and R ⁸ are individually selected for each X, and independently of each other represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and X represents carbon. In addition, R ³ , R ⁴ , R ⁵ ,
In R ⁶ , R ⁷ , and R ⁸ , other substituents such as a halogen atom, an alkyl group having 1 to 10 carbon atoms, and 1 to 1 carbon atoms are used as long as one or more hydrogen atoms do not adversely affect the reaction.
It may be substituted with an alkoxy group of 0, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group, an amide group, a nitro group or the like. )

As such a divalent aromatic group Ar,
For example, the one represented by the following chemical formula 3 can be mentioned.

Embedded image (In the formula, R ¹ , R ² , m and n are groups as described above.)

Further, the divalent aromatic group Ar is --Ar ₁
It may be one represented by —Z—Ar ₂ —. (In the formula, Ar ₁ and Ar ₂ are groups as described above, and Z is a single bond or —O—, —CO—, —S—, —SO ₂ —, —SO.
-, - COO -, - CON (R 1) - represents a divalent group, such as. However, R ¹ is a group as described above. )

As such a divalent aromatic group Ar,
For example, those represented by the following general formula can be mentioned.

Embedded image (In the formula, R ¹ , R ² , m and n are as described above.)

The aromatic dihydroxy compound used in the present invention may be a single kind or two or more kinds. A typical example of the aromatic dihydroxy compound is bisphenol A. Further, it is preferable that the content of chlorine atom and alkali or alkaline earth metal in these aromatic dihydroxy compounds is small, and it is preferable that they are substantially not contained.

The diaryl carbonate used in the present invention is represented by the following general formula.

Embedded image (In the formula, Ar ³ and Ar ⁴ each represent a monovalent aromatic group.)

Ar ³ and Ar ⁴ represent a monovalent carbocyclic or heterocyclic aromatic group, and in this Ar ³ and Ar ⁴ , one or more hydrogen atoms do not adversely affect the reaction. A substituent of, for example, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a phenyl group, a phenoxy group, a vinyl group, a cyano group, an ester group,
It may be substituted by an amide group, a nitro group or the like. Ar ³ and Ar ⁴ may be the same or different.

Typical examples of the monovalent aromatic groups Ar ³ and Ar ⁴ include a phenyl group, a naphthyl group, a biphenyl group and a pyridyl group. These may be substituted with one or more types of the above-mentioned substituents. Preferred Ar
Examples of ³ and Ar ⁴ include groups represented by the following general formulas.

[0022]

[Chemical 6]

Representative examples of diaryl carbonates include substituted or unsubstituted diphenyl carbonates represented by the following general formula.

[Chemical 7] (Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 ring carbon atoms, or phenyl Represents a group, p and q are integers of 1 to 5,
When p is 2 or more, each R ⁹ may be different, and when q is 2 or more, each R ¹⁰ may be different. )

Among these diphenyl carbonates,
Unsubstituted diphenyl carbonate, ditolyl carbonate, symmetric diaryl carbonates such as lower alkyl-substituted diphenyl carbonates such as di-t-butylphenyl carbonate are preferred, and diphenyl carbonate which is a diaryl carbonate having the simplest structure is particularly preferred. It is. These diaryl carbonates may be used alone or in combination of two or more. In addition, these diaryl carbonates,
It is preferable that the content of chlorine atoms and alkali or alkaline earth metal is small, and if possible, it is preferable that they are substantially not contained.

The usage ratio (charge ratio) of the aromatic dihydroxy compound and the diaryl carbonate is the kind of the aromatic dihydroxy compound and the diaryl carbonate used, the polymerization temperature and other polymerization conditions, and the molecular weight and terminal ratio of the polycarbonate to be obtained. Depending on the amount of diaryl carbonate, the amount of diaryl carbonate is usually 0.9 to 2.5 mol, preferably 0.
It is used in a proportion of 95 to 2.0 mol, more preferably 0.98 to 1.5 mol.

Examples of acrylic resins include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like. Further, vinyl monomers copolymerizable with these alkyl methacrylates, for example, alkyl methacrylates and alkyl acrylates other than the above, methacrylic acid, acrylic acid, fumaric acid, maleic acid, itaconic acid, butadiene, isoprene, chloroprene, styrene, α -A polymer obtained by copolymerizing methylstyrene, acrylonitrile, and the like, and an acrylic rubber having a layered grain-shaped structure obtained by crosslinking these are listed.

As the styrene resin, polystyrene (PS), rubber-reinforced polystyrene (HIPS), styrene-acrylonitrile copolymer (AS), styrene-
Examples thereof include butadiene-acrylonitrile copolymer (ABS). Furthermore, as a polyolefin resin,
Low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDP)
E), polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-acrylic acid copolymer (EA)
A), ethylene-propylene copolymer (EPR), ionomer and the like.

Examples of polyamide resins include nylon 6, nylon 6,6, nylon 6,10, nylon 12, nylon 11, nylon 7, nylon 2, polyetheramide resin, polyesteramide resin, polyetheresteramide resin. Etc. Next, the polyphenylene ether resin is a PS or HIP containing polyphenylene ether resin (PPE) and PPE as constituent components.
Examples of the modified PPE include alloys with S, ABS, polyamide resins and the like.

Further, as the fluororesin, for example, polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-
Ethylene copolymer (ETFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), polytetrafluoroethylene (PTFE), hexafluoropropylene-vinylidene Examples thereof include fluoride copolymers.

As the polyester resin, polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT),
Examples thereof include polypentamethylene terephthalate and polyhexamethylene terephthalate. The polybutadiene resin is a styrene-butadiene copolymer (SB
R), acrylonitrile-butadiene copolymer (NB
R) can be mentioned.

These resins may be used alone or in combination of two or more, and may be a copolymer or a mixture. Further, the thermoplastic resin (A) and the thermoplastic resin (B) may be the same resin or different. Of these thermoplastic resins, preferred are polycarbonate resins, acrylic resins, fluorine resins, styrene resins, vinyl chloride resins, and polyolefin resins. More preferably, a polycarbonate resin, an acrylic resin, or a fluorine resin is used.

If necessary, these thermoplastic resins may include ultraviolet absorbers, antioxidants, antistatic agents, heat stabilizers, light stabilizers, flame retardants, mold release agents, surfactants, dispersants, lubricants, anti-static agents. Blocking agent, light diffusing agent, colorant, inorganic filler,
Additives such as glass fiber, a cross-linking agent, a foaming agent, a plasticizer, and an organic cross-linked body may be contained.

The thermoplastic resin laminate of the present invention has a bonding layer between the thermoplastic resin (A) and the thermoplastic resin (B), and the bonding layer is adjusted to a specific shape, property and thickness. It shows that it is necessary to do. The bonding layer is always present at the laminated interface and is preferably composed of both components of the thermoplastic resin (A) and (B). The number of layers of the laminated structure is not limited, and the components constituting the bonding layer between the layers may be the same or different.

As a molding form of the joining layer of the present invention, when the thermoplastic resins (A) and (B) are laminated in a molten state, either (A) or (B) is molten. In some cases, they may be laminated in a state of being laminated, or may be laminated in a state where neither (A) nor (B) is melted. In either case, they contribute to adhesion such as resin pressure at the layer interfaces of the thermoplastic resins (A) and (B). A phenomenon in which both layers come into contact with each other due to the force exerted to cause the two layers to be adhered, and as a result, the laminated interface has the composition of both resins (A) and (B).

The conditions for forming a laminate are (A) and (B)
When the resin layers are laminated in a molten state, it is important to match the fluidity of both resins. Also (A) (B)
When either of the resin layers is laminated in the molten state, the heat of the molten resin melts the unmelted resin and mutual entrapment occurs, creating a bonding layer and bonding, thus contributing to temperature and adhesion Technology is required to adjust the external pressure. Further, when both resins are laminated in a state where they are not melted, a large pressure from the outside is required. In this case, a temperature close to the melting points of both resins is required, and it is generally difficult to form the bonding layer at room temperature.

The thickness of the bonding layer is preferably 0.1 to 2 μm, more preferably 0.15 to 1.8 μm.
It is. If the thickness is less than 0.1 μm, a substantial penetration phenomenon does not occur and the bonding strength is weak, and the adhesive layer is easily peeled off by subjecting the laminate to secondary processing such as bending or drilling or by long-term use. On the other hand, if it exceeds 2 μm, the surface of the laminate is disturbed, resulting in poor appearance and deterioration of physical properties such as mechanical strength.

The maximum amplitude of waviness of the bonding layer is preferably 10 μm or less per 5 mm width. More preferably, it is 5 μm or less. If it exceeds 10 μm, the appearance may be poor or stress may be concentrated on the corrugated concave and convex portions, in which case the physical properties such as strength may be deteriorated.

The joining layer is a mixed layer made of a mixture of thermoplastic resins (A) and (B) as described above. The composition of the mixed layer is preferably 0.1 to 99.9 of the thermoplastic resin (A).
The thermoplastic resin (B) is 99.9 to 0.1 wt% with respect to wt%. More preferably, the thermoplastic resin (A) 0.5
(B) 99.5 to 0.5% by weight with respect to 99.5% by weight
It is. When the thermoplastic resins (A) and (B) are not mixed, the bonding layer is not formed and the (A) and (B) layers are not bonded. The mixing ratio is preferably changed stepwise in the thickness direction of the bonding layer. What is the bite phenomenon? The above-mentioned thermoplastic resin (A)
It means that the thermoplastic resins (A) and (B) are entangled with each other when they are mixed, not to mention the mixed state of (B).

In the present invention, a preferred combination of the thermoplastic resins (A) and (B) is a laminate using a polycarbonate resin as the substrate layer thermoplastic resin (A) and an acrylic resin as the coating layer thermoplastic resin (B). This is a molded product. Polycarbonate resin is a resin that is widely used in signboards, civil engineering and construction materials, etc., because it has excellent impact resistance, heat resistance, flame retardancy, etc., but is generally inferior in weather resistance, especially when used outdoors, causing yellowing and It tends to lose transparency, whiten, and deteriorate in physical properties. Therefore, as a method for improving the weather resistance of the polycarbonate resin, a method of laminating an acrylic resin containing an ultraviolet absorber has been reported (for example, JP-A-4-1).
19838, Japanese Patent Publication No. 47-19119).

However, the compatibility between the polycarbonate resin and the acrylic resin is poor, and when clouded, it becomes cloudy and loses transparency in the case of a transparent body. As the simultaneous molding method of the present invention, a co-extrusion method, which has a low flow rate at the time of merging each resin and a small shear stress generated at the lamination interface, is most preferable.

In the simultaneous molding, the laminated thickness of the thermoplastic resin (B) for the coating layer is preferably 3 to 500 μm, more preferably 5 to 300 μm. If the thickness is less than 3 μm, the coating layer does not flow uniformly during molding, resulting in turbulent flow in the surface layer portion, which causes a spiral appearance defect. When it exceeds 500 μm, problems in physical properties occur, for example, mechanical strength is lowered.

The present invention is characterized in that the fluidity of the resin for each layer is adjusted so as not to cause the disturbance at the laminating interface. The melt flow rate of the coating layer thermoplastic resin (B) is preferably 0.5 to 2 times, more preferably 0.6 to 1.8 times the melt flow rate of the substrate layer thermoplastic resin (A). Is. If it is less than 0.5 times, the coating layer resin pushes the substrate layer resin during the merging of the layers, and the shear stress at the layering interface becomes non-uniform, resulting in turbidity. On the other hand, if it exceeds 2 times, conversely, the coating layer resin is pressed into the substrate layer resin to cause turbidity or the coating layer resin becomes difficult to flow, and the lamination interface becomes wavy, resulting in a streak pattern appearance defect.

As described above, the bonding layer is formed by mixing both the resin of the substrate layer and the resin of the coating layer melted in the mold or outside the mold, and therefore cannot be directly controlled and it is difficult to obtain a smooth layer. . Of course, the mold design is important as a means for forming a smooth layer. Specifically, a method of reducing the merging angle of each resin to reduce the pushing force between the resin layers due to back pressure, or designing and manufacturing so as not to disturb the flow state at the time of merging If used together, the effect is further increased.

[0044]

EXAMPLES The effects of the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. The evaluation and test methods used in each example and comparative example are shown below. (1) Thickness of bonding layer, maximum amplitude of waviness Visually judge the surface of the sheet and the appearance due to transmitted light. Five points are sampled almost evenly and a length of 5 mm is measured. In addition, when the appearance defect is recognized only in a very small part, a maximum of 5 defective parts are sampled and measured at a length of 5 mm. The thickness of the bonding layer was measured at five points per sample at substantially equal intervals, and the average value of the five points was used as the measured value. The maximum amplitude of the waviness was the maximum value of all measurements. The measurement was performed by observing the cross section of the laminate at a maximum of 100,000 times with an ultra-high resolution operation electron microscope (model: S-5000) manufactured by Hitachi Ltd. The maximum amplitude of the waviness was measured by measuring the width of t shown in FIG. 1 by the above method.

(2) Coating Layer Thickness The cross section of the laminate was observed and measured with an inverted metal microscope (model: PME-3) manufactured by Olympus Optical.

(3) Bonding Layer Composition One sample of the thickness of the bonding layer was arbitrarily sampled, and a laser Raman spectroscope (model: PE1) manufactured by JASCO Corporation
The composition of the bonding layer was analyzed by focusing on the cross section of the laminated sheet using 700X), and the presence or absence of specific peaks derived from the thermoplastic resins (A) and (B) was confirmed. The meanings of the symbols in Table 1 are as follows. Symbol M: Both peaks of the thermoplastic resins (A) and (B) are present. It is a mixture of thermoplastic resins (A) and (B). A: Only the peak of the thermoplastic resin (A) is present. B: Only the peak of the thermoplastic resin (B) is present.

(4) Appearance Based on JIS K7105, the value of the diffused light transmittance (D%) at the laminate plate thickness was evaluated according to the following criteria. ◯: D% <2% Δ: 2% ≦ D% <4% ×: 4% ≦ D%

(5) Surface property The surface condition of the produced laminated sheet was visually evaluated according to the following criteria. ◯: Smooth, glossy and good appearance Δ: Some unevenness on the surface is observed under a fluorescent lamp. X: The surface is highly uneven and has no gloss.

(6) Delamination Test The produced laminated sheet was bent at about 90 degrees and the presence or absence of delamination was visually determined. (Result symbol ○: No peeling ×: Delamination occurred)

(7) Strength Test Using a DuPont drop weight impact test device (missile diameter 1/2 inch, saucer hole diameter 3/4 inch) manufactured by Toyo Seiki Co., Ltd.,
A weight of 2 kg was dropped from a height of 1 m on the produced laminated sheet, and a falling weight impact was applied to evaluate whether or not the test piece was broken. (Result symbol ○: No breakage ×: Breakage or crack occurrence)

(8) Melt flow rate A test load of 2.16 kgf according to ASTM D1238.
It was measured at. However, the test temperature is the molding temperature (die temperature).

Example 1 A polycarbonate resin "Taflon IV2700" manufactured by Idemitsu Petrochemical Co., Ltd. was used as the substrate layer thermoplastic resin (A). As the coating layer thermoplastic resin (B), an acrylic resin "Delpet 70H" manufactured by Asahi Kasei Co., Ltd. was used. The MFR of the acrylic resin is 2 times the die temperature compared to the MFR of the polycarbonate resin for the substrate layer.
It was 0.9 times at 70 ° C.

The above-mentioned thermoplastic resin (A) for the substrate layer was manufactured by Pla Giken Co., Ltd. using an extruder having a diameter of 50 mm and L / D = 32 at an extruder cylinder temperature setting of 290 ° C. and a thermoplastic resin (B) for the coating layer. Manufactured by Pla Giken Co., Ltd. with a diameter of 25 mm,
Co-extrusion was performed at an extruder cylinder temperature setting of 255 ° C. using an extruder with L / D = 32. The coextrusion die was a multi-manifold system, and the die set temperature was 270 ° C. The thickness of the coating layer was adjusted to 30 μm by adjusting the discharge rate of the extruder. The laminated molten resin discharged from the die was adjusted to a plate thickness of 1.5 mm by a glazing roll whose temperature was adjusted to 120 ° C. to prepare a 2-kind 2-layer laminated plate.
The laminate interface thus produced was smooth, and the bonding layer was thin and smooth, and a laminate having a good appearance was obtained. The evaluation results are shown in Table 1 as Example 1.

(Example 2) As a thermoplastic resin (B) for the coating layer, an acrylic resin "Delpet 8" manufactured by Asahi Kasei Kogyo Co., Ltd. was used.
2N laminated sheet was produced in the same manner as in Example 1 except that "0N" was used. The MFR of the acrylic resin was 1.5 times the MFR of the substrate layer polycarbonate resin at a die temperature of 270 ° C. The evaluation results are shown in Table 1 as Example 2.

(Example 3) A two-layer laminated sheet was prepared in the same manner as in Example 1 except that the die temperature was changed to 290 ° C. The MFR of the acrylic resin was 1.1 times the MFR of the substrate layer polycarbonate resin at a die temperature of 290 ° C. The evaluation results are shown in Table 1 as Example 3.

(Comparative Example 1) As the coating layer thermoplastic resin (B), an acrylic resin "Delpet 6" manufactured by Asahi Kasei Kogyo Co., Ltd.
2N laminated sheet was produced in the same manner as in Example 1 except that "0N" was used. The MFR of the acrylic resin was 7.1 times that of the substrate layer polycarbonate resin.
The evaluation results are shown in Table 1 as Comparative Example 1.

Comparative Example 2 As the coating layer thermoplastic resin (B), an acrylic resin "Delpet 8" manufactured by Asahi Kasei Kogyo Co., Ltd. was used.
0NB ”was used to produce a two-layer laminated sheet in the same manner as in Example 1. The MFR of the acrylic resin was 0.4 times the MFR of the substrate layer polycarbonate resin. The evaluation results are shown in Table 1 as Comparative Example 2.

(Comparative Example 3) Coating layer Two layers were laminated under the same resin and conditions as in Example 1 except that the extruder discharge amount of the thermoplastic resin (B) was reduced and the coating layer thickness was adjusted to 1 μm. A sheet was prepared. However, the coating layer was not laminated with a uniform thickness, and the laminated thickness was partially 0 μm, resulting in unevenness or stripes on the surface. The evaluation results are shown in Table 1 as Comparative Example 3.

(Comparative Example 4) Coating layer A two-layer laminated sheet with the same resin and conditions as in Example 1 except that the extruder discharge amount of the thermoplastic resin (B) was increased and the coating layer thickness was adjusted to 700 μm. Was produced. Table 1 shows the evaluation results as Comparative Example 4.
Shown in

[0060]

[Table 1]

(Example 4) Polycarbonate resin "Taflon IV2700" manufactured by Idemitsu Petrochemical Co., Ltd. was used as the thermoplastic resin (A), and a diameter of 50 mm manufactured by Pla Giken Co., Ltd.
A polycarbonate resin sheet having a plate thickness of 3 mm was obtained with a sheet extruder. At this time, the extruder set temperature was 290 ° C., the die temperature was 270 ° C., and the plate thickness was adjusted by the clearance of the glazing roll.

An acrylic film "Delpet LP-1" manufactured by Asahi Kasei Kogyo Co., Ltd. was used as the thermoplastic resin (B) to obtain an acrylic film having a thickness of 500 μm with the same extruder. At this time, the extruder set temperature was 270 ° C. and the die temperature was 250 ° C.

The polycarbonate resin sheet having a plate thickness of 3 mm and the acrylic film having a thickness of 500 μm obtained as described above were heated at a temperature of 240 ° C. and a preheating time of 3 minutes using a 37 ton compression molding machine manufactured by Shoko Iron Works Co., Ltd. , Compression heating time 1
Min (compression pressure of 20 kgf / cm ² ) and compression cooling time of 4 minutes (compression pressure of 10 kgf / cm ² ). The laminated interface thus prepared had a smooth laminated interface and a thin bonding layer, and a laminated plate having a good appearance was obtained. The evaluation results are shown in Table 2 as Example 4.

(Comparative Example 5) The set temperature of the compression molding machine was set to 16
A laminated sheet was produced in the same manner as in Example 4 except that the temperature was 0 ° C. However, the bonding strength between the acrylic film and the polycarbonate resin sheet was weak, and many layer peelings occurred. Table 2 shows the evaluation results.

(Comparative Example 6) The set temperature of the compression molding machine was set to 30.
A laminated sheet was prepared in the same manner as in Example 4 except that the temperature was 0 ° C. When the lamination interface of the laminated sheet thus obtained was observed, the bonding layer was thick and wavy, and the appearance was poor. Table 2 shows the evaluation results.

[0066]

[Table 2]

[0067]

According to the present invention, it is possible to establish a technique for preventing the disturbance of the laminated interface in the simultaneous molding, and it is possible to improve the defective appearance which has been a problem up to now.

[Brief description of drawings]

FIG. 1 shows the width of t, which is the maximum amplitude of waviness.

[Explanation of symbols]

 1: thermoplastic resin (A) 2: same (B) 3: bonding layer t: maximum amplitude of bonding layer

Claims (8)

[Claims] 1. A thermoplastic resin laminate obtained by laminating a thermoplastic resin (B) on at least one surface of a thermoplastic resin (A) via a joining layer, wherein the thickness of the joining layer is 0.1 to 2.
μm and the maximum amplitude of waviness is 10μ per 5 mm width
A thermoplastic resin laminate characterized by being m or less. 2. The thermoplastic resin laminate according to claim 1, wherein the bonding layer is a mixed layer of the thermoplastic resin (A) and the thermoplastic resin (B). 3. The thermoplastic resin (A) 0.1-9 as the mixed layer.
The thermoplastic resin laminate according to claim 2, which is a layer having a mixing ratio of 9.9% by weight and a thermoplastic resin (B) of 99.9 to 0.1% by weight. 4. A thermoplastic resin (A) and a thermoplastic resin (B) having a melt flow rate of 0.5 to 2 times the melt flow rate of the thermoplastic resin (A) are molded at the same time. A method for producing a thermoplastic resin laminate having a bonding layer. 5. The thermoplastic resin laminate according to claim 1, wherein the thermoplastic resin (A) is a polycarbonate resin and the thermoplastic resin (B) is an acrylic resin. 6. The method for producing a thermoplastic resin laminate according to claim 4, wherein the thermoplastic resin (A) is a polycarbonate resin and the thermoplastic resin (B) is an acrylic resin. 7. A thermoplastic resin laminated sheet in which the thermoplastic resin (A) is a polycarbonate resin, the thermoplastic resin (B) is an acrylic resin, and the thermoplastic resin (B) layer has a thickness of 3 to 500 μm. The thermoplastic resin laminate according to claim 1. 8. A thermoplastic resin laminated sheet in which the thermoplastic resin (A) is a polycarbonate resin, the thermoplastic resin (B) is an acrylic resin, and the thickness of the thermoplastic resin (B) layer is 3 to 500 μm. The method for producing a thermoplastic resin laminate according to claim 4.