JP4614761B2 - Mixed resin composition and sheet and molded product using the same - Google Patents

Description

  The present invention relates to a mixed resin composition, a sheet and a molded product using the same, and more specifically, excellent fluidity and secondary processing without impairing the features such as transparency and impact resistance of a polycarbonate resin. The present invention relates to a mixed resin composition of a polycarbonate resin and a polyester resin, and a sheet and a molded article using the same.

  Polyvinyl chloride (hereinafter simply referred to as “PVC”) resin, which has been known as a resin that has transparency and chemical resistance and has a good balance of physical properties, can be used as a plasticizer or various kinds of resins. Since the glass transition temperature can be widely controlled by this compounding agent, it has been used in various applications. In recent years, from the viewpoint of environmental problems and the like, the conversion from PVC resin to PVC substitute resin has been actively studied. As one of the promising candidates for PVC substitute resins, there are polycarbonate resins excellent in transparency and impact resistance, which are used for various applications. However, since the polycarbonate-based resin has a high melt viscosity and low fluidity, it has a disadvantage that it is inferior in moldability when a secondary processed product such as a sheet, film, or molded product is molded. Furthermore, the polycarbonate resin has a high glass transition temperature and good heat resistance compared to the PVC resin, but the secondary processability (usually about 50 ° C. to 100 ° C.) is the same as that of the PVC resin ( There is a drawback in that it is difficult to sufficiently deal with products that require heat shrinkability, vacuum or pressure air formability).

  In order to solve such problems of polycarbonate resins, many mixed resin compositions of polycarbonate resins and polyester resins have been proposed. For example, a mixed resin composition in which a polycarbonate resin and a polyester resin such as polybutylene terephthalate or polyethylene phthalate are mixed is disclosed (for example, see Patent Document 1). However, the secondary processed product obtained from such a conventional mixed resin composition has not yet satisfied sufficient transparency. This is presumably because the transesterification reaction between the polycarbonate resin and the polyester resin does not proceed sufficiently.

  On the other hand, by controlling the transesterification rate of the polycarbonate resin and the polyester resin, a mixed resin composition having improved fluidity and excellent transparency, solvent resistance and impact resistance is disclosed. (For example, refer to Patent Document 2). However, there are problems such as difficulty in controlling the transesterification reaction and the need to use a polycarbonate resin having a functional group at the terminal.

  Further, in a polyester resin composed of terephthalic acid, ethylene glycol, and 1,4-cyclohexanedimethanol (hereinafter also referred to as “1,4-CHDM”), 1,4-CHDM is contained in an amount of 40 mol% or more. Discloses that a resin composition having a single glass transition temperature and good mechanical properties can be obtained by being simply melt-mixed with a polycarbonate resin (see, for example, Non-Patent Document 1). ). However, since a polyester resin containing 1,4-CHDM in an amount of 40 mol% or more usually has a glass transition temperature of 80 ° C. or more, the glass transition temperature of the mixed resin composition with the polycarbonate resin is set to be the same as that of the PVC resin. There was a limit to controlling the temperature range in which secondary processing is performed (usually about 50 ° C. or more and 100 ° C. or less).

Furthermore, for the purpose of improving fluidity without impairing the transparency, impact resistance, etc. of the polycarbonate resin, the polycarbonate resin is 5 parts by mass or more and 95 parts by mass or less, and the polyester resin is 5 parts by mass or more and 95 parts by mass or less. A polyester resin containing at least one kind of polyester resin containing a dicarboxylic acid-based polycondensation component composed of a terephthalic acid-based component and 40 mol% or more of 1,4-CHDM, A mixed resin composition in which the mass ratio of the resin is 10% or more of the entire polyester resin component is disclosed (for example, see Patent Document 3). However, this mixed resin composition does not have both transparency and impact resistance in a well-balanced manner and has not yet been satisfactory.
JP 58-18391 (Claims) Japanese Patent Laid-Open No. 10-87973 (Claims) JP 2002-12748 A (Claims) Res.Discl. (UK), 229,182 (1983).

  An object of the present invention is a polycarbonate resin and a polyester resin that are excellent in transparency, impact resistance, fluidity, secondary workability, etc., have a single glass transition temperature, and are suitably used as a PVC alternative material And a mixed resin composition, and a sheet and a molded product using the same.

  As a result of intensive studies, the inventor shows compatibility when a mixed resin composition of a polycarbonate resin and a specific polyester resin is melt-mixed, and the above problems can be solved by using the mixed resin composition. As a result, the present invention has been completed.

That is, the subject of this invention is achieved by the following mixed resin composition, the sheet | seat and molded article which use this composition.
(1) In the mixed resin composition consisting of 1% by mass to 99% by mass of the polycarbonate resin (A) and 1% by mass to 99% by mass of the polyester resin (B), the polyester resin (B) is The carboxylic acid monomer unit (A) contains 80 mol% or more and 100 mol% or less of an aromatic dicarboxylic acid unit in all carboxylic acid monomer units (I), and a glycol monomer unit (B) As the total glycol monomer unit (b), 1,4-cyclohexanedimethanol unit 0.1 mol% or more and 40 mol% or less and number average molecular weight 500 or more and 3000 or less polyalkylene glycol unit 0.5 mol% A mixed resin composition, which is a polyester resin containing 15 mol% or less.
(2) The glass transition temperature of the mixed resin composition measured at a heating rate of 10 ° C./min by differential scanning calorimetry is single, and the glass transition temperature is the glass transition of the polycarbonate resin (A). The mixed resin composition as described in said (1) located between temperature and the glass transition temperature of the said polyester-type resin (B).
(3) The mixed resin composition according to (1) or (2), wherein the polycarbonate-based resin (A) is an aromatic polycarbonate resin.
(4) The mixed resin composition according to any one of (1) to (3), wherein a glass transition temperature of the polyester-based resin (B) is 0 ° C. or higher and 50 ° C. or lower.
(5) Said (1) thru | or (4) in which said mixed resin composition consists of polycarbonate-type resin (A) 75 mass% or more and 95 mass% or less, and polyester-type resin (B) 5 mass% or more and 25 mass% or less. The mixed resin composition according to any one of the above.
(6) The above (1) to (4), wherein the mixed resin composition is composed of 30% by mass or more and 75% by mass or less of the polycarbonate resin (A) and 25% by mass or more and 70% by mass or less of the polyester resin (B). The mixed resin composition according to any one of the above.
(7) The mixed resin composition according to any one of (1) to (6), wherein the glass transition temperature of the mixed resin composition is 50 ° C. or higher and 100 ° C. or lower.
(8) A sheet comprising the mixed resin composition according to any one of (1) to (7).
(9) A molded product comprising the mixed resin composition according to any one of (1) to (7).

  According to the present invention, a polycarbonate-based resin and a polyester-based resin that are excellent in transparency, impact resistance, fluidity, secondary workability, etc., have a single glass transition temperature, and are suitably used as PVC substitute resins. And a mixed resin composition, and a sheet and a molded article using the same can be provided.

Hereinafter, the mixed resin composition, sheet and molded product of the present invention will be described in detail.
Note that the upper and lower limits of the numerical range in the present invention are equivalent to the present invention as long as they have the same effects as those in the numerical range even if they are slightly outside the numerical range specified by the present invention. It is included in the range.

[Mixed resin composition]
The mixed resin composition of the present invention comprises a polycarbonate-based resin (A) and a polyester-based resin (B), and the polyester-based resin (B) is all carboxylic acid as a carboxylic acid monomer unit (I). The monomer unit (a) contains an aromatic dicarboxylic acid unit in an amount of 80 mol% to 100 mol%, and the glycol monomer unit (b) contains 1, A polyester-based resin containing 0.1 to 40 mol% of 4-cyclohexanedimethanol units and 0.5 to 15 mol% of polyalkylene glycol units having a number average molecular weight of 500 to 3000.

  The polycarbonate resin (A) used in the present invention is preferably an aromatic polycarbonate resin. The aromatic polycarbonate resin may be either a homopolymer or a copolymer. In addition, the aromatic polycarbonate resin may have a branched structure, a linear structure, or a mixture of a branched structure and a linear structure.

  As a method for producing the aromatic polycarbonate resin used in the present invention, any known method such as a phosgene method, a transesterification method or a pyridine method may be used. As an example, a method for producing an aromatic polycarbonate resin by a transesterification method will be described below.

  The transesterification method is a production method in which a divalent phenol and a carbonic acid diester are added with a basic catalyst, and further an acidic substance that neutralizes the basic catalyst is added, and melt transesterification condensation polymerization is performed. Representative examples of the dihydric phenol include bisphenols, and 2,2-bis (4-hydroxyphenyl) propane, that is, bisphenol A is particularly preferably used. Further, part or all of bisphenol A may be replaced with other dihydric phenols. Other dihydric phenols include hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkanes such as bis (4-hydroxyphenyl) methane and 1,1-bis (4-hydroxyphenyl) ethane, Bis (4-hydroxyphenyl) cycloalkane such as 1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, Compounds such as bis (4-hydroxyphenyl) ether, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane Alkylated bisphenols, 2,2-bis ( , May be mentioned 5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) halogenated bisphenols such as propane.

  Representative examples of carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate. Can be mentioned. Of these, diphenyl carbonate is particularly preferably used.

  The weight average molecular weight of the polycarbonate-based resin (A) used in the present invention is usually in the range of 10,000 to 100,000, preferably 20,000 to 50,000, from the balance of mechanical properties and moldability. . In the present invention, the polycarbonate resin (A) may be used alone or in combination of two or more.

  Next, the polyester resin (B) constituting the mixed resin composition of the present invention will be described. The carboxylic acid monomer unit (a) of the polyester resin (B) is an aromatic dicarboxylic acid unit in the total carboxylic acid monomer unit (a) of 80 mol% or more, preferably 85 mol% or more, more preferably It is desirable to contain 90 mol% or more. The aromatic dicarboxylic acid imparts heat resistance and mechanical strength to the polyester resin (B) to be obtained, and the polyester is obtained as long as it is contained in an amount of 80 mol% or more in the total carboxylic acid monomer units (a). The resin (B) exhibits good heat resistance and mechanical strength. On the other hand, the upper limit of the content of the aromatic dicarboxylic acid unit is not particularly limited, but is preferably 100 mol% or less.

  The aromatic dicarboxylic acid unit contained is not particularly limited. For example, terephthalic acid, isophthalic acid, naphthalene-1,4 or 2,6-dicarboxylic acid, anthracene dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4, Examples of the units include 4′-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate. The aromatic dicarboxylic acid unit may be subjected to polymerization as its ester. The ester unit of the aromatic dicarboxylic acid is not particularly limited, but the ester unit of the above aromatic dicarboxylic acid is preferable, and specific examples include units such as lower alkyl ester, aryl ester, carbonate ester, acid halide and the like. .

  In addition, the carboxylic acid monomer unit (a) may contain a small amount of an aliphatic dicarboxylic acid unit (usually in a range of less than 20 mol%). The aliphatic dicarboxylic acid unit is not particularly limited. For example, oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, dodecanedioic acid, dimer acid, 1,3, or 1,4- Examples of the units include cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, and 4,4′-dicyclohexyldicarboxylic acid.

  The glycol monomer unit (b) constituting the polyester-based resin (B) is a polyalkylene glycol having 1,4-CHDM units of 0.1 mol% to 40 mol% and a number average molecular weight of 500 to 3000. It consists of glycol containing 0.5 mol% or more and 15 mol% or less of units. The glycol monomer unit (b) is not particularly limited other than the above-described glycol units, and examples thereof include ethylene glycol, diethylene glycol (including by-product components), 1,2-propylene glycol, and 1,3-propanediol. 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1, 5-pentanediol, 1,6-hexanediol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxy (Ethyl ether)) It may be.

  The glycol unit may contain only one kind or a mixture of two or more kinds. Moreover, color tone, transparency, heat resistance, impact resistance, and the like can be appropriately imparted to the polyester resin. Considering the point of imparting thermal stability at the time of molding of the obtained polyester resin and considering that it is inexpensive and easily available industrially, it is possible to use an ethylene glycol unit as the glycol monomer unit (b). preferable.

  1,4-CHDM contained in the glycol monomer unit (b) mainly imparts impact resistance to the resulting polyester resin (B). Conventionally, when a polyester resin composed of a terephthalic acid unit, an ethylene glycol unit and a 1,4-CHDM unit, and a polycarbonate resin are mixed to obtain a mixed resin composition, the polyester resin and the polycarbonate resin are combined. In order to obtain a resin composition having good compatibility and a transparent single Tg and good mechanical properties, it was common to contain at least 40 mol% of 1,4-CHDM units. (See, for example, Res. Discl. (UK), 229, 182 (1983)). However, polyester resins containing 40 mol% or more of 1,4-CHDM units usually have a Tg of about 80 ° C. or more, and therefore the glass transition temperature (Tg) of the mixed resin composition with the polycarbonate resin. It was difficult to control the temperature within a temperature range (usually about 50 ° C. or more and 100 ° C. or less) at which secondary processing of the PVC resin is performed. As a result of intensive studies, the present inventors have found that if the mixed resin composition is a polycarbonate resin and a specific polyester resin, the content of 1,4-CHDM units in the polyester resin is 40 mol%. It was found that the following are compatible.

  If the content of 1,4-CHDM units in the polyester resin (B) is 0.1 mol% or more in the glycol monomer unit (b), the resulting polyester resin (B) has impact resistance. If the upper limit is 40 mol%, the glass transition temperature of the resulting polyester resin (B) is preferably not extremely lowered. In the present invention, the content of 1,4-CHDM units is 1 mol% or more, more preferably 10 mol% or more, and the upper limit is 38 mol% or less in all glycol monomer units (b). Preferably it is 35 mol% or less. Note that 1,4-CHDM has two types of isomers, cis-type and trans-type, and any of them may be used.

  The polyalkylene glycol unit having a number average molecular weight of 500 or more and 3000 or less contained in the glycol monomer unit (b) is mainly flexible and has a low glass transition temperature (0 to 50 ° C.) in the resulting polyester resin. Is given. If the number average molecular weight of the polyalkylene glycol is 500 or more, sufficient flexibility can be imparted to the resulting polyester resin (B), and if the upper limit is 3000, the compatibility with other components and polymers decreases. It is possible to prevent the polymerization reaction from stagnating or the mechanical strength of the resulting polyester resin from being lowered. The number average molecular weight of the polyalkylene glycol is preferably 800 or more, more preferably 1000 or more, and the upper limit is preferably 2000.

  In addition, the polyalkylene glycol may be used in combination of plural kinds having different number average molecular weights. When a plurality of types are used in combination, the number average molecular weight in a uniformly mixed state is preferably within the above range. The number average molecular weight of the polyalkylene glycol can be measured by a general method such as gel permeation chromatography.

  If the content of the polyalkylene glycol is 0.5 mol% or more in all glycol monomer units (b), flexibility and low glass transition temperature can be imparted to the resulting polyester resin (B), Moreover, if an upper limit is 15 mol%, the fall of the thermal stability and mechanical strength of the obtained polyester-type resin (B) can be suppressed. In the present invention, the content of polyalkylene glycol having a number average molecular weight of 500 or more and 3000 or less is 1 mol% or more, more preferably 3 mol% or more, based on the total glycol monomer units (b), and the upper limit. Is desirably 12 mol%, preferably 10 mol%.

    Specific examples of the polyalkylene glycol unit include units such as polyethylene glycol, polypropylene glycol, polyethylene glycol-polypropylene glycol block copolymer, polytetramethylene glycol, polyhexamethylene glycol and the like. A glycol unit is preferred. These polyalkyl glycol units can be used alone or in combination of two or more.

  As described above, the polyester resin (B) used in the present invention comprises a carboxylic acid monomer unit (a) containing 80 to 100 mol% of aromatic dicarboxylic acid, and 0.1 mol of 1,4-CHDM. % Or more and 40 mol% or less, and a poly (alkylene glycol) having a number average molecular weight of 500 or more and 3000 or less and 0.5 mol% or more and 15 mol% or less. . In order to adjust the flexibility, melt viscosity, transparency, mechanical properties, solvent resistance, etc. of the resulting polyester resin (B), a trivalent or higher polyvalent carboxylic acid compound unit and / or a higher trivalent or higher polyvalent carboxylic acid compound unit. You may copolymerize a small amount (usually 0.05 mol% or more and 2 mol% or less) of a monohydric alcohol unit.

  Here, examples of the trivalent or higher polyvalent carboxylic acid compound unit include units such as trimellitic acid, pyromellitic acid, and anhydrides thereof. Examples of the trihydric or higher polyhydric alcohol unit include units such as trimethylolpropane, pentaerythritol, and glycerin. These can be used alone or in combination of two or more.

  In the case where only the polyvalent carboxylic acid compound unit is contained among the trivalent or higher polyvalent carboxylic acid compound unit and / or the trivalent or higher polyhydric alcohol unit, the content of the polyvalent carboxylic acid compound unit is the total carboxylic acid. In the monomer unit (a), it is usually 0.05 mol% or more, preferably 0.1 mol% or more, and the upper limit is 2 mol%, preferably 1 mol%.

  In the case where only the polyhydric alcohol unit is contained, the content of the polyhydric alcohol is usually 0.05 mol% or more, preferably 0.1 mol% or more in the total glycol monomer unit (b). The upper limit is 2 mol%, preferably 1 mol%.

  On the other hand, when the polyvalent carboxylic acid compound unit and the polyhydric alcohol unit are used in combination, the content of the trivalent or higher polyvalent carboxylic acid compound unit in the total carboxylic acid monomer unit (i) and the trivalent or higher valence. The total content of polyhydric alcohols in the above-mentioned all glycol monomer units (b) is usually 0.05 mol% or more, preferably 0.1 mol% or more, and 2 mol% or less, preferably Is 1 mol% or less. If the content of these polycarboxylic acid compound units and / or polyhydric alcohol units is 0.05 mol% or more in each case, the flexibility and melt viscosity of the resulting polyester resin (B) If the improvement effect is sufficiently obtained and the content is 2 mol% or less, gelation does not make it difficult to control the reaction, and generation of fish eyes can be suppressed in the obtained sheet or molded product.

  The polyester resin (B) used in the present invention can be produced by a known direct polymerization method or transesterification method, and an esterification catalyst such as titanium butoxide, dibutyltin oxide, magnesium acetate, manganese acetate, etc., if necessary. A transesterification catalyst, or a polymerization catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, or germanium dioxide can be used.

  The intrinsic viscosity of the polyester resin (B) used in the present invention, measured at 30 ° C. using tetrachloroethane / phenol (weight ratio 1/1) as a solvent, is 0.4 dl / g or more, preferably 0.7 dl / g or more. In the range of 1.5 dl / g or less, preferably 1.2 dl / g or less. If the intrinsic viscosity is 0.4 dl / g or more, the moisture resistance and mechanical strength of the resulting polyester-based resin (B) will not be extremely lowered, while if the intrinsic viscosity is 1.5 dl / g or less. Since the polymerization reaction can be performed in a relatively short time, it is preferable in terms of production cycle and cost.

  In the present invention, the polyester resin (B) may be used alone or in combination of two or more.

  The mixed resin composition of the present invention is a mixed resin composition composed of 1% by mass to 99% by mass of the polycarbonate resin (A) and 1% by mass to 99% by mass of the polyester resin (B). The mixing mass ratio is preferably adjusted according to the intended use. For example, when it is desired to improve the fluidity without impairing the heat resistance, transparency and impact resistance of the polycarbonate resin (B), the mixing mass ratio of the mixed resin composition is changed to the polycarbonate resin ( A) 75% by mass or more and 95% by mass or less, and polyester resin (B) may be 5% by mass or more and 25% by mass or less. In addition, in the case where it is desired to impart secondary workability (heat shrinkability, vacuum / pneumatic moldability, etc.) in the same temperature range as PVC resin (usually about 50 ° C. to 100 ° C.), the mixed resin composition The mixing mass ratio is 30% to 75% by weight of the polycarbonate resin (A), 25% to 70% by weight of the polyester resin (B), more preferably 40% to 70% by weight of the polycarbonate resin (A). % Or less, the polyester resin (B) may be 30% by mass or more and 60% by mass or less.

Next, the glass transition temperature of the mixed resin composition of the present invention will be described.
The mixed resin composition of the present invention has a single glass transition temperature measured at a heating rate of 10 ° C./min by differential scanning calorimetry, and the glass transition temperature is equal to the glass transition temperature of the polycarbonate resin (A). The temperature is preferably located between the glass transition temperatures of the polyester resin (B).

  Here, the single glass transition temperature of the mixed resin composition means that the mixed resin composition is made of glass using a differential scanning calorimeter (DSC) at a heating rate of 10 ° C./min according to Japanese Industrial Standard JISK7121. It means that only one peak indicating the glass transition temperature appears when the transition temperature is measured. When the glass transition temperature of the mixed resin composition is single, the resulting sheet can achieve good compatibility and excellent transparency. Good compatibility can be confirmed not only by the DSC measurement but also by a dynamic elasticity measurement.

  Since the aromatic polycarbonate resin has a glass transition temperature measured by differential scanning calorimetry of usually about 150 ° C., for example, the polycarbonate resin (A) is 30% by mass to 75% by mass, and the polyester resin (B). In order to impart secondary workability in the same temperature range as PVC resin (usually about 50 ° C. or more and about 100 ° C. or less) with a mixed resin composition of 25% by mass or more and 70% by mass or less, that is, the mixed resin composition In order to set the glass transition temperature of the glass resin to 50 ° C. or higher, preferably 55 ° C. or higher, more preferably 60 ° C. or higher, and the upper limit temperature to 100 ° C., preferably 95 ° C., more preferably 85 ° C. The glass transition temperature of (B) is 0 ° C. or higher, preferably 5 ° C. or higher, and the upper limit is 50 ° C., preferably 45 ° C.

  If the glass transition temperature of the mixed resin composition is 50 ° C. or higher, sufficient heat resistance is easily obtained. On the other hand, if the glass transition temperature is 100 ° C. or lower, secondary processing in the same temperature range as the PVC resin. Sex is obtained. Moreover, if the glass transition temperature of the polyester-based resin (B) is 0 ° C. or higher, the raw material pellets can be prevented from being difficult to handle due to blocking, while the glass transition temperature is 50 ° C. or lower, The effect of lowering the glass transition temperature of the mixed resin composition can be exhibited.

  The mixed resin composition of the present invention includes polyesters and polyethers other than the polyester resin (B) for the purpose of improving and adjusting molding processability and various physical properties of the sheet within a range that does not significantly impair the effects of the present invention. Resin such as polyamide, polyolefin, polymethylmethacrylate, rubber-like modifiers such as core-shell type, graft type or linear random and block copolymers, inorganic particles such as silica, talc, kaolin, calcium carbonate , Pigments such as titanium oxide and carbon black, flame retardants, weather resistance stabilizers, heat resistance stabilizers, hydrolysis inhibitors (carbodiimide compound monomers or polymers, etc.), antistatic agents, melt viscosity improvers, crosslinking agents Additives such as lubricants, nucleating agents, plasticizers and anti-aging agents may be added as appropriate.

  The mixed resin composition of the present invention is not particularly limited by a known method, for example, an extrusion casting method using a T die, a calendar method, an inflation method, or the like, but is usually 5 μm or more and 3000 μm or less. It is suitably formed into a film, sheet or plate of the thickness (hereinafter, the film, sheet or plate is simply abbreviated as sheet). For melt-kneading, commonly used single-screw extruders, twin-screw extruders, kneaders, mixers, and the like can be used. Although not particularly limited, uniform dispersibility of the mixed resin composition, obtained sheet It is preferable to use a twin screw extruder because of the stability of the mechanical strength.

  Moreover, in this invention, it is preferable to suppress as much as possible reaction (transesterification reaction etc.) which generate | occur | produces between a polycarbonate-type resin (A) and a polyester-type resin (B) at the time of melt-kneading. When the reaction proceeds excessively, it is not preferable because not only the thermal properties of the resulting mixed resin composition are deteriorated but also a foaming phenomenon may appear in the sheet due to coloring or gas generation. For this reason, the type of raw material catalyst used (Ge-based catalyst is preferably used) and the amount of catalyst remaining in the raw material, or the temperature and residence time during melt-kneading, if necessary, a phosphorus compound It is preferable to pay attention to addition of a transesterification inhibitor such as phosphoric acid or phosphorous acid compound.

  For example, the molding temperature in the extrusion casting method using a T-die is appropriately adjusted depending on the flow characteristics and film forming properties of the mixed resin composition, but is generally 320 ° C. or less, preferably 240 ° C. or more and 280 ° C. or less. Is preferred. Further, the obtained sheet can be further stretched in a uniaxial direction and / or a biaxial direction. Furthermore, surface treatment and surface processing such as printing, embossing, electron beam processing, coating, and vapor deposition can be performed on the sheet as necessary.

  The sheet obtained from the mixed resin composition of the present invention is excellent in mechanical properties such as transparency, impact resistance and breaking strength and elongation, and is in the same temperature range as PVC resin (usually about 50 ° C to 100 ° C). ) Secondary workability is possible. Therefore, the use of the mixed resin composition of the present invention is not particularly limited, but is suitably used for applications in which PVC resin has been conventionally used. For example, building materials, interior parts, transparent sheets, resin-coated metal plates Sheet, molding (vacuum / pressure-air molding, hot press molding, etc.) sheet, colored plate, transparent plate, shrink film, shrink label, shrink tube, etc.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.
In addition, the various measured values and evaluation about the raw material and sheet | seat displayed in this specification were performed as follows. Here, the flow direction of the sheet from the extruder is referred to as the vertical direction, and the orthogonal direction is referred to as the horizontal direction.

(1) Glass transition temperature (Tg)
Using DSC-7 manufactured by PerkinElmer Co., Ltd., 10 mg of a sample cut from the sheet was heated from −40 ° C. to 250 ° C. at a heating rate of 10 ° C./min according to JIS K7121, and at 250 ° C. for 1 minute. After being held, the temperature was lowered to −40 ° C. at a cooling rate of 10 ° C./min, held at −40 ° C. for 1 minute, and then reheated at a heating rate of 10 ° C./min. Asked.

(2) Composition analysis of polyester resin A solution (sample concentration: 100 mg / 1 milliliter solvent) in which a polyester resin is dissolved in deuterated chloroform (solvent) is used as a sample, and this solution sample is analyzed by a nuclear magnetic resonance apparatus (NMR). ^The analysis was conducted by monitoring ¹ H, and the mol% relative to the total carboxylic acid monomer unit was determined for the carboxylic acid monomer unit, and the mol% relative to the total glycol monomer unit was determined for the glycol monomer unit.

(3) Average refractive index According to JIS K7142, it measured using the Abago refractometer by an Atago Co., Ltd. by using sodium D line | wire (589 nm) as a light source.

(4) Haze (cloudiness value)
The haze value of the sheet obtained according to JIS K7105 was measured.

(5) Tensile modulus According to JIS K7127, the sample was measured in the transverse direction under the conditions of a temperature of 23 ° C. and a test speed of 5 mm / min.

(6) Tensile Fracture Strength, Tensile Fracture Elongation According to JIS K7127, measurement was performed in the transverse direction of the sample at a temperature of 23 ° C. and a test speed of 200 mm / min.

(7) Impact resistance Using a hydro-shot high-speed impact tester (“HTM-1 type” manufactured by Shimadzu Corporation), a sheet cut into a size of 100 mm in the vertical direction and 100 mm in the horizontal direction is used as a sample, and clamped. The sample was fixed at a temperature of 0 ° C., and a hitting core having a diameter of ½ inch was dropped at a dropping speed of 3 m / sec at the center of the sheet to give an impact. The energy (kgf · mm) when the sample was broken was measured.

(8) Flow start temperature The obtained sheet is chopped into small pieces with scissors, dried, and then lifted using a nozzle with an inner diameter of 1 mm and a length of 2 mm by “Koka Type Flow Tester CFT-500C Model” manufactured by Shimadzu Corporation. The measurement was performed under conditions of a temperature rate of 3 ° C./min and a load of 3.92 MPa (40 kgf / cm ² ).

Example 1
As shown in Table 1, as the polycarbonate resin (A), a dried aromatic polycarbonate resin (manufactured by Mitsubishi Engineering Plastics Co., Ltd., “Novalex 7025A”, Tg: 149.5 ° C., average refractive index: 1.5858) ) (Hereinafter sometimes simply abbreviated as PC) 75% by mass, and polyester resin (B), a transparent transparent soft polyester resin (manufactured by Mitsubishi Rayon Co., Ltd., “Dianite DN-124”, Tg: 19.1 ° C., carboxylic acid monomer unit (A): terephthalic acid 100 mol%, glycol monomer unit (B): ethylene glycol 66 mol%, diethylene glycol 2 mol%, 1,4-cyclohexanedimethanol 26 mol %, Polytetramethylene glycol having a number average molecular weight of 1000 mol%, average refractive index: 1.5461 A mixed resin composition consisting of 25% by mass (hereinafter sometimes simply abbreviated as PET-1) is set at a set temperature using a φ40 mm co-directional twin screw extruder (L / D = 36) equipped with a T die. Melting and kneading at 270 ° C., 80 ° C. (In Example 2 and later, the temperature of the cast roll was appropriately adjusted at a temperature around Tg−20 ° C. of the resin composition while confirming the adhesion state of the sheet to the cast roll. ) To obtain a sheet having a thickness of 150 μm. Table 1 shows evaluation results such as glass transition temperature (Tg) and mechanical properties evaluated using the obtained sheet.

(Example 2)
As shown in Table 1, in Example 1, the mixing ratio of PC-1 used as the polycarbonate resin (A) and PET-1 used as the polyester resin (B) was changed to 90% by mass and 10% by mass, respectively. Obtained a sheet in the same manner as in Example 1. Table 1 shows evaluation results such as glass transition temperature (Tg) and mechanical properties evaluated using the obtained sheet.

(Example 3)
As shown in Table 1, in Example 1, the mixing ratio of PC used as the polycarbonate resin (A) and PET-1 used as the polyester resin (B) was changed to 95% by mass and 5% by mass, respectively. Obtained a sheet in the same manner as in Example 1. Table 1 shows evaluation results such as glass transition temperature (Tg) and mechanical properties evaluated using the obtained sheet.

(Comparative Example 1)
As shown in Table 1, in Example 1, the mixing ratio of PC used as the polycarbonate resin (A) and PET-1 used as the polyester resin (B) was changed to 100% by mass and 0% by mass, respectively. Obtained a sheet in the same manner as in Example 1. Table 1 shows evaluation results such as glass transition temperature (Tg) and mechanical properties evaluated using the obtained sheet.

Example 4
As shown in Table 2, except that the mixing ratio of PC used as the polycarbonate resin (A) and PET-1 used as the polyester resin (B) in Example 1 was changed to 50% by mass and 50% by mass, respectively. Obtained a sheet in the same manner as in Example 1. Subsequently, the obtained sheet was stretched 3.0 times in the transverse direction at a stretching temperature of 95 ° C. using a tenter stretching facility, and then rapidly cooled with cold air to obtain a heat-shrinkable sheet having a thickness of 50 μm. Table 2 shows the evaluation results such as the glass transition temperature (Tg) evaluated using the obtained sheet (see FIG. 1) and the mechanical properties evaluated using the obtained heat-shrinkable film. The heat shrinkage rate was determined by cutting the obtained heat-shrinkable sheet into a size of 100 mm in the vertical direction × 100 mm in the horizontal direction, dipping in a hot water bath at 80 ° C. for 10 seconds, measuring the amount of shrinkage in the horizontal direction, and before shrinking. The ratio of the amount of shrinkage to the original size was obtained as a% value.

(Comparative Example 2)
As shown in Table 2, in place of PET-1 used as the polyester-based resin (B) in Example 4, an amorphous polyester resin [Eastman Chemical Co., Ltd., “EASTAR PETG Polyester 6663”, Tg: 79 0.0 ° C., carboxylic acid monomer unit (I): terephthalic acid 100 mol%, glycol monomer unit (B): ethylene glycol 68 mol%, 1,4-cyclohexanedimethanol 32 mol%, average refractive index: 1.5667] (hereinafter, sometimes simply abbreviated as PET-2), a sheet was obtained in the same manner as in Example 4. Subsequently, an attempt was made to stretch the obtained sheet 3.0 times in the transverse direction at a stretching temperature of 95 ° C. using a tenter-stretching facility, but the film was not stretchable due to film breakage. Moreover, the obtained sheet | seat showed the glass transition temperature (Tg) in two places, 79.4 degreeC and 134.8 degreeC (refer FIG. 2).

  From Tables 1 and 2, the mixed resin composition of the polycarbonate resin and the polyester resin specified in the present invention has a single glass transition temperature, and features such as transparency and impact resistance of the polycarbonate resin. It turns out that it is excellent in fluidity | liquidity (Examples 1-3), secondary workability (Example 4), etc., without impairing greatly. In contrast, the polycarbonate resin alone has good impact resistance and transparency, but is inferior in fluidity (Comparative Example 1), and when a polyester resin outside the range specified in the present invention is used. Is inferior in compatibility with polycarbonate resin, and it is difficult to impart secondary workability (such as heat shrinkability) in the same temperature range as PVC resin (usually about 50 ° C to 100 ° C). It can be seen (Comparative Example 2).

It is a DSC thermogram which shows the glass transition temperature (Tg) of the sheet | seat obtained in Example 4. 6 is a DSC thermogram showing the glass transition temperature (Tg) of the sheet obtained in Comparative Example 2.

Claims (9)

  In the mixed resin composition comprising 1% by mass to 99% by mass of the polycarbonate resin (A) and 1% by mass to 99% by mass of the polyester resin (B), the polyester resin (B) is a carboxylic acid. As monomer units (A), all carboxylic acid monomer units (I) contain aromatic dicarboxylic acid units in an amount of 80 mol% to 100 mol%, and glycol monomer units (B) In the glycol monomer unit (b), the 1,4-cyclohexanedimethanol unit is 0.1 mol% or more and 40 mol% or less, and the polyalkylene glycol unit having a number average molecular weight of 500 or more and 3000 or less is 0.5 mol% or more and 15 mol%. %, A mixed resin composition characterized by being a polyester-based resin.   The glass transition temperature of the mixed resin composition measured at a heating rate of 10 ° C./min by differential scanning calorimetry is single, and the glass transition temperature is equal to the glass transition temperature of the polycarbonate resin (A). The mixed resin composition of Claim 1 located between the glass transition temperatures of a polyester-type resin (B).   The mixed resin composition according to claim 1, wherein the polycarbonate resin (A) is an aromatic polycarbonate resin.   The mixed resin composition according to any one of claims 1 to 3, wherein a glass transition temperature of the polyester-based resin (B) is from 0C to 50C.   5. The mixed resin composition according to claim 1, wherein the mixed resin composition comprises 75% by mass or more and 95% by mass or less of the polycarbonate resin (A) and 5% by mass or more and 25% by mass or less of the polyester resin (B). Mixed resin composition.   5. The mixed resin composition according to claim 1, wherein the mixed resin composition comprises 30% to 75% by mass of the polycarbonate resin (A) and 25% to 70% by mass of the polyester resin (B). Mixed resin composition.   The mixed resin composition according to any one of claims 1 to 6, wherein a glass transition temperature of the mixed resin composition is 50 ° C or higher and 100 ° C or lower.   A sheet comprising the mixed resin composition according to claim 1.   A molded article comprising the mixed resin composition according to any one of claims 1 to 7.

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