KR101972165B1 - A laminated plate - Google Patents

Abstract

(assignment)
Transparency, impact resistance and surface hardness.
(Solution)
A methacrylic resin layer (B) is laminated on one surface of a polycarbonate resin layer (A), and a methacrylic resin layer (C) containing a rubber-like polymer is laminated on the other surface, The layer (C) is a laminate comprising a methacrylic resin composition containing a rubber-like polymer in an amount of 3 wt% or more and less than 30 wt% based on 100 wt% of a total of methacrylic resin and rubber-like polymer. The thickness of the methacrylic resin layer (B) is preferably 3 to 70 mu m.

Description

[0001] A LAMINATED PLATE [0002]

The present invention relates to a laminate including a polycarbonate resin layer.

Since the polycarbonate resin plate is excellent in transparency and impact resistance, it is used in a variety of fields such as exterior use, signboard use, and use for a front plate in lighting applications and displays.

However, there is a problem that the polycarbonate resin plate is inferior in surface hardness. In order to solve this problem, Patent Document 1 describes a laminated plate in which an acrylic resin layer is laminated on one side of a polycarbonate resin layer.

However, the laminated board described in Patent Document 1 has a problem that the impact resistance is low and it is fragile. Patent Document 2 discloses a laminate in which an acrylic resin layer containing a crosslinked acrylic elastomer in an amount of 25 parts by weight per 100 parts by weight of a methacrylic resin is laminated on both sides of a polycarbonate resin layer as a fragile laminate.

However, the laminate described in Patent Document 2 has a problem that the surface hardness is low. Therefore, development of a laminate having excellent transparency, impact resistance and surface hardness has been desired.

Japanese Laid-Open Patent Publication No. 08-025589 Japanese Patent Application Laid-Open No. 11-58627

An object of the present invention is to provide a laminated board excellent in transparency, impact resistance and surface hardness.

The present invention relates to the following invention.

(1) A methacrylic resin layer (B) is laminated on one surface of a polycarbonate resin layer (A), and a methacrylic resin layer (C) containing a rubber-like polymer is laminated on the other surface. The methacrylic resin layer (C) is characterized by comprising a methacrylic resin composition containing a rubber-like polymer in an amount of 3% by weight or more and less than 30% by weight based on 100% by weight of the total of a methacrylic resin and a rubber- Lt; / RTI >

(2) The laminate according to (1) above, wherein the thickness of the methacrylic resin layer (B) is 3 to 70 μm.

(3) The laminate according to the above (1) or (2), wherein the total thickness of the laminate is 0.2 to 3 mm.

Since the laminate of the present invention has excellent transparency, impact resistance and surface hardness, it can be suitably used for front panel use in displays and the like.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic explanatory view showing a method for producing a laminated board according to an embodiment of the present invention. Fig.

The laminate of the present invention is a laminate comprising a polycarbonate resin layer (A) composed of a polycarbonate resin, a methacrylic resin layer (B) composed of methacrylic resin, and a methacrylic resin composition containing a rubber- And a methacrylic resin layer (C) constituted by the methacrylic resin. Of these resin layers, the polycarbonate resin layer (A) is excellent in transparency and impact resistance, the methacrylic resin layer (B) is excellent in transparency and surface hardness, and the methacrylic resin layer (C) great.

In the laminate of the present invention, the resin layers described above are laminated as follows. That is, the methacrylic resin layer (B) is laminated on one surface of the polycarbonate resin layer (A), and the methacrylic resin layer (C) is laminated on the other surface of the polycarbonate resin layer (A). As a result, the transparency of the entire laminated board is excellent, and the surface of the both surfaces of the laminate, particularly the side of the methacrylic resin layer (B), is excellent in surface hardness and the surface of the methacrylic resin layer (B) The impact resistance is excellent. Hereinafter, the laminate of the present invention will be described in detail.

As the polycarbonate resin constituting the polycarbonate resin layer (A), for example, a resin obtained by reacting a divalent phenol and a carbonylating agent with an interfacial polycondensation method, a melt ester exchange method, etc., , A resin obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method, and the like.

Examples of the dihydric phenol include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis { (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2- Propane (commonly known as bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2- Bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis { (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- Bis (4-hydroxyphenyl) pentane, 2, 3-dimethylbutane, 2,4- Bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydro Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, Diisopropylbenzene,?,? '- bis (4-hydroxyphenyl) -m-diisopropylbenzene,?,?' (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'- Dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester, and the like can be given. , Two or more of them may be used.

Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2- (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and?,? '-Bis (4-hydroxyphenyl) -m-diisopropylbenzene; It is particularly preferable to use two or more kinds of bisphenol A alone, or use of bisphenol A alone, or a combination of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane with bisphenol A, It is preferable to use a combination of at least one divalent phenol selected from the group consisting of {(4-hydroxy-3-methyl) phenyl} propane and α, α'-bis (4-hydroxyphenyl) .

Examples of the carbonylating agent include a carbonyl halide such as phosgene, a carbonate ester such as diphenyl carbonate, and a haloformate such as dihaloformate of divalent phenol. Or more may be used.

On the other hand, as the methacrylic resin constituting the methacrylic resin layer (B) to be laminated on one surface of the above-described polycarbonate resin layer (A), a resin comprising a methyl methacrylate unit as a main component, The methyl methacrylate resin is preferably a methyl methacrylate resin containing usually not less than 50% by weight, preferably not less than 70% by weight of methyl acrylate units, and may be a methyl methacrylate homopolymer of 100% by weight of methyl methacrylate units, Or may be a copolymer of an acid methyl group and another monomer copolymerizable with the methyl methacrylate.

Examples of the other monomer copolymerizable with the methyl methacrylate include ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethyl methacrylate Methacrylic acid esters other than methyl methacrylate such as hexyl and 2-hydroxyethyl methacrylate, methacrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, And acrylic esters such as 2-hydroxyethyl. Further, styrene and substituted styrenes such as halogenated styrenes such as chlorostyrene and bromostyrene, alkylstyrenes such as vinyltoluene and? -Methylstyrene, and the like can be mentioned. Further, unsaturated acids such as methacrylic acid and acrylic acid, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, cyclohexylmaleimide and the like are also exemplified. These other monomers copolymerizable with methyl methacrylate may be used alone or in combination of two or more.

The methacrylic resin layer (B) may contain a rubber-like polymer, or may be composed of a methacrylic resin composition containing a methacrylic resin as a resin component and further containing a rubber-like polymer. As the methacrylic resin in the methacrylic resin composition, the same methacrylic resin as the methacrylic resin exemplified as the methacrylic resin constituting the above-described methacrylic resin layer (B) can be mentioned. As the rubber-like polymer, a rubber-like polymer similar to the rubber-like polymer exemplified by the methacrylic resin composition constituting the methacrylic resin layer (C) to be described later may be mentioned. The composition of the rubber-like polymer contained in the methacrylic resin composition constituting the methacrylic resin layer (B), and the composition of the methacrylic resin constituting the methacrylic resin layer (C) and the rubber-like polymer contained in the composition, May be the same or different.

The content of the rubber-like polymer in the methacrylic resin composition constituting the methacrylic resin layer (B) is preferably less than 3% by weight based on 100% by weight of the total amount of the methacrylic resin rubber-like polymer . When the content of the rubber-like polymer is too large, there is a fear that the surface hardness of the laminated plate is lowered.

The methacrylic resin layer (C) laminated on the other surface of the polycarbonate resin layer (A) is composed of a methacrylic resin composition. The methacrylic resin composition contains a methacrylic resin as a resin component. The methacrylic resin may be the same methacrylic resin as the methacrylic resin exemplified for the methacrylic resin constituting the above-described methacrylic resin layer (B). The composition of the methacrylic resin constituting the methacrylic resin layer (B) may be the same as or different from the composition of the methacrylic resin contained in the methacrylic resin layer (C).

The methacrylic resin composition contains a rubber-like polymer as an essential component. Examples of the rubber-like polymer include diene rubber such as polybutadiene rubber, acrylonitrile / butadiene copolymer rubber and styrene / butadiene copolymer rubber, acrylic rubber, ethylene / propylene / nonconjugated diene rubber and the like. A graft copolymer obtained by graft-polymerizing monomers such as alkyl methacrylate, alkyl acrylate, styrene, substituted styrene, acrylonitrile, and methacrylonitrile on these rubber-like polymers is also preferably used. In the case of a graft copolymer, the ratio of the rubber-like polymer to the grafted monomer is usually from 5 to 80 parts by weight, and the latter is from 95 to 20 parts by weight. As these graft copolymers, for example, copolymers described in JP-A-55-147514 and JP-A-47-9740 can be used.

As a preferable example of the graft copolymer, a multi-layer structure polymer comprising a rubber-like polymer as an inner layer and a graft polymerization chain as an outer layer can be mentioned. In this case, as the rubber-like polymer in the inner layer, it is preferable to use an acrylic rubber. The acrylic rubber may be a homopolymer of alkyl acrylate or a copolymer of 50 wt% or more of alkyl acrylate and 50 wt% or less of monomers other than alkyl acrylate Or may be a copolymer. Examples of the alkyl acrylate include propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like. Examples of the monomer other than the alkyl acrylate include alkyl methacrylate, alkyl alkoxyacrylate, cyanoethyl acrylate, acrylamide, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, acrylic acid, methacrylic acid, styrene, Substituted styrene, acrylonitrile, methacrylonitrile, and the like, and further, a crosslinkable monomer such as allyl methacrylate may be used. The glass transition point (Tg) of the acrylic rubber is preferably less than 25 占 폚.

The graft polymerization chain of the outer layer may be a homopolymer of alkyl methacrylate having an alkyl group of 1 to 4 carbon atoms or a copolymer of 50% by weight or more of the alkyl methacrylate and 50% by weight or less of a monomer other than the alkyl methacrylate Is preferably a copolymer. As the methacrylic acid alkyl, methyl methacrylate is preferably used. Examples of the monomer other than the alkyl methacrylate include alkyl methacrylate having 5 or more carbon atoms, alkyl acrylate, styrene, substituted styrene, acrylonitrile, methacrylonitrile and the like, A crosslinking monomer such as allyl acrylate may be used. The glass transition temperature (Tg) of the outer layer polymer is preferably at least 25 ° C.

Further, the same polymer as the outer layer polymer may be present further inside the acrylic rubber of the inner layer. The above-mentioned multi-layer structured polymer is preferably a polymer containing 20 to 60% by weight of the acrylic rubber layer based on the total weight of the multi-layer structured polymer. As such a multilayer structure polymer, for example, a polymer described in Japanese Patent Application Laid-Open No. 55-27576, Japanese Patent Application Laid-Open No. 6-80739, Japanese Laid-Open Patent Application No. 49-23292 or the like can be used.

The methacrylic resin composition contains 3 to 30% by weight, preferably 3 to 25% by weight, more preferably 5 to 23% by weight, based on 100% by weight of the total of the methacrylic resin and the rubber- By weight. When the proportion of the rubber-like polymer is too small, the impact resistance is lowered. When the proportion of the rubber-like polymer is too large, the surface hardness of the laminated board is lowered.

The polycarbonate resin layer (A) and the methacrylic resin layers (B) and (C) described above may further contain, for example, sodium alkylsulfonate, sodium alkylsulfate, stearic acid monoglyceride, polyetherester An antioxidant such as amide, an antioxidant such as hindered phenol, a flame retardant such as phosphoric acid ester, a light stabilizer such as palmitic acid and stearyl alcohol, a hindered amine, a benzotriazole-based ultraviolet absorber, a benzophenone- , A UV absorber such as a cyanoacrylate-based ultraviolet absorber, a malonic ester-based ultraviolet absorber, an oxalanilide-based ultraviolet absorber, an acetic ester-based ultraviolet absorber, a light diffusing agent, a dye or a fluorescent whitening agent. Two or more of them may be used as needed.

Examples of the method of blending the additive include a method of mechanically mixing the resin and the additive with a Henschel mixer or a tumbler, and then melt-kneading. The melt-kneading can be carried out using, for example, a single-screw extruder or a twin-screw extruder or various kneaders.

The laminate is formed by laminating and integrating a methacrylic resin layer (B) on one side of a polycarbonate resin layer (A) and a methacrylic resin layer (C) on the other side by coextrusion molding, . The co-extrusion molding is performed by melt-kneading the respective materials of the polycarbonate resin layer (A) and the methacrylic resin layers (B) and (C) using three single-screw or twin-screw extruders, A multi-manifold die, or the like. The laminated and integrated molten resin may be cooled and solidified by using, for example, a roll unit or the like. The laminate produced by co-extrusion molding is preferable to a laminate produced by bonding using a pressure-sensitive adhesive or an adhesive because of easy secondary molding.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, one embodiment relating to a method for producing a laminated board of the present invention will be described in detail with reference to Fig. As shown in the drawing, first, the respective materials of the polycarbonate resin layer (A) and the methacrylic resin layers (B) and (C) are heated and melted and kneaded by separate extruders 1, 2 and 3 , Respectively, are supplied to the feed block (4), melt-laminated and integrated, and then extruded from the die (5).

Subsequently, the sheet-like molten resin extruded from the die 5 is sandwiched between the first cooling roll 6 and the second cooling roll 7 arranged in the substantially horizontal direction. At least one of the first and second cooling rolls 6 and 7 is connected to a rotation drive means such as a motor and the both rolls are configured to rotate at a predetermined main speed. Of the two rolls, the second cooling roll 7 is a hoisting roll rolled up from the sheet-like to the laminated plate on the film after sandwiched between both rolls.

Examples of the first and second cooling rolls 6 and 7 include a metal roll having rigidity and a metal elastic roll having elasticity. The above metal rolls, for example, drilled rolls, spiral rolls and the like can be mentioned. The metallic elastic roll includes, for example, an axial roll, and a cylindrical metal thin film disposed so as to cover the outer circumferential surface of the axial roll and in contact with the molten resin. The metal roll A roll in which a controlled fluid is enclosed, a roll in which a metal belt is wound around the surface of the rubber roll, and the like.

The first and second cooling rolls 6 and 7 may be composed of one kind selected from a metal roll and a metal elastic roll, or may be a combination of a metal roll and a metal elastic roll.

In the case of obtaining a laminated board in which the retardation value is reduced, it is preferable that the first and second cooling rolls 6 and 7 are constituted by a combination of a metal roll and a metal elastic roll. That is, when the molten resin is sandwiched between the metal roll and the metal elastic roll, the metal elastic roll is elastically deformed concavely along the outer circumferential surface of the metal roll through the molten resin, and the metal elastic roll and the metal roll interpose the molten resin And contacts with a predetermined contact length. As a result, the metal roll and the metal elastic roll are pressed against each other by surface contact with the molten resin, and the molten resin sandwiched between these rolls is uniformly pressed in the form of a surface. As a result, the deformation at the time of film formation is reduced, and the retardation value is reduced.

When the metal roll and the metal elastic roll are combined, it is preferable that the metal elastic roll is used as the first cooling roll 6 and the metal roll is used as the second cooling roll 7. [ Thereby, the retardation value of the obtained laminated plate can be further reduced.

The molten resin sandwiched between the first cooling roll 6 and the second cooling roll 7 described above is wound in the order of the second cooling roll 7 and the third cooling roll 8 in this order. Concretely, the molten resin wound around the second cooling roll 7 is passed between the second cooling roll 7 and the third cooling roll 8 and wound around the third cooling roll 8 . Thereby, since the molten resin is gradually cooled, the retardation value of the obtained laminated plate can be reduced. Further, a predetermined gap may be formed between the second cooling roll 7 and the third cooling roll 8 so as to be in a released state, or even if the molten resin is sandwiched between the rolls without forming a predetermined gap do.

The third cooling roll 8 is not particularly limited, and a conventional metal roll which has been conventionally used in extrusion molding can be employed. Specific examples include drilled rolls and spiral rolls. The surface condition of the third cooling roll 8 is preferably a mirror surface. Further, after the third cooling roll 8, the fourth cooling roll, the fifth cooling roll, , N rolls (n is a natural number) and a plurality of cooling rolls may be formed, and the sheet-like laminated sheet laminated on the third cooling roll 8 may be sequentially wound around the following cooling roll.

The laminated sheet obtained by winding the laminate by winding it on the third cooling roll 8 and slowly cooling is taken by a drawing roll (not shown) and is wound thereon. The total thickness of the laminated plate is preferably 0.2 to 3 mm, more preferably 0.3 to 2 mm, and even more preferably 0.4 to 1.5 mm. If the thickness of the laminate is excessively thin, molding may be difficult, and if the thickness of the laminate is excessively large, the cooling time required for molding may become long and the productivity may be lowered.

In this laminated plate, the thickness of the polycarbonate resin layer (A) is preferably 20 to 2,900 占 퐉, the thickness of the methacrylic resin layer (B) is preferably 3 to 70 占 퐉, The thickness of the krill resin layer (C) is preferably 20 to 200 mu m. In particular, when the thickness of the methacrylic resin layer (B) is within the above-mentioned specific range, sufficient impact resistance can be obtained. The thicknesses of the methacrylic resin layer (B) and the methacrylic resin layer (C) may be the same or different from each other.

The thickness of the laminated plate can be arbitrarily adjusted by adjusting the thickness of the laminated plate in a molten state, the interval of rolls or belts provided in the cooling unit, the peripheral speed, and the like.

The laminate thus obtained can be suitably used for exterior use, for signboard use, for lighting use, for front plate use in displays, etc., and can be preferably used particularly as a front plate for displays. When the obtained laminated plate is used as the front plate of the display, it is preferable to use the methacrylic resin layer (B) to be the mark side (viewer side) and the methacrylic resin layer (C) to be the back side (display side). That is, the laminate of the present invention is used as a front plate of a display by disposing the methacrylic resin layer (B) as a side (viewer side) and the methacrylic resin layer (C) as a side And the laminate of the present invention are arranged so that the methacrylic resin layer (B) becomes the mark side (viewer side) and the methacrylic resin layer (C) becomes the other side (display side) The method also constitutes the present invention. By using in this way, the front plate of the display has excellent surface hardness on the viewer side and excellent impact resistance against impact from the viewer side. In addition, the laminate of the present invention is not limited to the exemplified uses, and can be preferably used in fields where transparency, impact resistance and surface hardness are required.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

The configuration of the extrusion apparatus used in the following examples and comparative examples is as follows.

Extruder (1): An extruder (Toshiba Machine Co., Ltd.) having a screw diameter of 65 mm and a uniaxial vents was used.

Extruder (2): An extruder (manufactured by Hitachi, Ltd.) having a screw diameter of 45 mm and uniaxial vents was used.

Extruder (3): An extruder (manufactured by Hitachi, Ltd.) having a screw diameter of 45 mm and a uniaxial vents was used.

Feed block (4): A three-kind three-layer distribution type feed block (manufactured by Hitachi, Ltd.) was used.

Die 5: A T-die (manufactured by Hitachi, Ltd.) having a lip width of 1400 mm and a lip interval of 1 mm was used.

First, second and third cooling rolls (6, 7 and 8): Horizontal, 1400 mm in surface length and 300 mm in diameter were used.

More specifically, for the first, second and third cooling rolls 6, 7 and 8, a metal elastic roll was used for the first cooling roll 6. The metal elastic roll was provided with a metal thin film so as to cover the outer circumferential surface of the shaft roll, and a roll in which a fluid was sealed between the shaft roll and the metal thin film was adopted.

Axial rolls, metal thin films and fluids are as follows.

Axial roll: Stainless steel roll was used.

Metal Thin Film: A 2 mm thick stainless steel specular metal sleeve was used.

· Fluid: By controlling the temperature of the oil with oil, the metal elastic roll was temperature-controllable. More specifically, the oil is heated and cooled by the ON / OFF control of the temperature regulator so that the temperature can be controlled, and circulated between the shaft roll and the metal thin film.

For the second and third cooling rolls 7 and 8, a high-rigidity metal roll was used. The metal roll is a stainless steel spiral roll whose surface state is mirror-finished.

The resins used in Examples and Comparative Examples are of the following three types.

Resin 1: Polycarbonate resin " Caliba 301-10 " manufactured by Sumitomo Dairy Company Limited having a thermal deformation temperature (Th) of 140 占 폚 was used.

Resin 2: Polymethyl methacrylate (PMMA) resin "SUMIPEX MH" manufactured by Sumitomo Chemical Co., Ltd. having a thermal deformation temperature (Th) of 100 ° C was used.

A resin having a methacrylic resin composition in which a copolymer of resin 3: methyl methacrylate / methyl acrylate = 98/2 (weight ratio) and the rubber-like polymer obtained in the following Reference Example were mixed in the ratios shown in Table 1 were used. "Copolymer" in Table 1 indicates a copolymer of methyl methacrylate / methyl acrylate = 98/2 (polymerization ratio), and "rubber" indicates a rubber-like polymer obtained in the following Reference Examples.

[Reference Example]

(Preparation of Rubbery Polymer)

First, 170 g of ion-exchanged water, 0.7 g of sodium carbonate and 0.3 g of sodium persulfate were poured into a glass reaction vessel having an internal volume of 5 L and stirred under a nitrogen stream. Then, 4.46 g of a dispersant ("Parex OT-P" manufactured by Kao Corporation), 150 g of ion-exchanged water, 150 g of methyl methacrylate and 0.3 g of allyl methacrylate were added and the temperature was raised to 75 ° C 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 dispersant ("Parex OT-P" manufactured by Kao Corporation) and 50 g of ion- Was added separately over 90 minutes, and the polymerization was continued for another 90 minutes.

After 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 separately over 30 minutes.

After completion of the addition, the addition was maintained for 60 minutes to complete the polymerization. The resultant latex was added to a 0.5 wt% aqueous solution of aluminum chloride to coagulate the rubber-like polymer. This was washed five times with hot water and then dried to obtain a rubber-like polymer.

[Examples 1 to 4 and Comparative Examples 1 to 3]

≪ Fabrication of laminates &

First, the extruders 1, 2 and 3, the feed block 4, the die 5, the first, second and third cooling rolls 6, 7 and 8 were arranged as shown in Fig. Then, the resin of the kind shown in Table 1 was melt-kneaded with the extruder 1 and the resin of the kind shown in Table 1 was melt-kneaded with the extruder 2 as the resin layer (B) (C) were melt-kneaded with an extruder (3) and supplied to the feed block (4).

A resin layer B supplied from the extruder 2 to the feed block 4 is laminated on one surface of the resin layer A supplied from the extruder 1 to the feed block 4, A molten resin in which a resin layer C fed from the extruder 3 to the feed block 4 was laminated was extruded from the die 5 on the other face of the die.

Subsequently, the melted resin on the film extruded from the die 5 is sandwiched between the first cooling roll 6 and the second cooling roll 7 arranged opposite to each other, and wound around the third cooling roll 8, Layer structure having a thickness shown in Table 1 in which a resin layer (B) is laminated on one surface of a resin layer (A) and a resin layer (C) is laminated on the other surface of the resin layer Was obtained.

The surface temperature of the first cooling roll 6 was 120 占 폚, the surface temperature of the second cooling roll 7 was 125 占 폚, and the surface temperature of the third cooling roll 8 was 130 占 폚. These temperatures are measured values of the surface temperature of each cooling roll. The "thickness" in the extruders 1, 2 and 3 in Table 1 indicates the thicknesses of the resin layers (A), (B) and (C) Total thickness.

<Evaluation>

The obtained laminate plates (Examples 1 to 4 and Comparative Examples 1 to 3) were evaluated for fall strength and pencil hardness. The evaluation methods are shown below, and the results are shown in Table 1.

(Evaluation method of strength of giraffe)

First, the test piece was cut from the obtained laminate into a size of 60 x 60 mm. Subsequently, the resin layer (B) and the resin layer (C) were placed on the upper side (the cavity side) and the lower side, respectively, of the resin layers (B) and (C) A metal sphere of? was dropped onto the test piece while increasing the height from the surface of the resin layer (B) by 5 cm. Then, the height at which cracks were generated in the test piece was evaluated as the girth strength. The higher the height at which cracks are generated in the test piece, the better the impact resistance.

(Evaluation method of pencil hardness)

The measurement surface was regarded as the resin layer (B) and measured according to JIS K 5400.

As apparent from Table 1, Examples 1 to 4 show excellent strength in fall (impact resistance) and pencil hardness (surface hardness). The laminates of Examples 1 to 4 were observed with naked eyes. As a result, each of the laminates had high transparency.

On the other hand, in Comparative Example 1 in which the resin layer (C) did not contain a rubber-like polymer, the height at the strength of the strength at the fall height was low and the impact resistance was inferior. In Comparative Example 2, since the resin layer (B) contained 14% by weight of the rubber-like polymer, the pencil hardness value was low and the resin layer (C) did not contain the rubber-like polymer, Of the total height. In Comparative Example 3 in which the resin layer (B) contained 14% by weight of the rubber-like polymer, the pencil hardness value was low.

1, 2, 3: extruder
4: Feed block
5: Die
6: first cooling roll
7: Second cooling roll
8: Third cooling roll

Claims (3)

A methacrylic resin layer (B) is laminated on one surface of a polycarbonate resin layer (A), and a methacrylic resin layer (C) containing a rubber-like polymer is laminated on the other surface,
Wherein the methacrylic resin layer (B) is formed of a methacrylic resin composition having a rubber-like polymer content of 0 wt% based on the total of 100 wt% of a methacrylic resin and a rubber-like polymer,
And the methacrylic resin layer (C) is composed of a methacrylic resin composition containing a rubber-like polymer in an amount of 3 wt% or more and less than 30 wt% based on 100 wt% of the total of a methacrylic resin and a rubber-like polymer . The method according to claim 1,
And the thickness of the methacrylic resin layer (B) is 3 to 70 탆. 3. The method according to claim 1 or 2,
And the thickness of the whole laminated plate is 0.2 to 3 mm.

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