KR20140103186A - Resin sheet for forming and formed object - Google Patents

Abstract

A resin sheet using a polycarbonate resin as a main material is provided with a resin sheet for molding which does not cause whitening, cracking and foaming even when subjected to thermoforming, particularly deep drawing. A coating layer composed mainly of an acrylic resin (B) is formed on one surface of a substrate layer composed mainly of a polycarbonate resin composition (A) comprising an aromatic polycarbonate (A1) and a polymer alloy of another resin (A2) And the absolute value of the glass transition temperature difference between the polycarbonate resin composition (A) and the acrylic resin (B) is within 30 占 폚.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a resin sheet for molding,

The present invention relates to a resin sheet using a polycarbonate-based resin as a main material, and relates to a resin sheet for molding suitable for thermoforming such as vacuum molding or air-molding, and a molded article obtained by molding the resin sheet for molding.

The polycarbonate resin is excellent in transparency and is superior in workability and impact resistance as compared with glass and has no worry about toxic gas compared with other plastic materials and is widely used in various fields. Is also used as a material for thermoforming.

However, since the polycarbonate-based resin generally has a low surface hardness, there is a problem that the surface of the molded article made of the polycarbonate-based resin tends to be scratched. Therefore, conventionally, proposals have been made to form a protective layer made of an acrylic resin on the surface of the polycarbonate resin layer to prevent scratches on the product surface.

For example, Patent Document 1 proposes a laminate in which an acrylic resin layer having a thickness of 50 to 120 탆 is co-extruded on one side of a polycarbonate resin layer to laminate the total thickness to 0.5 to 1.2 mm.

Patent Document 2 discloses a scratch-resistant acrylic film suitable for a display screen protection plate of a portable information terminal, which is obtained by applying hard coating treatment to an acrylic film containing an acrylic resin layer in which rubber particles are dispersed in methacrylic resin to impart scratch resistance A scratch-resistant acrylic film is disclosed.

Japanese Patent Application Laid-Open No. 2006-103169

Japanese Patent Application Laid-Open No. 2004-143365

As described above, when a protective layer made of an acrylic resin is formed on the surface of the polycarbonate resin layer, the acrylic resin is generally harder to stretch than the polycarbonate resin, and therefore, drawing, the interface between the polycarbonate resin layer and the acrylic resin layer was peeled off, resulting in whitening of the surface or cracking. In addition, if it is not sufficiently dried before thermoforming, foaming may occur.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a resin sheet for molding having such a laminated structure, a novel resin sheet for molding which does not cause whitening, cracking, and further foaming even when thermoforming, Thereby providing a molded article.

The present invention relates to an acrylic resin composition comprising a base layer composed mainly of a polycarbonate resin composition (A) comprising an aromatic polycarbonate (A1) and a polymer alloy of another resin (A2) Wherein the absolute value of the glass transition temperature difference between the polycarbonate resin composition (A) and the acrylic resin (B) is within 30 占 폚.

Since the molding resin sheet of the present invention is provided with the covering layer mainly composed of the acrylic resin (B), it is possible to prevent the surface of the covering layer of the molding resin sheet and the product surface formed by molding the molding resin sheet from being scar Lt; / RTI >

Further, by setting the difference (absolute value) of the glass transition temperature (absolute value) of the polycarbonate resin composition (A) as the main component of the substrate layer and the acrylic resin (B) as the main component of the coating layer within 30 DEG C, It was possible to prevent whitening, cracking, and further foaming even when deep drawing was performed.

Therefore, when the molding resin sheet of the present invention is used for thermoforming, not only a molded article having excellent designability but also an in-mold molded article having excellent designability can be provided.

On the other hand, there is a possibility that various methods exist in the method of making the difference (absolute value) of the glass transition temperature between the polycarbonate resin composition (A) and the acrylic resin (B) within 30 DEG C. However, , The aromatic polycarbonate (A1) and the other resin (A2) are polymerized to lower the glass transition temperature so that the glass transition temperature difference (absolute value) of both is lowered to 30 占 폚.

Next, an example of the embodiment of the present invention will be described, but the present invention is not limited to the following embodiments.

The resin sheet for molding (hereinafter referred to as " main molding resin sheet ") according to the present embodiment comprises a polycarbonate resin composition (A) comprising a polymer alloy of an aromatic polycarbonate (A1) (A) and the acrylic resin (B), wherein the glass transition temperature (Tg) difference between the polycarbonate resin composition (A) and the acrylic resin (B) is in the form of a laminate sheet having a coating layer composed mainly of an acrylic resin Is 0 ° C to 30 ° C, preferably 0 ° C to 20 ° C, and particularly preferably 0 ° C to 10 ° C.

<Base layer>

The substrate layer of the present molding resin sheet can be formed using a polycarbonate resin composition (A) composed mainly of an aromatic polycarbonate (A1) and a polymer alloy of another resin (A2) as a main component.

[Aromatic polycarbonate (A1)]

The aromatic polycarbonate used in the present molding resin sheet is not particularly limited as long as it is a polycarbonate having an aromatic ring. For example, an aromatic dihydroxy compound or an aromatic dihydroxy compound and a small amount of polyhydroxy compound are obtained by an interfacial polymerization method with phosgene, or an aromatic dihydroxy compound and an ester of a carbonate diester A thermoplastic polycarbonate polymer obtained by an exchange reaction, and the like. More specifically, for example, a carbonate ester polymer containing bisphenol A as a main raw material can be mentioned.

The molecular weight of the aromatic polycarbonate is not particularly limited as long as the sheet can be produced by ordinary extrusion molding, but it is preferable that the viscosity average molecular weight [Mv] converted from the solution viscosity is 15,000 to 40,000, particularly 20,000 to 35,000, To 30,000.

On the other hand, two or more kinds of aromatic polycarbonates having different viscosity average molecular weights may be mixed.

Herein, the viscosity average molecular weight [Mv] is determined by Schnell's viscosity formula, that is, the intrinsic viscosity [?] (Unit dl / g) at 20 ° C using a Ubbeloid viscometer using methylene chloride as a solvent means a value calculated from? = 1.23 占 10-4M0.83. The intrinsic viscosity [?] Is a value calculated by measuring the specific viscosity [? Sp] at each solution concentration [C] (g / dl).

The terminal hydroxyl group concentration of the aromatic polycarbonate is preferably 1000 ppm or less, particularly 800 ppm or less, particularly preferably 600 ppm or less. The lower limit value is preferably 10 ppm or more, particularly 30 ppm or more, particularly 40 ppm or more.

Here, the terminal hydroxyl group concentration represents the mass of the terminal hydroxyl group relative to the mass of the aromatic polycarbonate in ppm, for example, a colorimetric amount by the tetrachloride titanium / acetic acid method (Macromol. Chem. 88215 )). &Lt; / RTI &gt;

[Other Resins (A2)]

The other resin (A2) can be polymerized by melt blending (mixing with heating and melting) the aromatic polycarbonate (A1), and further the glass transition temperature (Tg) Is lower than the glass transition temperature (Tg) of the glass transition temperature.

In general, the glass transition temperature (Tg) of the aromatic polycarbonate is about 150 캜 and is higher than the glass transition temperature (Tg) of the acrylic resin by about 50 캜. Therefore, the polycarbonate resin composition (A) and the acrylic resin In order to set the glass transition temperature (Tg) difference (absolute value) within 30 DEG C, the aromatic polycarbonate (A1) and the other resin (A2) are polymerized to form a polymer alloy having a glass transition temperature (Tg) It is important to be able to do.

From this viewpoint, aromatic polyester is preferable as the other resin (A2). Next, the aromatic polyester will be described.

(Aromatic polyester)

Examples of the aromatic polyester used as the other resin (A2) include a resin obtained by condensation polymerization of an &quot; aromatic dicarboxylic acid component &quot; and a &quot; diol component &quot;.

Typical examples of the &quot; aromatic dicarboxylic acid component &quot; include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and the like. A part of terephthalic acid may be replaced with &quot; another dicarboxylic acid component &quot;.

Examples of the other dicarboxylic acid component include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, neopentylic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl ethanedicarboxylic acid, . These may be a mixture of two or more kinds of monomers, and the amount of other dicarboxylic acid to be substituted may be appropriately selected.

Representative examples of the "diol component" include ethylene glycol, diethylene glycol, triethylene glycol, cyclohexane dimethanol, and the like. And a part of ethylene glycol may be replaced with &quot; other diol component &quot;.

Examples of the "other diol component" include propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, neopentylglycol, polyalkyleneglycol, 1 , 4-cyclohexane dimethanol, glycerin, pentaerythritol, methoxy polyalkylene glycol and the like. These may be a mixture of two or more kinds of diols, and the amount of other diols to be substituted may be appropriately selected.

As specific examples of the &quot; aromatic polyester &quot;, polyethylene terephthalate condensed with terephthalic acid and ethylene glycol, polybutylene terephthalate condensed with terephthalic acid or dimethyl terephthalate and 1,4-butanediol, . A &quot; copolymerized polyester &quot; containing a dicarboxylic acid component other than terephthalic acid and / or a diol component other than ethylene glycol is also preferable as the aromatic polyester.

As a particularly preferable example, a copolymerized polyester having a structure in which a part of ethylene glycol in polyethylene terephthalate, preferably 55 to 75 mol%, is substituted with cyclohexane dimethanol, or polybutylene terephthalate , Preferably 10 to 30 mol% of terephthalic acid is replaced with isophthalic acid, or a mixture of these copolyesters.

Among the above-described aromatic polyesters, those capable of forming a polymer alloy by melt-blending with the aromatic polycarbonate (A1) and capable of sufficiently lowering the glass transition temperature (Tg) of the polymer alloy from the aromatic polycarbonate (A1) It is preferable to select it.

From this point of view, a copolymerized polyester having a structure in which 50 to 75 mol% of ethylene glycol as a diol component of polyethylene terephthalate (PET) is substituted with 1.4-cyclohexane dimethanol (1.4-CHDM) , "PCTG"), or a copolymerized polyester having a structure in which a part of terephthalic acid, preferably 10 to 30 mol%, of polybutylene terephthalate (PBT) is substituted with isophthalic acid, or a mixture thereof is the most preferable example . Such a copolymerized polyester is known to completely polymerize it by melt-blending with an aromatic polycarbonate, and furthermore, the glass transition temperature can be effectively lowered.

On the other hand, whether or not the polymer blend (mixed resin composition) is a polymer alloy, that is, whether the polymer blend is completely miscible can be determined, for example, by measuring the glass transition temperature measured by differential scanning calorimetry at a heating rate of 10 캜 / It can be judged whether or not it is done. Here, the single glass transition temperature of the mixed resin composition means that when the glass transition temperature of the mixed resin composition is measured using a differential scanning calorimeter at a heating rate of 10 占 폚 / minute in accordance with JIS K7121, This means that only one appears.

Further, when the mixed resin composition was measured by dynamic viscoelasticity measurement (dynamic viscoelasticity measurement by the method of JIS K-7198A) at a frequency of 10 Hz and a variation of 0.1%, it was judged whether or not a maximum value of the loss tangent can do.

When the polymer blend (mixed resin composition) is completely commercialized (polymerized), the blended components become compatible with each other to the order of nanometers (molecular level).

On the other hand, as a means for polymerizing the polymer, a compatibilizing agent may be used, a block polymerization or a graft polymerization may be performed secondarily, or a method of dispersing one polymer in a cluster may be employed.

[Mixing Ratio]

The mixing ratio of the aromatic polycarbonate (A1) and the aromatic polyester (A2) is such that the difference (absolute value) between the glass transition temperature (Tg) of the polycarbonate resin composition (A) A = A2: 20: 80 to 75: 25, and more preferably A1: A2 = 30: 70 to 60: 40, in view of transparency, It is particularly preferable that A1: A2 = 45:55 to 55:45.

&Lt; Coated layer &

The coating layer of the present thermoformable resin sheet can be formed from a resin composition containing an acrylic resin (B) as a main component.

[Acrylic resin (B)]

The acrylic resin used in the thermoforming resin sheet is not particularly limited as long as it is a resin having an acrylic group. For example, a copolymer of methyl methacrylate and methyl acrylate or ethyl acrylate. Among them, a methyl methacrylate resin (PMMA: also referred to as polymethyl methacrylate) in which the main component is polymerized from methyl methacrylic acid is preferable.

The copolymer composition of the acrylic resin is preferably selected appropriately according to the production conditions, for example, the co-extrusion conditions. For example, in the case of a copolymer of methyl methacrylate and methyl acrylate or ethyl acrylate, the molar ratio of methyl methacrylate: methyl or ethyl acrylate = 80: 20 to 1:99 is preferable.

In addition, it may contain a crosslinking component within a range in which extrusion molding is possible.

The molecular weight of the acrylic resin is generally from 30,000 to 300,000 in weight average molecular weight, but is not limited to this range.

Commercially available acrylic resins can also be used. For example, methyl methacrylate resins such as SUMIPEX series manufactured by Sumitomo Chemical Industry Co., Ltd., Acryphet series manufactured by Mitsubishi Rayon Co., Ltd., Parapet series manufactured by Kuraray Co., Ltd., Can be used. However, the present invention is not limited thereto.

The acrylic resin (B) may contain an ultraviolet absorber for the purpose of maintaining the weatherability for a long period of time. The content of the ultraviolet absorber is preferably 0.01 to 3.0% by mass of the acrylic resin.

In order to prevent thermal degradation of the acrylic resin during co-extrusion molding, an antioxidant, a coloring preventing agent and the like may be contained. At this time, the content of the antioxidant is preferably 0.01 to 3% by mass of the acrylic resin, and the content of the coloring preventing agent is preferably 0.01 to 3% by mass.

In either case, it is presumed that sufficient effect can not be obtained if the content of the acrylic resin is less than 0.01 mass%. On the other hand, if the content exceeds 5 mass%, further effects can not be expected and bleed- Or may cause deterioration of adhesion and impact strength, which is not preferable.

Further, in order to further increase the surface hardness, high Tg acrylic or the like may be dispersed in the acrylic resin to maintain transparency. In addition, by adding a methyl methacrylate-styrene copolymer resin (MS resin), the water absorption rate can be lowered to suppress foaming.

<Sheet Thickness>

The thickness of each layer and the entire sheet of the present molding resin sheet can be appropriately set within a range that does not cause problems in surface hardness and moldability. However, in general, the thickness of the entire sheet is preferably 0.2 mm to 2.0 mm, and the thickness of the coating layer is preferably 10 to 40 탆, particularly 30 to 40 탆.

<Manufacturing Method>

The production method of the present molding resin sheet is not particularly limited, but from the viewpoint of productivity, it is preferable to laminate the base layer and the coating layer by coextrusion.

For example, the polycarbonate resin composition (A) and the acrylic resin (B) are heated and melted in separate extruders, respectively, and extruded from the slit-shaped ejection openings of the T die to be laminated, And a manufacturing method.

The aromatic polycarbonate (A1) and the other resin (A2) may be mixed when the polycarbonate resin composition (A) is heated and melted by an extruder, but may be mixed and melted (melt blended) in advance and then mixed with a compatibilizer It is preferable to prepare a polymer alloy.

The temperature for heating and melting in the extruder is preferably 80 to 150 DEG C higher than the glass transition temperature (Tg) of each resin. In general, the temperature condition of the main extruder for extruding the polycarbonate resin composition (A) is preferably from 230 to 290 DEG C, preferably from 240 to 280 DEG C, and the temperature of the sub extruder Is usually from 220 to 270 캜, preferably from 230 to 260 캜.

A known method such as a feed block method or a multi-manifold method can be adopted as a method of pneumatically delivering two kinds of molten resins.

For example, in the case of the feed block type, the molten resin laminated with the feed block is brought into a sheet molding die such as a T-die and molded into a sheet, and then the surface is flowed into a mirror-finished molding roll (polishing roll) A bank is formed, and mirror-surface finishing and cooling may be performed during passing of the forming roll.

In the case of the multi-manifold method, the molten resin laminated in the multi-manifold die may be formed into a sheet inside the die, and then surface finishing and cooling may be performed with a forming roll.

In any case, the temperature of the die is usually set at 230 to 290 캜, preferably 250 to 280 캜, and the temperature of the forming roll is usually set at 100 to 190 캜, preferably 110 to 190 캜.

<Features and Uses>

Since the present molding resin sheet is provided with the covering layer mainly composed of the acrylic resin (B), the surface of the covering layer of the molding resin sheet and the product surface formed by molding the molding resin sheet are hardly scratched It is equipped. In addition, by setting the absolute value of the glass transition temperature difference of the polycarbonate resin composition (A) as the main component of the substrate layer and the acrylic resin (B) as the main component of the coating layer within 30 DEG C, It is possible to prevent whitening, cracking, and further foaming even when thermoforming is carried out as desired, particularly when deep drawing is performed.

Therefore, when the present molding resin sheet is used for thermoforming, it is possible to obtain a thermoformed article excellent in designability, particularly a thermoformed article excellent in designability obtained by deep drawing molding.

On the other hand, in the present invention, deep drawing is referred to as deep drawing when the deep drawing height at the time of molding is 3 mm or more, particularly 5 mm or more, and in the case of deep drawing with a deep drawing height of 7 mm or more, It is possible to prevent foaming.

Since the present molding resin sheet has the above-described characteristics, for example, a printing layer is formed on the substrate layer side of the molding resin sheet and thermoformed, and a molten resin is injection-molded on the printing layer side By forming the support layer, an in-mold shaped body having excellent design properties can be produced.

<Explanation of Terms>

In the present invention, the term &quot; main component &quot; includes the meaning allowing other components to be contained within a range not interfering with the function of the main component, unless otherwise specified. In this case, although the content ratio of the main component is not specified, the content of the main component (when the two or more components are main component resins, the total amount thereof) is 50 mass% or more, particularly 70 mass% or more, especially 90 mass% (Including 100%).

In general, a &quot; sheet &quot; refers to a product that is thinner in definition in JIS, and generally has a thickness smaller than the length and width and flat. In general, the term &quot; , A thin and flat product having a maximum thickness arbitrarily limited, and usually supplied in the form of a roll (Japanese Industrial Standard JIS K6900). However, since the boundary between the sheet and the film is not clear, it is not necessary to distinguish between the two in the present invention. Therefore, the term &quot; film &quot; The term &quot; film &quot;

In the present invention, in the case of "X to Y" (where X and Y are arbitrary numbers), "not less than X and not more than Y" unless otherwise stated, and "preferably greater than X" Quot; is preferably &quot; smaller than Y &quot;.

[Example]

Next, examples of the present invention will be described, but the present invention is not limited to these examples.

&Lt; Measurement method of glass transition temperature >

The sample was held at -40 캜 for 1 minute under a nitrogen atmosphere using a differential scanning calorimeter DSC-7 made by Perkin Elmer, and then measured at a rate of temperature increase of 10 캜 / minute. The temperature at which the differential maximum value of the DSC curve obtained was converted to glass transition Temperature.

(Example 1)

The polycarbonate resin composition (A) and the acrylic resin (B) were heated and melted in separate extruders, respectively, and two types of resins were melt-extruded from the slit-shaped discharge port of the T die to laminate two layers of two kinds.

The main extruder for extruding the polycarbonate resin composition (A) had a barrel diameter of 65 mm, a screw L / D of 35, and a cylinder temperature of 270 캜. The sub-extruder for extruding the acrylic resin (B) had a barrel diameter of 32 mm, a screw L / D of 32, and a cylinder temperature of 250 캜.

The polycarbonate resin composition (A) was prepared by mixing an aromatic polycarbonate (a bisphenol A aromatic polycarbonate prepared by an interfacial polymerization method, viscosity average molecular weight 28000, terminal hydroxyl group concentration = 150 ppm, Tg 145 캜), polycyclohexane Dimethyleneterephthalate resin (low crystalline copolymer polyester having a structure in which 65 mol% of ethylene glycol of PET is substituted with 1.4-CHDM, Tg 86 DEG C) was mixed at a mass ratio of 50:50, A polycarbonate resin composition in which a polymer alloy was obtained by melt kneading was prepared. As a result of measuring the glass transition temperature of the polycarbonate resin composition, it was confirmed that the DSC curve had a single peak (Tg 110 ° C) and was a polymer alloy.

As the acrylic resin (B), an acrylic resin (trade name: Acrypette MD, manufactured by Mitsubishi Rayon Co., Ltd., composition: polymethyl methacrylate, Tg 110 캜) was used.

Feed blocks were used to stack two layers of two layers. The temperature in the die head was set at 250 캜, and the laminated resin in the die was brought into three horizontally arranged casting rolls. At this time, the first roll temperature was set at 110 占 폚, the second roll temperature was set at 140 占 폚, and the third roll temperature was set at 185 占 폚.

The number of revolutions of the main extruder and the sub-extruder was set so that the discharge amount ratio was main / sub = 470/30 and co-extruded so as to have a thickness of 0.5 mm to form a resin sheet for molding (total sheet thickness: 0.5 mm, .

The evaluation results of the obtained molding resin sheet are shown in Table 1.

(Example 2)

A resin sheet for molding (total sheet thickness: 0.5 mm, coating layer thickness: 40 m) was obtained under the same manufacturing conditions as in Example 1, except that the kind of the polycarbonate resin composition (A) was changed.

The polycarbonate resin composition (A) used in this example was obtained by mixing an aromatic polycarbonate (bisphenol A aromatic polycarbonate prepared by an interfacial polymerization method, viscosity average molecular weight 28,000, terminal hydroxyl group concentration = 150 ppm, Tg 145 캜) Polycyclohexane dimethylene terephthalate resin (low crystalline copolymer polyester having a structure in which 65 mol% of ethylene glycol of PET is substituted with 1.4-CHDM, Tg 86 DEG C) was mixed at a mass ratio of 80:20 And melt-kneading the mixture with heating to polymerize the mixture, thereby using the polycarbonate resin composition. As a result of measuring the glass transition temperature of this polycarbonate resin composition, it was confirmed that the DSC curve had a single peak (Tg 135 ° C) and was a polymer alloy.

The evaluation results of the obtained molding resin sheet are shown in Table 1.

(Example 3)

A resin sheet for molding (total sheet thickness: 0.5 mm, coating layer thickness: 40 m) was obtained under the same manufacturing conditions as in Example 1, except that the kind of the polycarbonate resin composition (A) was changed.

The polycarbonate resin composition (A) used in this example was obtained by mixing an aromatic polycarbonate (bisphenol A aromatic polycarbonate prepared by an interfacial polymerization method, viscosity average molecular weight 28,000, terminal hydroxyl group concentration = 150 ppm, Tg 145 캜) Polycyclohexane dimethylene terephthalate resin (low crystalline copolymer polyester having a structure in which 65 mol% of ethylene glycol of PET is substituted with 1.4-CHDM, Tg 86 DEG C) and copolymerized polyester (polybutylene terephthalate (Copolymerized polyester having a structure in which 30 mol% of terephthalic acid in phthalate was substituted with isophthalic acid, Tg 30 DEG C) at a mass ratio of 70:20:10, melt-kneading the mixture with heating to form a polymerized polycarbonate Based resin composition was used. As a result of measuring the glass transition temperature of the polycarbonate resin composition, it was confirmed that the DSC curve had a single peak (Tg 140 ° C) and was a polymer alloy.

The evaluation results of the obtained molding resin sheet are shown in Table 1.

(Example 4)

A resin sheet for molding (total sheet thickness: 0.5 mm, coating layer thickness: 30 占 퐉) was obtained under the same manufacturing conditions as in Example 1 except that the kind of the polycarbonate resin composition (A) was changed.

The polycarbonate resin composition (A) used in this example was obtained by mixing an aromatic polycarbonate (bisphenol A aromatic polycarbonate prepared by an interfacial polymerization method, viscosity average molecular weight 28,000, terminal hydroxyl group concentration = 150 ppm, Tg 145 캜) Polycyclohexane dimethylene terephthalate resin (low crystalline copolymer polyester having a structure in which 65 mol% of ethylene glycol of PET was substituted with 1.4-CHDM, Tg 86 DEG C) was mixed at a ratio of 35:65 A polycarbonate resin composition obtained by mixing and melt-kneading with heating to obtain a polymer alloy. As a result of measuring the glass transition temperature of the polycarbonate resin composition, it was confirmed that the DSC curve had a single peak (Tg 105 ° C) and was a polymer alloy.

The evaluation results of the obtained molding resin sheet are shown in Table 1.

(Example 5)

A resin sheet for molding (total sheet thickness: 0.5 mm, coating layer thickness: 35 m) was obtained under the same manufacturing conditions as in Example 1, except that the kind of the polycarbonate resin composition (A) was changed.

The polycarbonate resin composition (A) used in this example was obtained by mixing an aromatic polycarbonate (bisphenol A aromatic polycarbonate prepared by an interfacial polymerization method, viscosity average molecular weight 28,000, terminal hydroxyl group concentration = 150 ppm, Tg 145 캜) Polycyclohexane dimethylene terephthalate resin (low crystalline copolymer polyester having a structure in which 65 mol% of ethylene glycol of PET is substituted with 1.4-CHDM, Tg 86 DEG C) was mixed at a ratio of 25:75 A polycarbonate resin composition obtained by mixing and melt-kneading with heating to obtain a polymer alloy. As a result of measuring the glass transition temperature of the polycarbonate resin composition, it was confirmed that the DSC curve had a single peak (Tg 90 ° C) and was a polymer alloy.

The evaluation results of the obtained molding resin sheet are shown in Table 1.

(Comparative Example 1)

A single-layered sheet (sheet thickness of 0.5 mm) of the polycarbonate resin composition (A) was obtained without co-extruding the acrylic resin (B) under the same molding conditions as in Example 1.

The extruder for extruding the polycarbonate resin composition (A) had a barrel diameter of 65 mm, a screw L / D of 35, and a cylinder temperature of 270 캜.

As the polycarbonate resin composition (A), an aromatic polycarbonate (bisphenol A type aromatic polycarbonate prepared by an interfacial polymerization method, viscosity average molecular weight 28000, terminal hydroxyl group concentration = 150 ppm, Tg 145 캜) was used.

The evaluation results of the obtained molding resin sheet are shown in Table 2.

(Comparative Example 2)

A resin sheet for molding (total sheet thickness: 0.5 mm, coating layer thickness: 35 m) was obtained under the same manufacturing conditions as in Example 1, except that the kind of the polycarbonate resin composition (A) was changed.

An aromatic polycarbonate (bisphenol A aromatic polycarbonate prepared by an interfacial polymerization method, viscosity average molecular weight 28,000, terminal hydroxyl group concentration = 150 ppm, Tg 145 DEG C) was used as the polycarbonate resin composition (A) Used.

The evaluation results of the obtained molding resin sheet are shown in Table 2.

(Comparative Example 3)

A resin sheet for molding (total sheet thickness: 0.5 mm, coating layer thickness: 35 m) was obtained under the same manufacturing conditions as in Comparative Example 2, except that the molding temperature was changed to 110 占 폚.

The evaluation results of the obtained molding resin sheet are shown in Table 2.

<Test and Evaluation>

1) Pencil Hardness

The pencil hardness was measured on the surface of the molding resin sheet (the surface of the coating layer when a covering layer was formed) obtained in Examples and Comparative Example under a load of 1 kg in accordance with JIS K5400.

Then, "H", "2H", etc., which are more than the above, are evaluated as pass ("○") and "B" less than this is evaluated as " I appreciated.

2) Moldability (Deep Drawability)

The resin sheet for molding obtained in Examples and Comparative Examples was cut into 100 mm x 200 mm x 0.5 mm thick and the obtained sample sheet was preheated at 120 to 150 ° C to obtain a pressure of 5 MPa (see Table 1 and Table 2) Pressure air at a deep drawing height shown in Tables 1 and 2 by high-pressure air. On the other hand, the deep drawing height was set using a mold in which the deep drawing height was changed in units of 1 mm, such as 1 mm, 2 mm ... 5 mm.

The appearance (cracks, whitening, foaming, non-uniformity) of the obtained molded article was observed. When any of cracks, whitening, foaming and unevenness was not observed, (&Quot;? &Quot;) that the molded article could be molded into a state without appearance abnormality.

(Review)

As a result, it was confirmed that the hardness of the molding resin sheet surface (coating layer surface) can be sufficiently increased by forming the coating layer containing the acrylic resin (B) as a main component. Therefore, it is possible to make the surface of the product formed by molding the resin sheet as well as the resin sheet difficult to be scratched.

By setting the absolute value of the glass transition temperature difference of the polycarbonate resin composition (A) as the main component of the substrate layer and the acrylic resin (B) as the main component of the coating layer within 30 DEG C, even if the deep drawing is performed at a deep drawing height of 7 mm or more It has been found that a molded article can be obtained without causing appearance defects such as cracks, whitening, foaming and unevenness.

Thus, when the resin sheet for molding according to the present invention is used, it is expected that a molded article having excellent surface hardness and excellent moldability can be obtained, and an in-mold molded article free from the desire for printing ink can be produced.

As a method for setting the absolute value of the glass transition temperature difference between the polycarbonate resin composition (A) and the acrylic resin (B) within 30 占 폚, the aromatic polycarbonate (A1) (A) is preferably lowered by preparing a polymer alloy with a polyolefin (for example, polyolefin resin), and then the glass transition temperature of the polycarbonate resin composition (A) A copolymerized polyester obtained by replacing a part of glycols with cyclohexane dimethanol or a copolymerized polyester obtained by substituting a part of terephthalic acid with isophthalic acid in polybutylene terephthalate or a mixture thereof I think.

Claims (8)

(B) on one surface of a substrate layer comprising a polycarbonate resin composition (A) comprising an aromatic polycarbonate (A1) and a polymer alloy of a resin (A2) other than the above (A1) (A) and the acrylic resin (B), and the acrylic resin (B) is a laminated sheet having a coating layer containing an acrylic resin Wherein the thermoplastic resin sheet is thermoformed so that the coating layer side becomes the surface of the product, wherein the thermoplastic resin sheet is thermoformed at a deep drawing height of 5 mm or more. The method according to claim 1,
Wherein the resin (A2) is an aromatic polyester. 3. The method of claim 2,
Wherein the aromatic polyester is a copolymerized polyester obtained by replacing a part of ethylene glycol in polyethylene terephthalate with cyclohexane dimethanol or a copolymer polyester obtained by replacing part of terephthalic acid in polybutylene terephthalate with isophthalic acid Or a mixture thereof. &Lt; Desc / Clms Page number 19 &gt; 4. The method according to any one of claims 1 to 3,
And the pencil hardness of the coating layer measured at a load of 1 kg according to JIS K5400 is not less than H. (B) on one surface of a substrate layer comprising a polycarbonate resin composition (A) comprising an aromatic polycarbonate (A1) and a polymer alloy of a resin (A2) other than the above (A1) (A) and the acrylic resin (B), and the acrylic resin (B) is a laminated sheet having a coating layer containing an acrylic resin Wherein the thermosetting resin composition is thermoformed at a deep drawing height of 5 mm or more so that the coated layer side becomes the surface of the product, Is formed by injection molding to form a support layer. 6. The method of claim 5,
Wherein the resin (A2) is an aromatic polyester. The method according to claim 6,
Wherein the aromatic polyester is a copolymerized polyester obtained by replacing a part of ethylene glycol in polyethylene terephthalate with cyclohexane dimethanol or a copolymer polyester obtained by replacing part of terephthalic acid in polybutylene terephthalate with isophthalic acid Or a mixture thereof. &Lt; IMAGE &gt; 8. The method according to any one of claims 5 to 7,
Characterized in that the pencil hardness of the coating layer measured at a load of 1 kg according to JIS K5400 is not less than H.