KR20120007979A - Process for preparing a laminate - Google Patents

Abstract

PURPOSE: A method for manufacturing a laminated plate is provided to restraint line-shaped defects along extrusion flow direction by forming small size holes for polymer filter. CONSTITUTION: A method for manufacturing a laminated plate is as follows. Polycarbonate resin is supplied to feed block(10) after melting and mulling in a first extruding machine(2). Methacryl resin containing rubbery polymer is melted and mulled in a second extruding machine(5) and it passes a polymer filter to be supplied to the feed block. After polycarbonate resin and Methacryl resin are laminated and integrated on the feed block, the laminated material is pressed to plate shape from a die(15). When the width of a feed block resin eject hole and die resin eject hole is W1 and W2 respectively, it is W1:W2 = 1:7~20.

Description

Manufacturing method of laminated board {PROCESS FOR PREPARING A LAMINATE}

TECHNICAL FIELD This invention relates to the manufacturing method of the laminated board by which the methacryl resin layer containing a rubbery polymer is laminated | stacked on at least one surface of a polycarbonate resin layer.

Since polycarbonate resin plates are excellent in transparency, impact resistance, etc., they are used in various fields, such as an exterior use, a signboard use, a front plate use in lighting use, and a display.

However, a polycarbonate resin plate has a problem that durability and surface hardness are inferior. In order to solve this problem, the laminated board which laminated | stacked the acrylic resin layer on the at least single side | surface of a polycarbonate resin layer is proposed (for example, refer patent document 1). Moreover, since an acrylic resin layer is inferior in impact resistance and may be cracked, the laminated board which laminated | stacked the methacryl resin layer containing a crosslinked acrylic elastomer on at least one side of a polycarbonate resin layer is also proposed (for example, a patent document 2).

These laminated sheets are usually obtained by extrusion molding. In particular, the technique of extruding and integrating a methacryl resin layer and a polycarbonate resin layer containing a rubbery polymer such as a crosslinked acrylic elastomer and the like is very useful, and the use range is also wide.

However, when the polycarbonate resin layer and the methacrylic resin layer containing the rubbery polymer are extruded and laminated together, a large number of linear defects occur along the extrusion flow direction at the interface between the polycarbonate resin layer and the methacrylic resin layer. There was a case. Moreover, this linear defect tends to be dark in color. Such laminated defects, which have caused such a linear defect, have been reduced in appearance, cannot be used in a field in which the appearance typical of the front plate in a display is very important.

JP08-025589A JP11-58627A

The subject of this invention is providing the manufacturing method of the laminated board which has the outstanding external appearance as a manufacturing method of the laminated board which can suppress that a linear defect generate | occur | produces in the laminated board manufactured along the extrusion flow direction.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the present inventors discovered the solution which consists of the following structures, and came to complete this invention.

(1) A method for producing a laminate in which a methacrylic resin layer containing a rubbery polymer is laminated (or formed) on at least one side of the polycarbonate resin layer, wherein the polycarbonate resin is melt kneaded with a first extruder to feed Supplying the block to the block, melting and kneading the methacryl resin containing the rubbery polymer with a second extruder, passing the polymer filter to the feed block, and feeding the polycarbonate resin and the methacryl resin to the feed block. Laminating into a block and integrating the same; and extruding the sheet into a plate shape. When the resin discharge port width of the feed block is W1 and the resin discharge port width of the die is W2, W1 and W2 are W1. : W2 = 1: It has a relationship of 7-20, The manufacturing method of the laminated board characterized by the above-mentioned.

(2) The manufacturing method of the laminated board as described in said (1) in which the said methacryl resin layer is laminated | stacked on both surfaces of the said polycarbonate resin layer.

(3) The manufacturing method of the laminated board as described in said (1) or (2) whose filter hole size of the said polymer filter is 5-20 micrometers.

(4) The manufacturing method of the laminated board in any one of said (1)-(3) whose thickness of a laminated board is 0.2-3 mm.

According to this invention, generation | occurrence | production of a linear defect in a laminated board can be suppressed along an extrusion flow direction, and there exists an effect that a laminated board which has the outstanding external appearance can be obtained. There is also an effect that the color of the linear defect can be made light.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic explanatory drawing which shows the extrusion apparatus used for the manufacturing method of the laminated board which concerns on one Embodiment of this invention.
It is a schematic explanatory drawing which shows the feed block of the extrusion apparatus of FIG.
3 is a schematic explanatory view showing a die of the extrusion apparatus of FIG. 1.

In the laminated board of the present invention, a methacryl resin layer containing a rubbery polymer is laminated on at least one side of the polycarbonate resin layer.

The polycarbonate resin constituting the polycarbonate resin layer generally refers to a polycarbonate resin, and is not particularly limited as long as the laminate according to the present invention can be obtained. As such a polycarbonate resin, what is obtained by making a dihydric phenol and a carbonylating agent react by an interfacial polycondensation method, a melt transesterification method, etc., for example, is obtained by superposing | polymerizing a carbonate prepolymer by a solid-phase transesterification method, a cyclic carbonate compound What is obtained by superposing | polymerizing in a ring-opening polymerization method etc. can be illustrated.

Examples of the dihydric phenol include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, and bisquel (4-hydroxy-3,5- Dimethyl) phenyl ethanemethane, 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-methylphene , 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-bisbis (4-hydroxy-3-methyl) phenyl｝ fluorene, α, α- Bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy Sidiphenyl sulfoxide, 4,4'- dihydroxy diphenyl sulfide, 4,4'- dihydroxy diphenyl ketone, 4,4'- dihydroxy diphenyl ether, 4,4'- dihydroxy A cidi phenyl ester etc. are mentioned, These 2 or more types can also be used as needed.

Among them, bisphenol A, 2,2-bis (4-hydroxy-3-methyl) phenyl｝ propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxy Phenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1- Divalent phenols selected from bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene alone, or It is preferable to use 2 or more types, Particularly, bisphenol A is used alone, or 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis Combination with at least one divalent phenol selected from ｛(4-hydroxy-3-methyl) phenyl｝ propane and α, α＇-bis (4-hydroxyphenyl) -m-diisopropylbenzene is preferred. .

Examples of the carbonylating agent include carbonyl halides such as phosgene, carbonate esters such as diphenyl carbonate, haloformates such as dihaloformates of dihydric phenol, and the like. The above can also be used.

In addition, the methacryl resin which comprises the said methacryl resin layer says what is generally called methacryl resin, and it does not restrict | limit in particular as long as the laminated body which concerns on this invention can be obtained. As such methacryl resin, it is preferable to have a methyl methacrylate unit as a main component, and it is more preferable to contain 50 weight% or more of methyl methacrylate units normally, specifically, 70 weight% or more of methyl methacrylate units It is especially preferable that it is methyl methacrylate resin containing. Methyl methacrylate homopolymer of 100 weight% of methyl methacrylate units may be sufficient as methacrylic resin, and the copolymer of methyl methacrylate and the other monomer copolymerizable with this methyl methacrylate may be sufficient.

The other monomer copolymerizable with the methyl methacrylate is not particularly limited as long as it can copolymerize with methyl methacrylate and obtain a laminate according to the present invention. Generally, a radical having an ethylenic double bond is used. The monomer which can superpose | polymerize. As such a monomer, for example, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, etc. Methacrylic acid esters other than methyl methacrylate, acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate. Can be illustrated. Moreover, halogenated styrenes, such as styrene and substituted styrenes, for example, chloro styrene and bromostyrene, alkyl styrenes, such as vinyltoluene and (alpha) -methylstyrene, can be illustrated. Moreover, unsaturated acids, such as methacrylic acid and acrylic acid, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, cyclohexyl maleimide, etc. can also be illustrated. The other monomer copolymerizable with these methyl methacrylates may be used independently, respectively and may be used in combination of 2 or more type.

The rubbery polymer contained in the methacryl resin layer generally means what is called a rubbery polymer, and is not particularly limited as long as the laminate of the present invention can be obtained. For example, diene rubbers, such as a polybutadiene rubber, an acrylonitrile / butadiene copolymer rubber, a styrene / butadiene copolymer rubber, an acrylic rubber, ethylene / propylene / nonconjugated diene rubber, etc. are mentioned. Moreover, the graft copolymer formed by graft-polymerizing monomers, such as alkyl methacrylate, alkyl acrylate, styrene, substituted styrene, acrylonitrile, methacrylonitrile, to these rubbery polymers is also used preferably. When it is set as a graft copolymer, the ratio of the rubbery polymer and the monomer to be grafted is 5 to 80 weight part of the former, and 95 to 20 weight part of the latter. As these graft copolymers, what is described, for example in JP55-147514A, JP47-9740B, etc. can be used.

Moreover, as a preferable example of a graft copolymer, the multilayer structure polymer which uses a rubbery polymer as an inner layer and a graft polymerization chain as an outer layer is mentioned. In this case, it is preferable to use an acrylic rubber as a rubber polymer of an inner layer, The homopolymer of alkyl acrylate may be sufficient as this acrylic rubber, and 50 weight% or less of monomers other than alkyl acrylate and 50 weight% or less of alkyl acrylate may be sufficient as it. A copolymer may be sufficient. Here, as this alkyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc. are mentioned, for example. As monomers other than alkyl acrylate, for example, alkyl methacrylate, alkyl alkoxyacrylate, cyanoethyl acrylate, acrylamide, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylic acid, methacrylic acid, styrene, Substituted styrene, acrylonitrile, methacrylonitrile, etc. are mentioned, Crosslinkable monomers, such as allyl methacrylate, can also be used. It is preferable that the glass transition point (Tg) of acrylic rubber is less than 25 degreeC.

In addition, the graft polymerization chain of the outer layer is a homopolymer of alkyl methacrylate having 1 to 4 carbon atoms of an alkyl group or 50% by weight or less of monomers other than the alkyl methacrylate and 50% by weight of the alkyl methacrylate. It is preferable that it is a copolymer. As the alkyl methacrylate, methyl methacrylate is preferably used. Moreover, as monomers other than this alkyl methacrylate, a C5 or more alkyl methacrylate, alkyl acrylate, styrene, substituted styrene, acrylonitrile, methacrylonitrile, etc. are mentioned, for example, methacryl Crosslinkable monomers, such as acid allyl, can also be used. It is preferable that the glass transition point (Tg) of this outer layer polymer is 25 degreeC or more.

Moreover, the polymer similar to the said outer layer polymer can be made further inside of the acrylic rubber of an inner layer. It is preferable that the multilayer structure polymer as mentioned above contains 20-60 weight% of acrylic rubber layers based on the weight of the whole. As these multilayered structure polymers, what is described, for example in JP55-27576A, JP6-80739A, JP49-23292A, etc. can be used.

It is preferable that the ratio of a rubbery polymer is 3-50 weight part normally with respect to a total of 100 weight part of a methacryl resin and a rubbery polymer, More preferably, it is 4-30 weight part, More preferably, it is 5-20 weight It is wealth. If the proportion of the rubbery polymer is too small, the laminated sheet is likely to crack, and if the ratio is too large, the surface hardness of the laminated sheet may decrease, which is not preferable.

In addition, in the polycarbonate resin and methacryl resin mentioned above, oxidation, such as antistatic agents, such as sodium alkyl sulfonate, sodium alkyl sulfate, monoglyceride, polyetheresteramide, and a hindered phenol, respectively as needed, for example, Flame retardants such as inhibitors, phosphate esters, lubricants such as palmitic acid and stearyl alcohol, light stabilizers such as hindered amines, benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, cyanoacrylate ultraviolet absorbers and malonic acid esters Ultraviolet absorbers, such as an ultraviolet absorber, an oxalate-based ultraviolet absorber, and an acetate ester ultraviolet absorber, a light diffusing agent, dye, a fluorescent brightener, etc. may be added, and these additives may use these 2 or more types as needed. .

As a method of mix | blending the said additive, the method of melt-kneading after mechanically mixing resin and an additive with a Henschel mixer, a tumbler, etc. is mentioned, for example. In addition, this melt kneading | mixing can be performed using a single-axis or twin-screw extruder, various kneaders, etc., for example.

The laminated board of this invention which has the laminated constitution mentioned above can be manufactured as follows. EMBODIMENT OF THE INVENTION Hereinafter, one Embodiment of the manufacturing method of the laminated board which concerns on this invention is described in detail with reference to FIGS.

In the manufacturing method of the laminated board of this embodiment, it is preferable to use the extrusion apparatus 1 shown in FIG. This extrusion apparatus 1 is equipped with the 1st and 2nd extruders 2 and 5, the feed block 10, and the die 15 formed in order from the upstream along the resin extrusion direction shown by arrow A. FIG. Doing.

The 1st extruder 2 and the feed block 10 are connected through the 1st pipe 3. One end of the first pipe 3 is connected to the first extruder 2, and the other end thereof is connected to the resin supply port 11 of the feed block 10. It is preferable that the polymer filter 4 is formed between the both ends of the 1st pipe 3.

Similarly, the 2nd extruder 5 and the feed block 10 are connected through the 2nd pipe 6. One end of the second pipe 6 is connected to the second extruder 5, and the other end thereof is connected to the resin supply port 12 of the feed block 10, and between the two ends of the second pipe 6. The polymer filter 7 is formed in the.

The manufacturing method of the laminated board of this embodiment using this extrusion apparatus 1 includes the process of the following (i)-(i).

(Iii) The process of melt-kneading the polycarbonate resin mentioned above with the 1st extruder 2, and supplying it to the feed block 10. FIG.

(Ii) The process of melt-kneading the methacrylic resin containing the rubbery polymer mentioned above with the 2nd extruder 5, and passing it through the polymer filter 7 and supplying it to the feed block 10. FIG.

(Iii) A step of extrusion molding into a plate shape from the die 15 after laminating and integrating the polycarbonate resin and methacryl resin with the feed block 10.

Here, in the process of said (ii), after melt-kneading a methacryl resin containing a rubbery polymer with the 2nd extruder 5, the reason for passing the polymer filter 7 is mentioned, for the following reasons. have. That is, the rubbery polymer tends to aggregate during melt kneading with the second extruder 5. Therefore, when the methacryl resin does not pass through the polymer filter 7, the aggregate of the rubbery polymer contained in the methacryl resin is discharged as it is from the die 15, and linear defects increase due to this. Moreover, since the aggregate which discharge | aggregates and a particle size has become large is discharged, there exists a possibility that the linear defect which arises may become thick and long, and become more prominent, ie, a color deep defect. In order to solve such a problem, in this embodiment, after melt-kneading the methacryl resin containing a rubbery polymer with the 2nd extruder 5, it is made to pass through the polymer filter 7, and the aggregate of a rubbery polymer is removed. Then, the feed block 10 is supplied to the feed block 10.

Although the polymer filter 7 is not specifically limited as long as the laminated body made into the objective of this invention can be obtained, It is preferable that about 3 to 12 inch leaf disc type filters are laminated | stacked about 10-40 sheets, and it is commercially available. It can employ | adopt. As a filter hole size of the polymer filter 7, what is necessary is just what can filter the aggregate of a rubbery polymer. Specifically, as the filter pore size of the polymer filter 7, it is preferable that it is 5-20 micrometers, It is more preferable that it is 5-15 micrometers, It is further more preferable that it is 5-10 micrometers. The smaller the filter pore size of the polymer filter 7 tends to be less noticeable linear defects.

It is preferable to also pass the polymer filter 4 also about polycarbonate resin. Thereby, there exists a tendency for the external appearance of the laminated board obtained by removing the gel component and the foreign material of a polycarbonate resin to be improved. As filter pore size of the polymer filter 4, it is preferable that it is 10-30 micrometers, It is more preferable that it is 10-20 micrometers, It is further more preferable that it is 10-15 micrometers. The other structure of the polymer filter 4 is the same as that of the polymer filter 7 mentioned above.

Here, in this embodiment, in addition to forming the polymer filter 7, the method of laminating the methacryl resin layer containing a polycarbonate resin layer and a rubbery polymer is also important. That is, in the case of extruding and integrating a polycarbonate resin layer and a methacryl resin layer containing a rubbery polymer, generally, a feed block method in which both layers are laminated in a feed block and then widened in the die, It is conceivable to use any of a multi-manifold system in which both layers are widened and then stacked integrally.

In the case of extrusion molding different materials such as polycarbonate resin and methacryl resin, a multi-manifold system that does not depend on the viscosity characteristics of each resin is often used.

However, when the multi-manifold system is used, the rubbery polymer contained in the methacrylic resin layer penetrates into the polycarbonate resin layer near the interface between the polycarbonate resin layer and the methacrylic resin layer containing the rubbery polymer. This occurred a lot and it was confirmed that the part becomes a linear defect along the extrusion flow direction.

On the other hand, in the case of lamination using the feed block method, it was confirmed that the occurrence of linear defects was significantly reduced when the ratio between the resin discharge port width of the feed block and the resin discharge port width of the die was in a specific relationship. Specifically, as shown in FIG. 2, the width of the resin discharge port 13 of the feed block 10 is represented by W1, and as shown in FIG. 3, the width of the resin discharge port 16 of the die 15 is represented by W2. When W1 and W2 have a relationship of W1: W2 = 1: 1-7-20, preferably 1: 7-15, more preferably 1: 7-13, the occurrence of linear defects is remarkable. Can be reduced. On the other hand, when the resin discharge port width ratio (W2 / W1, hereinafter referred to as "resin discharge port width ratio") of the feed block 10 and the die 15 is less than 7, the effect of reducing the linear defect is small, and the resin discharge port width ratio W2. / W1) exceeds 20, the variation tends to occur in the layer thickness ratio at the time of lamination, and the appearance defects, such as a flow mark, tend to arise.

In addition, as long as the polymer filter 7 is formed and a resin discharge port width ratio is comprised by the above-mentioned specific relationship, it does not specifically limit about the other structure of the extrusion apparatus 1. As the 1st and 2nd extruder 2 and (5), a single axis | shaft or a biaxial extruder etc. can be employ | adopted, for example. Moreover, you may use two or more extruders as needed. As the feed block 10, a 2 type 2 layer distribution type, a 2 type 3 layer distribution type, etc. are mentioned, for example. As the die 15, a T die etc. are mentioned, for example.

The laminated board of the molten state co-extruded from the die 15 to plate shape is cooled by cooling units, such as a metal roll, a rubber roll, a metal elastic roll, a metal belt, a rubber belt, for example. In order to prepare the surface of a laminated board, it is preferable to perform cooling, pressing and pinching the laminated board in a molten state with a roll, a belt, etc. According to this method, the unevenness | corrugation and engraving process by a blast are given to a roll and a belt, and the shape can also be transferred to a laminated board.

As a laminated constitution of the laminated board obtained, the two-layered constitution in which the methacryl resin layer was laminated | stacked on the single side | surface of a polycarbonate resin layer may be sufficient, and the three-layered constitution in which the methacryl resin layer was laminated | stacked on both surfaces of a polycarbonate resin layer may be sufficient. Since the environment resistance of a laminated board, ie, it does not bend easily when a laminated board is exposed to high temperature or high humidity, the laminated board of the three-layered constitution in which a methacryl resin layer is laminated | stacked on both surfaces of a polycarbonate resin layer is preferable.

It is preferable that the thickness of a laminated board is 0.2-3 mm normally, More preferably, it is 0.3-2 mm, More preferably, it is 0.4-1.5 mm. If the thickness of the laminated sheet is too thin, it becomes difficult to mold, and if the thickness of the laminated sheet is too thick, the cooling time required at the time of molding becomes long and productivity is lowered.

If the layer thickness ratio of each layer of a laminated board is a 2-layered constitution, it is preferable that the ratio of the methacryl resin layer containing the polycarbonate resin layer / rubber polymer is 1/99-99/1 normally, More preferably, 2/98-98/2, More preferably, they are 5/95-95/5. If it is a three-layered constitution, it is preferable that the ratio of the methacryl resin layer containing a rubbery polymer / polycarbonate resin layer / methacryl resin layer containing a rubbery polymer is 1/98/1-49/2/49 normally. More preferably, they are 2/96/2-48/4/48, More preferably, they are 3/92/3-45/10/45.

In addition, when a laminated board is a three-layered constitution, the composition and thickness of both sides of the methacryl resin layer may be mutually same or different. The thickness of a laminated board can be arbitrarily adjusted by adjusting the thickness of the laminated board in a molten state, the space | interval of the roll or belt with which a cooling unit is equipped, the circumferential speed, etc.

The obtained laminated board can be used suitably for an exterior use, a signboard use, a lighting use, a front plate use in a display, etc., and can be especially used as a front plate in a display. In addition, the laminated board which concerns on this invention is not limited to the use illustrated above, It can use suitably in the field where an external appearance is important.

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited only to a following example.

The structure of the extrusion apparatus used by the following example and the comparative example is as follows.

1st extruder: The extruder (made by Hitachi Shipbuilding Co., Ltd.) with a screw diameter of 110 mm, a single shaft, and the vent was used.

2nd extruder: The screw diameter 45 mm, the single screw, the extruder with a vent (made by Hitachi Shipbuilding Co., Ltd.) was used.

Polymer filter (a): It laminated | stacked 30 sheets of 7-inch leaf disc type filters, and used 15 micrometers of filter hole sizes (made by Fuji Filter Co., Ltd.).

Polymer filter (b): A 15-inch leaf disc filter was laminated with 15 sheets, and a filter pore size of 20 µm (manufactured by Fuji Filter Co., Ltd.) was used.

Polymer filter (c): A 15-inch leaf disc filter was laminated with 15 sheets, and a filter pore size of 10 µm (manufactured by Fuji Filter Co., Ltd.) was used.

Polymer filter (d): A 15-inch leaf disc filter was laminated with 15 sheets, and a filter pore size of 5 µm (manufactured by Fuji Filter Co., Ltd.) was used.

Feed block (I): The resin discharge port width W1 used 150 mm and 2 types and 3 layers distribution (made by Hitachi Shipbuilding Co., Ltd.).

Feed block (II): The resin discharge port width W1 used 150 mm and two types of two-layer distribution (made by Hitachi Shipbuilding Co., Ltd.).

Multi-manifold die: The resin discharge port width | variety 1650 mm, 2 types and 3 layers distribution (made by Hitachi Shipbuilding Co., Ltd.) were used.

Die: T-die (manufactured by Hitachi Shipbuilding Co., Ltd.) having a resin discharge port width W2 of 1650 mm and a lip spacing of 1 mm was used.

Die (ii): A T die (manufactured by Hitachi Shipbuilding Co., Ltd.) having a resin discharge port width W2 of 1150 mm and a lip spacing of 1 mm was used.

Die: T-die (made by Hitachi Shipbuilding Co., Ltd.) whose resin discharge port width W2 was 900 mm and a lip spacing 1.5 mm was used.

Cooling unit: Three cooling rolls of horizontal type, surface length of 1800 mm and diameter of 400 mmφ were used.

Resin used by the Example and the comparative example is as follows.

Polycarbonate resin 1: "Caliber 301-10" by Sumitomo Dow Co., Ltd. was used.

Polycarbonate resin 2: "Teflon IN2200" by Idemitsu Heungsan Co., Ltd. was used.

A mixture of 86 parts by weight of a copolymer of methacrylic resin 3: methyl methacrylate / methyl acrylate = 94/6 (weight ratio) and 14 parts by weight of the rubbery polymer obtained in the following reference example was used.

A mixture of 86 parts by weight of a copolymer of methacrylic resin 4: methyl methacrylate / methyl acrylate = 98/2 (weight ratio) and 14 parts by weight of the rubbery polymer obtained in the following reference example was used.

[Reference example]

(Manufacture of rubber polymer)

First, 1700 g of ion-exchange water, 0.7 g of sodium carbonate, and 0.3 g of sodium persulfate were injected | poured into the glass reaction container of the internal volume of 5L, and it stirred under nitrogen stream. Subsequently, after adding 4.46 g of dispersing agents ("Perex OT-P" by Kao Corporation), 150 g of ion-exchange water, 150 g of methyl methacrylate, and 0.3 g of allyl methacrylate, it heated up at 75 degreeC Stirring was continued for 150 minutes.

Subsequently, a mixture of 689 g of butyl acrylate, 162 g of styrene, and 17 g of allyl methacrylate, 0.85 g of sodium persulfate, 7.4 g of a dispersant ("Ferex OT-P" manufactured by Kao Corporation), and 50 g of ion-exchanged water The mixtures were each added over 90 minutes and the polymerization continued for another 90 minutes.

After the completion of the polymerization, a mixture of 326 g of methyl methacrylate and 14 g of ethyl acrylate and 30 g of ion-exchanged water in which 0.34 g of sodium persulfate was dissolved were added over 30 minutes each.

After the addition was completed, the mixture was held for 60 minutes to complete the polymerization. The obtained latex was poured into a 0.5 wt% aluminum chloride aqueous solution to coagulate the rubbery polymer. This was washed 5 times with warm water and dried to obtain a rubbery polymer.

[Examples 1-7 and Comparative Examples 1, 2, 6]

<Production of laminated board>

First, while using the 1st and 2nd extruder, a polymer filter, a feed block, and a die in the combination shown in Table 1, it arranged as shown in FIG. Subsequently, polycarbonate resins 1 and 2 and methacryl resins 3 and 4 are used in the combinations shown in Table 1, and polycarbonate resins 1 and 2 are used as the first extruder and methacrylic resins 3 and 4 are used as the second extruder, respectively. Melt kneading. And the resin layer A was supplied from the 1st extruder, and the resin layer B was supplied from the 2nd extruder in order of a feed block and die, respectively, and coextruded from the die to plate shape.

At this time, about Example 1, 3, 5, 6, and Comparative Examples 1 and 6, the resin layer A supplied to a feed block from a 1st extruder becomes an intermediate | middle layer, and the resin layer B supplied to a feed block from a 2nd extruder. Co-extrusion was performed so that both surface layers would be.

And the laminated board of the molten state which coextruded-molded in plate shape from the die was formed into three cooling rolls, and the laminated board which consists of a 2-layer or 3-layer structure of the laminated constitution shown in Table 1 and thickness was obtained. "Thickness" in the 1st, 2nd extruder of Table 1 has shown the thickness of each of the polycarbonate resin layer and the methacryl resin layer, and "total thickness" has shown the total thickness of the obtained laminated board. In addition, Example 1, 3, 5, 6 and Comparative Examples 1, 6 are the laminated boards which consist of a 3-layered constitution. In these Examples and Comparative Examples, the value described in the column of "thickness" in the second extruder represents "one surface layer thickness / the other surface layer thickness".

[Comparative Examples 3 to 5, 7]

Instead of the feed block and the die, a multi-manifold die was used, except that the first and second extruders and the polymer filters were used in the combinations shown in Table 1, except that the laminates having a three-layer configuration were formed in the same manner as in Examples 1 to 7. Got it.

<Evaluation>

About each obtained laminated board (Examples 1-7 and Comparative Examples 1-7), the linear defect was evaluated. While the evaluation method is shown below, the result is shown in Table 1.

(Evaluation method of linear defect)

First, the test piece was cut out in the size of 400x500 mm from the obtained laminated board. Subsequently, in the environment which blocked external light, the said test piece was mounted on the black sheet | seat, and the three wavelength fluorescent lamp was arrange | positioned 45 degree incline with respect to the surface of the test piece.

And white light was irradiated to the surface of a test piece from the said three wavelength white fluorescent lamp, and the color of the linear defect which exists in a test piece, and the number thereof were visually observed and evaluated. In addition, the color of the linear defect was evaluated by the following criteria.

◎ very thin.

○: light.

(Triangle | delta): Although it is a little dark, it is a degree with which there is no problem in actual use.

X: dark.

As is apparent from Table 1, Examples 1-7 have few numbers of linear defects, and it turns out that the color is also light. On the other hand, Comparative Examples 1 to 2 using the resin discharge port width ratios W2 / W1 of less than 7 and Comparative Examples 3 to 5 using the multi-manifold die showed that the number of linear defects was larger than that of Examples 1 to 7. . In addition, Comparative Example 7 in which the methacryl resin containing the rubbery polymer did not pass through the polymer filter was used, and Comparative Example 7 in which the methacryl resin containing the rubbery polymer did not pass through the polymer filter was used. A large number of dark colored linear defects occurred.

1: extrusion device
2: first extruder
3: first pipe
4, 7: polymer filter
5: second extruder
6: second pipe
10: feed block
11, 12: resin supply port
13, 16: resin discharge port
15: die

Claims (4)

As a manufacturing method of the laminated board in which the methacryl resin layer containing a rubbery polymer is laminated | stacked on the at least single side | surface of a polycarbonate resin layer,
Melt kneading the polycarbonate resin with a first extruder and feeding the polycarbonate resin to a feed block;
Melt kneading a methacryl resin containing a rubbery polymer with a second extruder, passing the polymer filter through the polymer filter and supplying the feed block to the feed block;
And laminating and integrating the polycarbonate resin and methacryl resin into the feed block, and extruding the die into a plate shape from a die.
When the resin discharge port width of the feed block is W1 and the resin discharge port width of the die is W2, W1 and W2 have a relationship of W1: W2 = 1: 1 to 7-20. The method of claim 1,
The manufacturing method of the laminated board in which the said methacryl resin layer is laminated | stacked on both surfaces of the said polycarbonate resin layer. The method according to claim 1 or 2,
The manufacturing method of the laminated board whose filter hole size of the said polymer filter is 5-20 micrometers. The method according to any one of claims 1 to 3,
The manufacturing method of the laminated board whose thickness of a laminated board is 0.2-3 mm.

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