Particle and particle production method, resin composition and method for producing the same

Abstract

To provide particles which are excellent in powder flowability and blocking resistance.SOLUTION: Particles contain a block copolymer and / or a graft copolymer (A), wherein the block copolymer and / or the graft copolymer (A) contains a (meth)acrylic polymer (A1) and a (meth)acrylic polymer (A2), and the (meth)acrylic polymer (A1) includes a structural unit derived from methacrylate having a glass transition temperature (Tg) of a homopolymer higher than 80°C, and a structural unit derived from (meth)acrylate having a refractive index (nD20) of the homopolymer of 1.50 or more, the particles having an angle of repose of 50° or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to particles having excellent powder flowability and blocking resistance and a method for producing the same, and to a resin composition containing the particles and a polycarbonate resin and a method for producing the same. [Background technology]

[0002] Polycarbonate resins are generally produced using raw materials derived from petroleum resources. However, in recent years, concerns have arisen about the depletion of petroleum resources, and there is a demand for polycarbonate resins made from raw materials obtained from biomass resources such as plants. In addition, there are concerns that global warming due to the increase and accumulation of carbon dioxide emissions will lead to climate change, and therefore there is a demand for the development of polycarbonate resins made from plant-derived monomers that are carbon-neutral even when disposed of after use. For example, it has been proposed to use isosorbide (ISB) as a plant-derived monomer and obtain a polycarbonate resin by transesterification with diphenyl carbonate (see, for example, Patent Document 1).

[0003] Polycarbonate resins obtained from dihydroxy compounds such as isosorbide not only have excellent optical properties but also significantly superior weather resistance and surface hardness compared to conventionally used aromatic polycarbonate resins. However, further improvements in mechanical properties such as tensile elongation and impact resistance in areas where stress is concentrated are required. To address this issue, it is known that adding a core-shell polymer to polycarbonate resin improves impact resistance (see, for example, Patent Document 2).

[0004] In addition, a method has been proposed in which a block copolymer and / or a graft copolymer is added to a polycarbonate resin using isosorbide as a monomer, thereby achieving both transparency and impact resistance over a wide temperature range (Patent Document 3). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] British Patent No. 1079686 [Patent Document 2] Patent No. 5927299 [Patent Document 3] International Publication No. 2022 / 114157 Summary of the Invention [Problem to be solved by the invention]

[0006] According to the investigations of the present inventors, a resin composition containing a core-shell polymer in a polycarbonate resin using isosorbide as a monomer, as in Patent Document 2, is transparent at room temperature and has excellent impact resistance. However, there is a problem in that the transparency decreases and the haze value increases when the molded product is heated.

[0007] Patent Document 3 discloses a resin composition obtained by adding a block copolymer and / or a graft copolymer to a polycarbonate resin using isosorbide as a monomer, which can improve the impact resistance of molded articles while maintaining transparency over a wide temperature range. Examples of methods for producing the block copolymer and / or graft copolymer used here include a method in which the copolymer is obtained as particles using a suspension polymerization method. Suspension polymerization is a superior polymerization method to other polymerization methods, such as emulsion polymerization and bulk polymerization, in that it is easy to control the heat generated by polymerization and impurities can be removed by washing the particles. On the other hand, good powder flowability of particles obtained by suspension polymerization is important for improving processability in manufacturing sites, and blocking resistance of particles is important for improving the handleability of particles after long-term storage. However, the block copolymer and / or graft copolymer described in Patent Document 3 was insufficient in terms of blocking resistance and processability.

[0008] The present invention has been made in view of the above background, and aims to provide particles having excellent powder fluidity and blocking resistance, a method for producing the particles, a resin composition containing the particles, and a method for producing the resin composition. [Means for solving the problem]

[0009] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by particles containing a block copolymer and / or a graft copolymer (A) containing a specific (meth)acrylic polymer (A1) and a (meth)acrylic polymer (A2). That is, the present invention provides the following: <1> ~ <14> The summary is as follows.

[0010] <1> Particles containing a block copolymer and / or a graft copolymer (A), the block copolymer and / or graft copolymer (A) contains a (meth)acrylic polymer (A1) and a (meth)acrylic polymer (A2); the (meth)acrylic polymer (A1) contains structural units derived from a methacrylate having a homopolymer glass transition temperature (Tg) of higher than 80°C and structural units derived from a (meth)acrylate having a homopolymer refractive index (nD20) of 1.50 or higher, Particles having an angle of repose of 50° or less as measured by the following method: <Method for measuring angle of repose> Using a Tsutsui A, B, D powder property measuring instrument (A, B, D-72 model) manufactured by Rikagaku Kikaisha, the particles are gently poured onto a circular plate with a diameter of 80 mm, forming a mound. The angle of the left base of the mound formed on the circular plate is measured as the angle of repose.

[0011] <2> the (meth)acrylic polymer (A2) contains a structural unit derived from an alkyl acrylate having a homopolymer glass transition temperature (Tg) of less than 0°C and a structural unit derived from an aromatic vinyl; <1> The particle according to claim 1.

[0012] <3> The composition further comprises a (meth)acrylic copolymer (B) different from the block copolymer and / or graft copolymer (A), and the glass transition temperature (Tg) of the (meth)acrylic copolymer (B) is 40°C or higher and 75°C or lower. <1> or <2> The particle according to claim 1.

[0013] <4> The mass average molecular weight (Mw) of the block copolymer and / or graft copolymer (A) is 20,000 or more and 10,000,000 or less. <1> ~ <3> 1. The particle according to any one of the preceding items.

[0014] <5> The (meth)acrylic polymer (A2) further contains a structural unit derived from an aromatic acrylate. <1> ~ <4> 1. The particle according to any one of the preceding items.

[0015] <6> The (meth)acrylic polymer (A1) contains a structural unit derived from a macromonomer (a1) represented by the following general formula (1): <1> ~ <5> 1. The particle according to any one of the preceding items.

[0016] [ka]

[0017] (In formula (1), R 0 ~R n are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. 1 ~X n are each independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10,000.

[0018] <7> <1> ~ <6> A method for producing particles according to any one of the above, a step of obtaining the block copolymer and / or graft copolymer (A) by polymerizing a polymerizable composition (X) containing the (meth)acrylic polymer (A1) and the (meth)acrylic polymer (A2) by suspension polymerization; and mixing the block copolymer and / or graft copolymer (A) with the (meth)acrylic copolymer (B), and then heat-treating the mixture at a temperature equal to or higher than the glass transition temperature (Tg) of the (meth)acrylic copolymer (B).

[0019] <8> The method further comprises a step of producing the (meth)acrylic copolymer (B) by an emulsion polymerization method. <7> A method for producing the particles described in .

[0020] <9> The polymerizable composition (X) contains a macromonomer (a1) represented by the following general formula (1): <7> or <8> A method for producing the particles described in .

[0021] [ka]

[0022] (In formula (1), R 0 ~R n are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. 1 ~X n are each independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10,000.

[0023] <10> The polymerizable composition (X) contains a monomer (a2), and the monomer (a2) contains an alkyl acrylate having a glass transition temperature (Tg) of a homopolymer of less than 0°C and an aromatic vinyl. <7> ~ <9> 1. A method for producing particles according to any one of the preceding claims.

[0024] <11> Polycarbonate resin (C) and <1> ~ <6> A resin composition comprising the particles according to any one of the above items.

[0025] <12> the (meth)acrylic polymer (A2) has a glass transition temperature (Tg) of less than 0°C; the difference in refractive index (nD20) between the polycarbonate resin (C) and the (meth)acrylic polymer (A2) is less than 0.026; <11> The resin composition according to claim 1.

[0026] <13> the difference in refractive index (nD20) between the polycarbonate resin (C) and the (meth)acrylic polymer (A1) is less than 0.030; <11> or <12> The resin composition according to claim 1.

[0027] <14> <11> ~ <13> 2. A method for producing the resin composition according to any one of the above items 1 to 11, comprising melt-kneading the polycarbonate resin (C) and the particles. [Effects of the Invention]

[0028] The particles of the present invention have excellent powder flowability and blocking resistance. Furthermore, the resin composition of the present invention containing the particles of the present invention and a polycarbonate resin (C) and a molded article obtained by molding the resin composition have good appearance and impact resistance. [Brief explanation of the drawings]

[0029] [Figure 1] FIG. 1 is an exploded perspective view showing an apparatus for preparing a sample for evaluating blocking resistance. DETAILED DESCRIPTION OF THE INVENTION

[0030] The present invention will be described in detail below. However, the following description is an example of an embodiment of the present invention, and the present invention is not limited to the following description as long as it does not deviate from the gist of the present invention. The present invention can be implemented in any modified form without departing from the gist of the present invention. In the present invention, "(meth)acrylic" means one or both of "acrylic" and "methacrylic". Furthermore, "(meth)acrylate" means one or both of "methacrylate" and "acrylate". The same applies to "(meth)acryloyl".

[0031] In the present invention, "monomer" refers to an unpolymerized compound (monomer component before polymerization), and "repeating unit" and "structural unit" refer to a structural unit constituting a polymer derived from a monomer formed by polymerization of the monomer. Furthermore, a structural unit constituting a polymer is referred to as a "monomer unit." A "repeating unit" or a "structural unit" may be a unit formed directly by a polymerization reaction, or may be a unit in which a portion of the unit is converted into a different structure by processing the polymer. In the present invention, "parts by mass" indicates the content of a specific component contained in a total amount of 100 parts by mass. In the present invention, unless otherwise specified, a numerical range expressed using "to" in this specification means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits, and "A to B" means A or more and B or less.

[0032] In the present invention, the mass average molecular weight (Mw) of the block copolymer and / or graft copolymer (A) and the (meth)acrylic copolymer (B) refers to the mass average molecular weight, which is the relative molecular weight determined using gel permeation chromatography (GPC) in terms of polymethyl methacrylate (PMMA).

[0033] <Particle> The particles of the present invention (hereinafter sometimes referred to as "particles (P)") contain a block copolymer and / or a graft copolymer (A) as an essential component.

[0034] [Particle angle of repose] The upper limit of the angle of repose of the particles of the present invention, measured using an 80 mm diameter disk as a substrate as described below, is 50° or less, preferably 45° or less, and more preferably 40° or less. A particle angle of repose of 50° or less improves processability in the particle recovery process and the process for producing a molding material containing the particles, improving productivity. Processability here refers to, for example, whether most of the particles can fall under their own weight when they are added to a hopper during the production process. The lower limit of the angle of repose of the particles is not particularly limited. Here, the angle of repose of the particles is a value measured using the device described in the Examples section below.

[0035] [Particle blocking resistance] As an indicator of the blocking resistance of the particles of the present invention, the 60% crushing time measured by the method described in the Examples section below is preferably less than 600 seconds, more preferably less than 300 seconds, and even more preferably less than 100 seconds. If the 60% crushing time, which is an indicator of the blocking resistance of the particles, is less than 600 seconds, the particles will be easy to handle after long-term storage. There is no particular limitation on the lower limit of this 60% crushing time.

[0036] <Block Copolymer and / or Graft Copolymer (A)> The block copolymer and / or graft copolymer (A) according to the present invention may have any structure such as diblock, triblock, multiblock, graft, cyclic, star, comb, dendritic, or ladder structure, or may have a structure in which a plurality of these structures are combined. Among these structures, it is preferable to have at least one of the diblock, triblock, and graft structures, since this can impart excellent impact resistance and flexibility and is relatively easy to produce.

[0037] The block copolymer and / or graft copolymer (A) according to the present invention must contain a (meth)acrylic polymer (A1) and a (meth)acrylic copolymer (A2) in the polymer molecule. In this case, for example, the block copolymer and / or graft copolymer (A) may be a graft copolymer in which the main chain is constituted by a (meth)acrylic polymer (A1), and a graft chain made of a (meth)acrylic copolymer (A2) is branched and connected to the main chain made of the (meth)acrylic polymer (A1). Conversely, the main chain may be a (meth)acrylic copolymer (A2) and the side chain may be a (meth)acrylic polymer (A1). The block copolymer and / or graft copolymer (A) may be a block copolymer in which a polymer made of a (meth)acrylic polymer (A1) and a polymer made of a (meth)acrylic copolymer (A2) are connected in series. Furthermore, the main chain and / or side chain of the graft copolymer may have a structure containing a block copolymer.

[0038] In the block copolymer and / or graft copolymer (A), the (meth)acrylic polymer (A1) preferably has the function of imparting miscibility or compatibility with the matrix resin when the block copolymer and / or graft copolymer (A) contains another matrix resin, or the function of enabling the particles of the present invention to be handled as a solid. In addition, the (meth)acrylic copolymer (A2) in the block copolymer and / or graft copolymer (A) preferably has the function of imparting flexibility, impact resistance, moldability, etc.

[0039] The mass average molecular weight (Mw) of the block copolymer and / or graft copolymer (A) is preferably 20,000 or more, more preferably 30,000 or more, even more preferably 100,000 or more, and particularly preferably 300,000 or more, from the viewpoint of the mechanical properties of the resin composition containing the particles of the present invention and the molded article obtained therefrom. On the other hand, the mass average molecular weight (Mw) of the block copolymer and / or graft copolymer (A) is preferably 10,000,000 or less, more preferably 9,000,000 or less, even more preferably 8,000,000 or less, and particularly preferably 7,000,000 or less, from the viewpoint of the optical properties of the resin composition containing the particles of the present invention and the molded article obtained therefrom and the fluidity during melt molding.

[0040] The number average molecular weight (Mn) of the block copolymer and / or graft copolymer (A) is preferably 10,000 or more, more preferably 20,000 or more, even more preferably 40,000 or more, and particularly preferably 60,000 or more, from the viewpoint of the mechanical properties of the resin composition containing the particles of the present invention and the molded article obtained therefrom. On the other hand, the number average molecular weight (Mn) of the block copolymer and / or graft copolymer (A) is preferably 5,000,000 or less, more preferably 1,000,000 or less, even more preferably 500,000 or less, and particularly preferably 200,000 or less, from the viewpoint of the optical properties of the resin composition containing the particles of the present invention and the molded article obtained therefrom and the fluidity during melt molding.

[0041] [(Meth)acrylic polymer (A1)] The (meth)acrylic polymer (A1) in the present invention contains a structural unit derived from a methacrylate having a homopolymer glass transition temperature (Tg) of higher than 80°C (hereinafter, also referred to as a "methacrylate unit") and a structural unit derived from a (meth)acrylate having a homopolymer refractive index (nD20) of 1.50 or higher (hereinafter, also referred to as a "(meth)acrylate unit").

[0042] The (meth)acrylic polymer (A1) adjusts the miscibility and compatibility of the block copolymer and / or graft copolymer (A) when mixed with the polycarbonate resin (C), thereby controlling the size and morphology of the phase separation. Therefore, the (meth)acrylic polymer (A1) is preferably designed to have good compatibility with the polycarbonate resin (C). To improve the compatibility between the (meth)acrylic polymer (A1) and the polycarbonate resin (C) and to prevent a decrease in the heat resistance of the resin composition of the present invention containing the particles of the present invention and the polycarbonate resin (C) and the molded article obtained therefrom, it is preferable that the (meth)acrylic polymer (A1) have a relatively high glass transition temperature (Tg). Furthermore, a relatively high glass transition temperature (Tg) of the (meth)acrylic polymer (A1) increases the melt viscosity of the (meth)acrylic polymer (A1) and the block copolymer and / or graft copolymer (A), thereby reducing the difference in melt viscosity with the polycarbonate resin (C). As a result, when the resin composition of the present invention containing the particles of the present invention and the polycarbonate resin (C) is melt-kneaded, the compatibility between the polycarbonate resin (C) and the block copolymer and / or graft copolymer (A) is improved, and the particles are easily dispersed in small particles, which allows the resin composition and molded articles obtained therefrom to exhibit transparency over a wide temperature range.

[0043] The (meth)acrylic polymer (A1) contains methacrylate units having a homopolymer glass transition temperature (Tg) of higher than 80°C. In this case, the block copolymer and / or graft copolymer (A) has sufficient heat resistance, and the resulting resin composition has good heat resistance. (Hereinafter, the Tg of the methacrylate homopolymer constituting this (meth)acrylic polymer (A1) may be referred to as the "Tg of the polymethacrylate.")

[0044] From the viewpoint of the heat resistance, the glass transition temperature (Tg) of the (meth)acrylic polymer (A1) is preferably 85°C or higher, more preferably 90°C or higher, and even more preferably 98°C or higher. If the Tg of the polymethacrylate is 80°C or lower, a resin composition having sufficient heat resistance cannot be obtained. On the other hand, if the Tg of the (meth)acrylic polymer (A1) is too high, the resin composition and a molded article obtained therefrom become hard and brittle. Therefore, the Tg of the (meth)acrylic polymer (A1) is preferably 150°C or lower, more preferably 130°C or lower, and even more preferably 120°C or lower. From the same viewpoint, the Tg of the (meth)acrylic polymer (A1) is preferably close to the Tg of the polycarbonate resin (C). The difference (absolute value) between the Tg of the polycarbonate resin (C) and the Tg of the polymethacrylate is preferably 50°C or less, more preferably 40°C or less, and even more preferably 30°C or less.

[0045] In general, the glass transition temperature of a polymer can be determined using differential scanning calorimetry (DSC). Alternatively, the temperature at which the loss tangent (tan δ) peaks using dynamic mechanical analysis (DMA) can be used as the glass transition temperature. The glass transition temperatures of the resin composition may be determined separately for the polycarbonate resin (C), the (meth)acrylic polymer (A1), and the (meth)acrylic polymer (A2). When the (meth)acrylic polymer (A2) functions as a rubber in the resin composition and provides good impact resistance, the glass transition temperature derived from the (meth)acrylic polymer (A2) may be determined.

[0046] Examples of methacrylates having a Tg of higher than 80° C. include alkyl methacrylates, cycloalkyl methacrylates, and aryl group-containing methacrylates. Examples of alkyl methacrylates that provide polymethacrylates with a Tg of greater than 80° C. include methyl methacrylate, isopropyl methacrylate, and t-butyl methacrylate. Examples of cycloalkyl methacrylates having a polymethacrylate Tg of greater than 80° C. include cyclohexyl methacrylate, isobornyl methacrylate, t-butylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, dicyclopentadienyl methacrylate, dicyclopentanyl methacrylate, and adamantyl methacrylate. An example of an aryl group-containing methacrylate having a polymethacrylate Tg of greater than 80° C. is phenyl methacrylate. These may be used alone or in combination of two or more. Of these, methyl methacrylate and phenyl methacrylate are preferred, and it is particularly preferred that the (meth)acrylic polymer (A1) contains a methyl methacrylate unit in terms of the glass transition temperature, availability, etc.

[0047] Furthermore, the closer the refractive indexes of the polycarbonate resin (C) and the (meth)acrylic polymer (A1), the better the transparency of the resin composition of the present invention containing the particles of the present invention and the polycarbonate resin (C) and the molded article obtained therefrom.

[0048] The refractive index of a polymer is expressed as nD20, using a temperature of 20°C and the D line of the sodium spectrum as the light beam. In the present invention, the nD20 value is measured using an Abbe refractometer, but similar refractive index values ​​can also be obtained using a V-block refractometer or a prism coupling refractometer.

[0049] The refractive index difference between the polycarbonate resin (C) and the (meth)acrylic polymer (A1) is determined as the difference in nD20 value, and this refractive index difference is preferably less than 0.030, more preferably less than 0.015, even more preferably less than 0.010, and particularly preferably less than 0.005. When the refractive index difference between the polycarbonate resin (C) and the (meth)acrylic polymer (A1) is less than 0.030, the transparency of the resin composition and the molded article obtained therefrom becomes good over a wide temperature range.

[0050] To achieve such transparency, the (meth)acrylic polymer (A1) contains a (meth)acrylate unit having a homopolymer refractive index of 1.50 or higher. In this case, it becomes easier to design a small difference in refractive index between the polycarbonate resin (C) and the (meth)acrylic polymer (A1), and the resin composition of the present invention containing the particles of the present invention and the polycarbonate resin (C) has good transparency. Examples of the (meth)acrylate unit having a homopolymer refractive index of 1.50 or higher include cycloalkyl (meth)acrylates and aryl group-containing (meth)acrylates. An example of a cycloalkyl(meth)acrylate having a homopolymer refractive index of 1.50 or more is adamantyl(meth)acrylate. Examples of aryl group-containing (meth)acrylates having a homopolymer refractive index of 1.50 or higher include phenyl (meth)acrylate, benzyl (meth)acrylate, and 2-phenoxyethyl (meth)acrylate. These may be used alone or in combination of two or more.

[0051] As a result of extensive investigations, the present inventors have found that, among these monomer units, phenyl methacrylate units are not only effective as high-refractive-index components for adjusting the refractive index, but also contribute to improving compatibility with the polycarbonate resin (C) and improving heat resistance. Therefore, it is particularly preferred that the (meth)acrylic polymer (A1) contains phenyl methacrylate units.

[0052] In order to obtain both the effects of heat resistance and transparency due to the (meth)acrylic polymer (A1) containing methacrylate units having a homopolymer glass transition temperature (Tg) of greater than 80°C and (meth)acrylate units having a homopolymer refractive index of 1.50 or greater, the content ratio of the methacrylate units having a homopolymer glass transition temperature (Tg) of greater than 80°C to the (meth)acrylate units having a homopolymer refractive index of 1.50 or greater in the (meth)acrylic polymer (A1) is preferably in the range of 70 to 95 parts by mass:5 to 30 parts by mass, particularly 75 to 90 parts by mass:10 to 25 parts by mass. When the (meth)acrylic polymer (A1) further contains phenyl methacrylate units, the content of the phenyl methacrylate units is preferably 5 to 25 parts by mass, and more preferably 10 to 20 parts by mass, per 100 parts by mass of the total of the methacrylate units having a homopolymer glass transition temperature (Tg) of higher than 80°C, the (meth)acrylate units having a homopolymer refractive index of 1.50 or higher, and the phenyl methacrylate units.

[0053] The content of the (meth)acrylic polymer (A1) is preferably 35 to 75 parts by mass per 100 parts by mass of the total weight of the block copolymer and / or graft copolymer (A). If the lower limit of the content of the (meth)acrylic polymer (A1) is 35 parts by mass or more, particles containing the block copolymer and / or graft copolymer (A) with excellent miscibility and compatibility with the matrix resin are easily obtained. The lower limit of the content of the (meth)acrylic polymer (A1) is more preferably 40 parts by mass or more, even more preferably 45 parts by mass or more, and particularly preferably 50 parts by mass or more. On the other hand, if the upper limit of the content of the (meth)acrylic polymer (A1) is 75 parts by mass or less, the content of the (meth)acrylic polymer (A2) is relatively ensured, making it easier to obtain the flexibility-imparting effect and improved impact resistance of the (meth)acrylic polymer (A2). The upper limit of the content of the (meth)acrylic copolymer (A1) is more preferably 70 parts by mass or less, even more preferably 65 parts by mass or less.

[0054] [(Meth)acrylic copolymer (A2)] The (meth)acrylic copolymer (A2) preferably contains a structural unit derived from an alkyl acrylate (hereinafter sometimes referred to as an "alkyl acrylate unit") whose homopolymer has a glass transition temperature (Tg) of less than 0° C., and a structural unit derived from an aromatic vinyl (hereinafter sometimes referred to as an "aromatic vinyl unit"). Hereinafter, the glass transition temperature (Tg) of the alkyl acrylate homopolymer will be referred to as the "Tg of the polyalkyl acrylate."

[0055] The (meth)acrylic copolymer (A2) serves to improve impact resistance as a flexible rubber component when the block copolymer and / or graft copolymer (A) is mixed with the polycarbonate resin (C). Therefore, it is preferable that the (meth)acrylic copolymer (A2) is incompatible with the polycarbonate resin (C) and has a low glass transition temperature. When the Tg of the polyalkyl acrylate constituting the (meth)acrylic copolymer (A2) is less than 0°C, the impact resistance of the resin composition of the present invention containing the particles of the present invention and the polycarbonate resin (C) is improved. The Tg of the polyalkyl acrylate is more preferably -5°C or lower, even more preferably -10°C or lower, and particularly preferably -20°C or lower. There is no particular limit on the lower limit of this Tg. From the same viewpoint, the Tg of the (meth)acrylic polymer (A2) is also preferably less than 0° C., more preferably not more than −5° C., even more preferably not more than −10° C., and particularly preferably not more than −20° C. There is no particular restriction on the lower limit of this Tg.

[0056] In the present invention, the refractive index difference between the polycarbonate resin (C) and the (meth)acrylic copolymer (A2) is determined as the difference in nD20 value, and this refractive index difference is preferably less than 0.026, more preferably less than 0.020. When the refractive index difference between the polycarbonate resin (C) and the (meth)acrylic copolymer (A2) is less than 0.026, the transparency of the resin composition and the molded article obtained therefrom is improved. The closer the refractive indexes of the polycarbonate resin (C) and the (meth)acrylic copolymer (A2), the better the transparency of the resin composition and the molded article obtained therefrom. Therefore, the refractive index difference is more preferably less than 0.010, particularly preferably less than 0.008, and most preferably less than 0.004.

[0057] For the transparency of a resin composition to be good, the relationship between the refractive index of the polycarbonate resin (C) and the refractive index of the block copolymer and / or graft copolymer (A) is also important. As mentioned above, the (meth)acrylic copolymer (A1) and the polycarbonate resin (C) are highly compatible, and the (meth)acrylic copolymer (A1) and the polycarbonate resin (C) are partially integrated, while the (meth)acrylic copolymer (A2) is incompatible with the polycarbonate resin (C). Therefore, a small difference in refractive index between the (meth)acrylic copolymer (A2) and the polycarbonate resin (C) is considered to be more important for the transparency of the resin composition. In contrast, the influence of the difference in refractive index between the (meth)acrylic copolymer (A1) and the polycarbonate resin (C) on the transparency of the resin composition is considered to be smaller than that of the (meth)acrylic copolymer (A2). For this reason, the block copolymer and / or graft copolymer (A) has a (meth)acrylic copolymer (A1) and a (meth)acrylic copolymer (A2), and as described above, as long as the refractive index difference between the (meth)acrylic copolymer (A2) and the polycarbonate resin (C) is less than 0.026, transparency can be maintained over a wide temperature range, and the refractive index difference between the (meth)acrylic copolymer (A1) and the polycarbonate resin (C) is not particularly limited. In other words, when comparing the (meth)acrylic copolymer (A1) and the (meth)acrylic copolymer (A2), the (meth)acrylic copolymer (A1) has a wider allowable range for the refractive index difference.

[0058] The (meth)acrylic copolymer (A2) preferably contains an alkyl acrylate unit having a polyalkyl acrylate Tg of less than 0°C. In this case, the impact resistance of the resin composition of the present invention containing the particles of the present invention and the polycarbonate resin (C) is improved. Examples of alkyl acrylates having a polyalkyl acrylate Tg of less than 0°C include 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, n-butyl acrylate, n-propyl acrylate, ethyl acrylate, and 2-hydroxyethyl acrylate. Alternatively, methyl acrylate, ethyl acrylate, and n-butyl acrylate are preferred as the alkyl acrylate, since they improve the compatibility between the (meth)acrylic copolymer (A1) and the (meth)acrylic copolymer (A2) and can improve the transparency and impact resistance of the resin composition and the molded article obtained therefrom. These may be used alone or in combination of two or more.

[0059] Furthermore, from the viewpoint of making it easier to adjust the refractive index difference between the (meth)acrylic copolymer (A2) and the polycarbonate resin (C), the (meth)acrylic copolymer (A2) preferably contains a radically polymerizable monomer unit containing an aromatic ring, and more preferably contains an aromatic vinyl unit. The aromatic vinyl unit serves as a high refractive index component and can further improve the transparency of the resin composition of the present invention containing the particles of the present invention and the polycarbonate resin (C).

[0060] Examples of aromatic vinyls include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, pt-butylstyrene, vinylethylbenzene, vinyltoluene, vinylxylene, vinylnaphthalene, diphenylethylene, and divinylbenzene. These may be used alone or in combination of two or more. Among these, styrene is preferred from the viewpoints of practical properties and productivity.

[0061] The (meth)acrylic polymer (A2) preferably further contains a structural unit derived from an aromatic acrylate (hereinafter, sometimes referred to as an "aromatic acrylate unit"). Examples of aromatic acrylates include phenyl acrylate, 2-phenoxyethyl acrylate, and benzyl acrylate. These may be used alone or in combination of two or more. Among these, benzyl acrylate is preferred from the viewpoints of easy availability of the (meth)acrylic polymer (A2) and a low glass transition temperature, which improves the impact resistance of a resin composition containing the particles of the present invention.

[0062] In order to effectively obtain the above-mentioned effects of containing alkyl acrylate units of polyalkyl acrylate having a Tg of less than 0°C and aromatic vinyl units, the (meth)acrylic polymer (A2) preferably has a content ratio of alkyl acrylate units of polyalkyl acrylate having a Tg of less than 0°C to aromatic vinyl units of 60 to 99 parts by mass:1 to 40 parts by mass, particularly 70 to 97 parts by mass:3 to 30 parts by mass, and particularly 75 to 95 parts by mass:5 to 25 parts by mass. Furthermore, when the (meth)acrylic polymer (A2) further contains an aromatic acrylate unit, the content ratio thereof is preferably 5 to 40 parts by mass, particularly 10 to 35 parts by mass, based on the total monomer units constituting the (meth)acrylic polymer (A2).

[0063] The content of the (meth)acrylic polymer (A2) is preferably 25 to 65 parts by mass per 100 parts by mass of the total weight of the block copolymer and / or graft copolymer (A). When the lower limit of the content of the (meth)acrylic polymer (A2) is 25 parts by mass or more, the (meth)acrylic polymer (A2) can provide excellent flexibility and impact resistance. The lower limit of the content of the (meth)acrylic polymer (A2) is more preferably 30 parts by mass or more, even more preferably 35 parts by mass or more, and particularly preferably 40 parts by mass or more. On the other hand, when the upper limit of the content of the (meth)acrylic polymer (A2) is 65 parts by mass or less, the content of the (meth)acrylic polymer (A1) can be relatively ensured, making it easier to obtain miscibility and compatibility of the (meth)acrylic polymer (A1) with the matrix resin. The upper limit of the content of the (meth)acrylic copolymer (A2) is preferably 60 parts by mass or less, more preferably 55 parts by mass or less, and even more preferably 50 parts by mass or less.

[0064] [(Meth)acrylic copolymer (B)] The particles of the present invention preferably further contain a (meth)acrylic copolymer (B) different from the above-mentioned block copolymer and / or graft copolymer (A).

[0065] The monomer units constituting the (meth)acrylic copolymer (B) are not particularly limited, but preferably contain a monomer unit (b1) represented by the following formula (2).

[0066] [ka]

[0067] In the formula (2), R 10 represents a hydrogen atom or a methyl group, and R 11 are hydrogen atoms, halogen atoms, OH, OR 36 , C.N., N.R. 40 R 41 or R 42 and R 36 , R 40 , R 41each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted non-aromatic heterocyclic group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkaryl group, or a substituted or unsubstituted organosilyl group; R 42 represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0068] Examples of the monomer that forms the monomer unit (b1) (hereinafter, may be referred to as "monomer (b1)") include the following monomers. Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, hexadecyl (meth)acrylate, (meth)acrylate Hydrocarbon group-containing (meth)acrylic acid esters such as stearyl (meth)acrylate, isostearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, 3,5,5-trimethylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, terpene acrylate and derivatives thereof, hydrogenated rosin acrylate and derivatives thereof, and docosyl (meth)acrylate.

[0069] Hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerol (meth)acrylate. Carboxyl group-containing vinyl monomers such as crotonic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monooctyl maleate, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, monooctyl itaconate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, and monoethyl citraconic acid.

[0070] Vinyl monomers containing an acid anhydride group such as maleic anhydride and itaconic anhydride. Unsaturated dicarboxylic acid diester monomers such as dimethyl maleate, dibutyl maleate, dimethyl fumarate, dibutyl fumarate, butyl itaconate, and diperfluorocyclohexyl fumarate. Epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate, α-ethyl glycidyl acrylate, and 3,4-epoxybutyl (meth)acrylate. Amino group-containing (meth)acrylic acid ester vinyl monomers such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.

[0071] Vinyl monomers containing an amide group, such as (meth)acrylamide, dimethyl(meth)acrylamide, diethyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-isopropylacrylamide, hydroxyethylacrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetone acrylamide, maleic acid amide, and maleimide.

[0072] Vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, (meth)acrylonitrile, vinyl chloride, vinyl acetate, and vinyl propionate. Polyfunctional vinyl monomers such as divinylbenzene, ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol diallyl ether, and N,N'-methylenebis(meth)acrylamide. Heterocyclic monomers such as (meth)acryloylmorpholine, vinylpyrrolidone, vinylpyridine, and vinylcarbazole.

[0073] Polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, n-butoxyethyl (meth)acrylate, isobutoxyethyl (meth)acrylate, t-butoxyethyl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, acetoxyethyl (meth)acrylate, "Placcel FM" (trade name of caprolactone addition monomer manufactured by Daicel Chemical Industries, Ltd.), "Blemmer PME-100" (trade name of methoxypolyethylene glycol methacrylate (ethylene glycol chain length: 2) manufactured by NOF Corporation), "Blemmer PME-200" (trade name of methoxypolyethylene glycol methacrylate manufactured by NOF Corporation) glycol ester monomers such as acrylate (having four ethylene glycol chains), trade name), "BLEMMER PME-400" (NOF Corporation, methoxypolyethylene glycol methacrylate (having nine ethylene glycol chains), trade name), "BLEMMER 50POEP-800B" (NOF Corporation, octoxypolyethylene glycol-polypropylene glycol-methacrylate (having eight ethylene glycol chains and six propylene glycol chains), trade name), "BLEMMER 20ANEP-600" (NOF Corporation, nonylphenoxy (ethylene glycol-polypropylene glycol) monoacrylate, trade name), "BLEMMER AME-100" (NOF Corporation, trade name), "BLEMMER AME-200" (NOF Corporation, trade name), and "BLEMMER 50AOEP-800B" (NOF Corporation, trade name). Monomers containing silane coupling agents such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, tri-n-propylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, tri-n-amylsilyl (meth)acrylate, tri-n-hexylsilyl (meth)acrylate, tri-n-octylsilyl (meth)acrylate, tri-n-dodecylsilyl (meth)acrylate, triisopropylsilylmethyl fumarate, triisopropylsilylamyl fumarate, tri-n-butylsilyl-n-butylfumarate, tert-butyldiphenylsilylmethyl fumarate, tert-butyldiphenylsilyl-n-butylfumarate, Silaprene FM- Organosilyl group-containing monomers other than silane coupling agent-containing monomers, such as 0711 (manufactured by JNC Corporation, trade name), Silaplane FM-0721 (manufactured by JNC Corporation, trade name), Silaplane FM-0725 (manufactured by JNC Corporation, trade name), Silaplane TM-0701 (manufactured by JNC Corporation, trade name), Silaplane TM-0701T (manufactured by JNC Corporation, trade name), X-22-174ASX (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), X-22-174BX (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), KF-2012 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), X-22-2426 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name), and X-22-2404 (manufactured by Shin-Etsu Chemical Co., Ltd., trade name).

[0074] Halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and chlorotrifluoroethylene. 2-Isocyanatoethyl (meth)acrylate. 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluorophenyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 3-(perfluorobutyl)-2-hydroxypropyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth)acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl Fluorine-containing monomers (excluding halogenated olefins), such as 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)methacrylate, 1H,1H,2H,2H-tridecafluorooctyl (meth)acrylate, and 1H-1-(trifluoromethyl)trifluoroethyl (meth)acrylate. Monomers with an acetal structure such as 1-butoxyethyl (meth)acrylate, 1-(2-ethylhexyloxy)ethyl (meth)acrylate, 1-(cyclohexyloxy)ethyl methacrylate, and 2-tetrahydropyranyl (meth)acrylate. 4-Methacryloyloxybenzophenone, and 2-isocyanatoethyl (meth)acrylate. The hydrocarbon group-containing (meth)acrylic acid esters, hydroxyl group-containing (meth)acrylic acid esters, carboxyl group-containing vinyl monomers, acid anhydride group-containing vinyl monomers, unsaturated dicarboxylic acid diester monomers, epoxy group-containing vinyl monomers, amino group-containing (meth)acrylic acid ester-based vinyl monomers, and amide group-containing vinyl monomers are examples of the above-mentioned.

[0075] The monomer (b1) is preferably at least one selected from the group consisting of the following monomers, from the viewpoint of ease of handling. Hydrocarbon group-containing (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, hexadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, and terpene acrylates and derivatives thereof.

[0076] Hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. Carboxyl group-containing vinyl monomers such as (meth)acrylic acid. Epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate and glycidyl α-ethylacrylate. Amino group-containing (meth)acrylic acid ester vinyl monomers such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate.

[0077] Vinyl monomers containing an amide group, such as (meth)acrylamide, N-methyl(meth)acrylamide, N,N'-dimethyl(meth)acrylamide, N-isopropylacrylamide, and N-(hydroxymethyl)acrylamide. Polyfunctional vinyl monomers such as ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, allyl (meth)acrylate, and N,N'-methylenebis(meth)acrylamide.

[0078] Heterocyclic monomers such as (meth)acryloylmorpholine, vinylpyrrolidone, vinylpyridine, and vinylcarbazole. Monomers containing silane coupling agents such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane. Organosilyl group-containing monomers other than silane coupling agent-containing monomers, such as trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, tri-n-propylsilyl (meth)acrylate, and tri-n-butylsilyl (meth)acrylate.

[0079] Fluorine-containing monomers such as 2,2,2-trifluoroethyl (meth)acrylate and 2,2,3,3-tetrafluoropropyl (meth)acrylate (however, halogenated olefins are excluded). Monomers with an acetal structure such as 1-butoxyethyl (meth)acrylate and 1-(2-ethylhexyloxy)ethyl (meth)acrylate.

[0080] Among these, methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate are more preferred, and methyl (meth)acrylate and butyl (meth)acrylate are even more preferred.

[0081] The lower limit of the mass average molecular weight of the (meth)acrylic copolymer (B) is not particularly limited, but is preferably at least 500,000, more preferably at least 600,000, even more preferably at least 700,000, and particularly preferably at least 800,000. When the mass average molecular weight of the (meth)acrylic copolymer (B) is at least 500,000, the mechanical properties of the particles of the present invention and the resin composition of the present invention containing the particles of the present invention and the polycarbonate resin (C) are good. The upper limit of the mass average molecular weight of the (meth)acrylic copolymer (B) is not particularly limited, but is preferably not more than 5,000,000, more preferably not more than 4,000,000, even more preferably not more than 3,000,000, and particularly preferably not more than 2,000,000. When the mass average molecular weight of the (meth)acrylic copolymer (B) is 5,000,000, the melt fluidity of the particles of the present invention can be maintained good, and the moldability of the resin composition of the present invention containing the particles of the present invention and the polycarbonate resin (C) is improved, resulting in excellent appearance.

[0082] The lower limit of the glass transition temperature (Tg) of the (meth)acrylic copolymer (B) is preferably at least 40° C., more preferably at least 45° C., and even more preferably at least 50° C. When the (meth)acrylic copolymer (B) has a Tg of at least 40° C., the powder fluidity of the particles containing the block copolymer and / or graft copolymer (A) can be improved, and blocking can be prevented. The upper limit of the glass transition temperature (Tg) of the (meth)acrylic copolymer (B) is preferably not more than 75° C., more preferably not more than 70° C. When the (meth)acrylic copolymer (B) has a Tg of not more than 75° C., the (meth)acrylic copolymer (B) can efficiently coat the surface of the block copolymer and / or graft copolymer (A), improving the powder flowability of the particles.

[0083] The Tg is a value calculated from the glass transition temperature and mass fraction of a homopolymer by the Fox formula described in Polymer Handbook [Polymer Handbook, J. Brandrup, Interscience, 1989]. The Fox formula is as follows: 1 / (273+Tg)=Σ(Wi / (273+Tgi)) In the formula, Wi is the mass fraction of monomer i, and Tgi is the glass transition temperature (°C) of the homopolymer of monomer i.

[0084] When a monomer whose homopolymer glass transition temperature is not described in the Polymer Handbook is used, the Tg used is a value measured by a differential scanning calorimeter (DSC).

[0085] The particle size of the (meth)acrylic copolymer (B) is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less, and particularly preferably 1 μm or less, as measured using a particle size distribution analyzer. The particle size of the (meth)acrylic copolymer (B) is preferably 1 nm or more, more preferably 10 nm or more, even more preferably 50 nm or more, and particularly preferably 100 nm or more, as measured using a particle size distribution analyzer. If the particle size of the (meth)acrylic copolymer (B) is 20 μm or less, the block copolymer and / or graft copolymer (A) can be efficiently coated with the (meth)acrylic copolymer (B). If the particle size of the (meth)acrylic copolymer (B) is 1 nm or more, blocking can be prevented. The median size refers to the median value when particle size data are arranged in order from minimum to maximum.

[0086] The (meth)acrylic copolymer (B) can be used either individually or in combination of two or more.

[0087] In the particles of the present invention, the content of the (meth)acrylic copolymer (B) is not particularly limited, but is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 7 parts by mass or less, per 100 parts by mass of the block copolymer and / or graft copolymer (A). It is preferable that the content of the (meth)acrylic copolymer (B) is 10 parts by mass or less, per 100 parts by mass of the block copolymer and / or graft copolymer (A), because the performance of the block copolymer and / or graft copolymer (A) is not impaired in articles using the particles of the present invention. Furthermore, the content of the (meth)acrylic copolymer (B) in the particles of the present invention is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more, per 100 parts by mass of the block copolymer and / or graft copolymer (A). It is preferable that the content of the (meth)acrylic copolymer (B) is 0.1 parts by mass or more relative to 100 parts by mass of the total of the block copolymer and / or graft copolymer (A), since this can improve the powder fluidity of the particles of the present invention and further suppress blocking.

[0088] [Particle manufacturing method] The particles (P) of the present invention are preferably produced by suspension polymerization, from the viewpoints that the heat generated by polymerization can be easily controlled and impurities can be removed by washing. That is, the method for producing the particles (P) preferably includes the steps of: obtaining a block copolymer and / or graft copolymer (A) by polymerizing a polymerizable composition (X) containing a (meth)acrylic polymer (A1) and a (meth)acrylic polymer (A2) by suspension polymerization; and mixing the block copolymer and / or graft copolymer (A) with a (meth)acrylic copolymer (B), followed by heat treatment at a temperature equal to or higher than the glass transition temperature (Tg) of the (meth)acrylic copolymer (B). The form of the (meth)acrylic copolymer (B) is not particularly limited, and may be, for example, a powder, an aqueous suspension, or a slurry solution.

[0089] The heating temperature of the mixture of the block copolymer and / or graft copolymer (A) and the (meth)acrylic copolymer (B) is preferably 75° C. or higher, more preferably 80° C. or higher. When the heating temperature is 75° C. or higher, the powder flowability improving effect of the particles (P) can be further enhanced.

[0090] When the mixture of the block copolymer and / or graft copolymer (A) and the (meth)acrylic copolymer (B) is heated, if the (meth)acrylic copolymer (B) is in a slurry state, a coagulant may be used to promote coagulation. The coagulant is not particularly limited, but examples thereof include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, organic acids such as acetic acid, and salts of inorganic and organic acids with sodium, potassium, calcium, magnesium, and aluminum. These coagulants can be used alone or in combination of two or more.

[0091] [Method for producing block copolymer and / or graft copolymer (A)] The block copolymer and / or graft copolymer (A) according to the present invention can be produced by a living polymerization method or a method using a macromonomer (a1) described below.

[0092] Examples of living polymerization methods include living radical polymerization and living anionic polymerization. Examples of living radical polymerization methods include reversible addition-fragmentation chain transfer polymerization (RAFT), atom transfer radical polymerization (ATRP), nitroxide-mediated polymerization (NMP), and living radical polymerization with organotellurium as a growing end (TERP). The method using macromonomer (a1) is advantageous in that it allows for relatively easy production of block copolymers and / or graft copolymers (A), and is preferred because it has the advantage of eliminating the need for processes for removing catalyst and auxiliary residues and for terminal treatment, which are required in living polymerization methods.

[0093] In a method for producing a block copolymer and / or a graft copolymer (A) using a macromonomer, the macromonomer may be used as a raw material for either the (meth)acrylic polymer (A1) or the (meth)acrylic polymer (A2). The macromonomer may be copolymerized with a comonomer copolymerizable with the macromonomer to obtain a macromonomer copolymer, which may then be used as the block copolymer and / or graft copolymer (A). Here, as an example, a method for producing a macromonomer copolymer by copolymerizing a macromonomer (a1) with a monomer (a2) using a macromonomer (a1) as a raw material of a (meth)acrylic polymer (A1) will be described. In this case, the (meth)acrylic polymer (A2) has the monomer (a2) as a monomer unit.

[0094] [Method for producing macromonomer (a1)] The macromonomer (a1) can be produced by a known method. Examples of methods for producing the macromonomer include a method using a cobalt chain transfer agent (U.S. Patent No. 4,680,352), a method using an α-substituted unsaturated compound such as α-bromomethylstyrene as a chain transfer agent (WO 88 / 04304), a method of chemically bonding a polymerizable group (JP-A-60-133007, U.S. Patent No. 5,147,952, and JP-A-06-298921), and a method using thermal decomposition (JP-A-11-240854). Among these, the method for producing the macromonomer (a1) using a cobalt chain transfer agent is preferred because it requires fewer production steps and uses a catalyst with a high chain transfer constant.

[0095] Examples of methods for producing the macromonomer (a1) using a cobalt chain transfer agent include bulk polymerization, solution polymerization, and aqueous dispersion polymerization methods such as suspension polymerization, emulsion polymerization, etc. Among these, the aqueous dispersion polymerization method is preferred from the viewpoint of simplifying the recovery process of the macromonomer (a1).

[0096] The cobalt chain transfer agent used in the present invention may be a cobalt chain transfer agent represented by the following general formula (3):

[0097] [ka]

[0098] [In the formula, R 11 ~R 14 are each independently an alkyl group, a cycloalkyl group, or an aryl group. 11 ~X 14 are each independently an F atom, a Cl atom, a Br atom, an OH group, an alkoxy group, an aryloxy group, an alkyl group, or an aryl group.

[0099] Specific examples of cobalt chain transfer agents include bis(borondifluorodimethyldioximinocyclohexane)cobalt(II), bis(borondifluorodimethylglyoximate)cobalt(II), bis(borondifluorodiphenylglyoximate)cobalt(II), cobalt(II) complexes of vicinaliminohydroxyimino compounds, cobalt(II) complexes of tetraazatetraalkylcyclotetradecatetraenes, N,N'-bis(salicylidene)ethylenediaminocobalt(II) complexes, cobalt(II) complexes of dialkyldiazadioxodialkyldodecadienes, and cobalt(II) porphyrin complexes. Among these, bis(borondifluorodiphenylglyoximate)cobalt(II)(R 11 ~R 14 : phenyl group, X 11 ~X 14: F atom) are preferred. One or more of these can be appropriately selected and used.

[0100] The amount of the cobalt chain transfer agent used is preferably 5 ppm to 350 ppm relative to 100 parts by mass of the monomer for obtaining macromonomer (a1). If the amount of the cobalt chain transfer agent used is 5 ppm or more, the molecular weight is likely to be sufficiently reduced, and if it is 350 ppm or less, the obtained macromonomer (a1) is less likely to be discolored.

[0101] Examples of solvents used when obtaining macromonomer (a1) by solution polymerization include hydrocarbons such as toluene, ethers such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and chloroform, ketones such as acetone, alcohols such as methanol, nitriles such as acetonitrile, vinyl esters such as ethyl acetate, carbonates such as ethylene carbonate, and supercritical carbon dioxide. These can be used alone or in combination of two or more.

[0102] [Method of manufacturing macromonomer copolymer] The method for producing the macromonomer copolymer includes a step of polymerizing a polymerizable mixture containing the polymerizable composition (X) described below and a polymerization initiator.

[0103] The polymerizable composition (X) contains a macromonomer (a1) and a comonomer copolymerizable with the macromonomer (a1). The comonomer is appropriately selected from the monomers (a2) that are copolymerizable with the macromonomer (a1). In the present invention, it is particularly preferred to use the macromonomer (a1) represented by the following general formula (1), since this facilitates the preparation of the block copolymer and / or graft copolymer (A).

[0104] [ka]

[0105] (In formula (1), R 0 ~Rn are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. 1 ~X n are each independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10,000.

[0106] <R 0 ~R n > In the formula (1), R 0 ~R n The alkyl group, cycloalkyl group, aryl group or heterocyclic group may have a substituent.

[0107] R 0 ~R n Examples of the alkyl group include branched or linear alkyl groups having 1 to 20 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl. Among these, in terms of availability, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, and octyl are preferred, with methyl, ethyl, n-propyl, i-propyl, n-butyl, and t-butyl being more preferred, and methyl being particularly preferred.

[0108] R 0 ~R n Examples of the cycloalkyl group include cycloalkyl groups having 3 to 20 carbon atoms. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a t-butylcyclohexyl group, an isobornyl group, an adamantyl group, etc. In view of availability, a cyclopropyl group, a cyclobutyl group, and an adamantyl group are preferred.

[0109] R 0 ~R n The aryl group may be, for example, an aryl group having a carbon number of 6 to 18. Specific examples include a phenyl group, a benzyl group, and a naphthyl group.

[0110] R 0 ~R n Examples of the heterocyclic group include heterocyclic groups having 5 to 18 carbon atoms. Specific examples include a γ-lactone group, an ε-caprolactone group, a morpholine group, etc. Examples of heteroatoms contained in the heterocycle include an oxygen atom, a nitrogen atom, a sulfur atom, etc.

[0111] R 0 ~R n The substituents of each independently include a group or atom selected from the group consisting of an alkyl group, an aryl group, a carboxy group, an alkoxycarbonyl group (-COOR'), a carbamoyl group (-CONR'R''), a cyano group, a hydroxy group, an amino group, an amide group (-NR'R''), a halogen atom, an allyl group, an epoxy group, an alkoxy group (-OR'), and a group exhibiting hydrophilicity or ionicity. Examples of R' or R'' each independently include R 0 ~R n and the like (excluding heterocyclic groups).

[0112] R 0 ~R n Examples of the alkoxycarbonyl group as a substituent of include a methoxycarbonyl group. R 0 ~R n Examples of the carbamoyl group as a substituent of include an N-methylcarbamoyl group and an N,N-dimethylcarbamoyl group. R 0 ~R n The amide group as the substituent of the formula (I) may be, for example, a dimethylamide group. R 0 ~R nExamples of the halogen atom as a substituent of include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 0 ~R n Examples of the alkoxy group as the substituent include an alkoxy group having 1 to 12 carbon atoms. A specific example is a methoxy group. R 0 ~R n Examples of the hydrophilic or ionic group as a substituent include an alkali salt of a carboxy group or an alkali salt of a sulfoxyl group, a poly(alkylene oxide) group such as a polyethylene oxide group or a polypropylene oxide group, and a cationic substituent such as a quaternary ammonium base.

[0113] R 0 ~R n is preferably at least one selected from an alkyl group and a cycloalkyl group, and more preferably an alkyl group. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, and from the viewpoint of availability, a methyl group is more preferred.

[0114] <X 1 ~X n > In the formula (1), X 1 ~X n are each a hydrogen atom or a methyl group, and a methyl group is preferred. Furthermore, from the viewpoint of ease of synthesis of the macromonomer (a1), X 1 ~X n It is preferable that at least half of the groups are methyl groups.

[0115] <z> In the formula (1), Z is a terminal group of the macromonomer (a1). Examples of the terminal group of the macromonomer (a1) include a hydrogen atom and a group derived from a radical polymerization initiator, similar to terminal groups of polymers obtained by known radical polymerization.

[0116] As the monomer constituting the macromonomer (a1), it is preferable to use methyl methacrylate in terms of glass transition temperature, availability, etc. The proportion of methyl methacrylate in 100 parts by mass of the macromonomer (a1) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more.

[0117] Furthermore, as a monomer constituting macromonomer (a1), it is preferable to use a methacrylate having an aryl group, such as phenyl methacrylate, benzyl methacrylate, or phenoxyethyl methacrylate, because this contributes to improving the compatibility of macromonomer (a1) with polycarbonate resin (C) and can also be used as a high-refractive index component in adjusting the refractive index of macromonomer (a1). Phenyl methacrylate is more preferable because it increases the glass transition temperature of macromonomer (a1). The proportion of the methacrylate having an aryl group in a total of 100 parts by mass of macromonomer (a1) is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more. When the proportion of the methacrylate having an aryl group in macromonomer (a1) is 2 parts by mass or more, the compatibility of macromonomer (a1) with polycarbonate resin (C) can be improved, making it easier to adjust the refractive index. Furthermore, the proportion of the methacrylate having an aryl group in a total of 100 parts by mass of the macromonomer (a1) is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, and particularly preferably 30 parts by mass or less. When the proportion of the methacrylate having an aryl group in the macromonomer (a1) is 70 parts by mass or less, yellowing of the resin composition and the molded article obtained therefrom can be prevented.

[0118] The content of methacrylate in the monomer composition for obtaining macromonomer (a1) is preferably 80 parts by mass or more and 100 parts by mass or less, from the viewpoint of the heat resistance of the product macromonomer copolymer, the resin composition containing it, and the molded article obtained therefrom. The content of methacrylate is more preferably 82 parts by mass or more and 99 parts by mass or less, and even more preferably 84 parts by mass or more and 98 parts by mass or less. The content of acrylate in the monomer composition for obtaining macromonomer (a1) is preferably 0 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 18 parts by mass or less, and even more preferably 2 parts by mass or more and 16 parts by mass or less.

[0119] In the method for producing the macromonomer copolymer, the polymerization reaction is preferably carried out by radical polymerization.

[0120] In the method for producing a macromonomer copolymer according to the present invention, the upper limit of the content of the sulfur-containing chain transfer agent contained in the polymerizable mixture is preferably less than 0.01 parts by mass relative to 100 parts by mass of the polymerizable composition (X). If the upper limit of the content of the sulfur-containing chain transfer agent is less than 0.01 parts by mass, the composition distribution of the copolymer can be prevented from becoming broad, thereby improving the impact resistance of the resulting molded article. The lower limit of the content of the sulfur-containing chain transfer agent is not particularly limited, and it is more preferable that no sulfur-containing chain transfer agent is contained. The sulfur-containing chain transfer agent refers to a mercaptan compound such as n-butyl mercaptan or n-octyl mercaptan, which is added as a chain transfer agent to adjust the molecular weight of the copolymer during polymerization.

[0121] The mass average molecular weight (Mw) of the macromonomer copolymer is preferably 20,000 or more, more preferably 30,000 or more, even more preferably 100,000 or more, and particularly preferably 300,000 or more, from the viewpoint of the mechanical properties of the resin composition of the present invention containing the particles of the present invention containing the macromonomer copolymer and polycarbonate resin (C) and the molded article obtained therefrom. On the other hand, the mass average molecular weight (Mw) of the macromonomer copolymer is preferably 10,000,000 or less, more preferably 9,000,000 or less, even more preferably 8,000,000 or less, and particularly preferably 7,000,000 or less, from the viewpoint of the optical properties and fluidity during melt molding of the resin composition of the present invention containing the particles of the present invention containing the macromonomer copolymer and polycarbonate resin (C) and the molded article obtained therefrom.

[0122] The number average molecular weight (Mn) of the macromonomer copolymer is preferably 10,000 or more, more preferably 20,000 or more, even more preferably 40,000 or more, and particularly preferably 60,000 or more, from the viewpoint of the mechanical properties of the resin composition of the present invention containing the particles of the present invention containing the macromonomer copolymer and polycarbonate resin (C) and the molded article obtained therefrom. On the other hand, the number average molecular weight (Mn) of the macromonomer copolymer is preferably 5,000,000 or less, more preferably 1,000,000 or less, even more preferably 500,000 or less, and particularly preferably 200,000 or less, from the viewpoint of the optical properties and fluidity during melt molding of the resin composition of the present invention containing the particles of the present invention containing the macromonomer copolymer and polycarbonate resin (C) and the molded article obtained therefrom. When the mass average molecular weight (Mw) of the macromonomer copolymer is 20,000 or more, the macromonomer copolymer is more likely to exhibit its inherent properties, such as heat resistance, hardness, scratch resistance, weather resistance, and transparency. When the mass average molecular weight (Mw) of the macromonomer copolymer is 10,000,000 or less, the melt viscosity falls within an appropriate range, resulting in good melt-kneadability and processability. The above upper and lower limits can be combined arbitrarily. The method for controlling the mass average molecular weight (Mw) of the macromonomer copolymer within the above range is not particularly limited, and can be controlled by adjusting the polymerization method, the type and amount of polymerization initiator, the amount of chain transfer agent, the polymerization temperature, etc., according to well-known techniques.

[0123] [Polymerizable composition (X)] The polymerizable composition (X) is one of the raw materials for the block copolymer and / or graft copolymer (A). The content ratios of the macromonomer (a1) (a1, units: parts by mass) and the monomer (a2) (a2, units: parts by mass) contained in the polymerizable composition (X), relative to 100 parts by mass of the total mass of the polymerizable composition (X), are preferably a1:a2 = 35 to 75 parts by mass: 65 to 25 parts by mass, more preferably a1:a2 = 40 to 70 parts by mass: 60 to 30 parts by mass, even more preferably a1:a2 = 45 to 70 parts by mass: 55 to 30 parts by mass, particularly preferably a1:a2 = 45 to 65: 55 to 35 parts by mass, and most preferably a1:a2 = 45 to 55: 55 to 45 parts by mass. When the lower limit of the content of macromonomer (a1) in polymerizable composition (X) is 35 parts by mass or more, or the upper limit of the content of monomer (a2) is 65 parts by mass or less, per 100 parts by mass of the total mass of the polymerizable composition (X), the handleability of the macromonomer copolymer is good. Furthermore, when the lower limit of the content of monomer (a2) in polymerizable composition (X) is 25 parts by mass or more, or the upper limit of the content of macromonomer (a1) is 75 parts by mass or less, per 100 parts by mass of the total mass of the polymerizable composition (X), the impact resistance of a molding material containing the macromonomer copolymer and the resulting molded article can be maintained good.

[0124] For ease of explanation, the polymerizable composition (X) containing the macromonomer (a1) and the monomer (a2) is referred to as the "polymerizable composition (X)." However, it is not necessary to prepare the polymerizable composition (X) by previously mixing the macromonomer (a1) and the monomer (a2). It is sufficient that the polymerizable composition (X) is in a state in which the macromonomer (a1) and the monomer (a2) coexist in the polymerization step.

[0125] [Production of macromonomer copolymers by suspension polymerization] The case where the polymerization reaction is carried out by suspension polymerization will be described in detail below as one embodiment of the present invention. In the method for producing a macromonomer copolymer, when the macromonomer copolymer is produced by suspension polymerization, examples include a method in which the production of the macromonomer (a1) of the present invention and the production of the macromonomer copolymer are carried out separately, which include the following steps i) to iv), and a method in which the production of the macromonomer (a1) of the present invention and the production of the macromonomer copolymer of the present invention are carried out continuously, which includes the following steps I) to II) instead of the following steps i) to ii) among the following steps i) to v).

[0126] i) Syrup preparation process A bead-like macromonomer (a1) produced by suspension polymerization is dissolved in a solution containing a monomer (a2) to prepare a syrup, which is designated as a polymerizable composition (X). When preparing the polymerizable composition (X), a mixture containing the macromonomer (a1) and the monomer (a2) can be heated at a temperature equal to or lower than the boiling point of the monomer (a2) to promote dissolution of the macromonomer (a1). The temperature at which the polymerizable composition (X) is prepared is preferably in the range of 20°C to 100°C, more preferably in the range of 40°C to 80°C. If the radical polymerization initiator used does not react at the temperature at which the polymerizable composition (X) is prepared, the radical polymerization initiator can be mixed with the polymerizable composition (X) to obtain a polymerizable mixture, and then the polymerizable mixture can be heated.

[0127] ii) Radical polymerization initiator dissolution step When the radical polymerization initiator reacts at the temperature at which the polymerizable composition (X) obtained in step i) is prepared, the polymerizable composition (X) is first cooled to room temperature or below, and then the radical polymerization initiator is added and dissolved uniformly to obtain a polymerizable mixture. The temperature of the polymerizable composition (X) when the radical polymerization initiator is added is preferably set to a temperature equal to or lower than the 10-hour half-life temperature of the radical polymerization initiator minus 15°C.

[0128] iii) Preparation of aqueous solution The polymerizable mixture and the aqueous solution are mixed and then stirred to prepare a suspension in which droplets of the polymerizable mixture are dispersed in the aqueous solution. The aqueous solution is an aqueous solution for dispersing the polymerizable mixture, and may contain a dispersant, an electrolyte, and other auxiliary agents. By appropriately selecting the combination of the dispersant and the electrolyte, the dispersibility of the droplets of the polymerizable mixture formed in the aqueous solution when the polymerizable mixture is dispersed in the aqueous solution can be controlled. The water used in the aqueous solution is preferably deionized water, since this improves the dispersibility of the droplets of the polymerizable mixture.

[0129] Examples of dispersants include alkali metal salts of poly(meth)acrylic acid, copolymers of alkali metal salts of (meth)acrylic acid and (meth)acrylic acid esters, copolymers of alkali metal salts of (meth)acrylic acid sulfoalkyl and (meth)acrylic acid esters, alkali metal salts of polystyrene sulfonates, copolymers of alkali metal salts of styrene sulfonates and (meth)acrylic acid esters, or copolymers formed from combinations of these monomers; polyvinyl alcohol with a saponification degree of 70 to 100%, methyl cellulose, starch, and hydroxyapatite. These can be used alone or in combination of two or more. Among these, copolymers of alkali metal salts of (meth)acrylic acid sulfoalkyl and (meth)acrylic acid esters and copolymers of alkali metal salts of (meth)acrylic acid and (meth)acrylic acid esters are preferred, as they exhibit good dispersion stability during suspension polymerization. The amount of dispersant added is, for example, in the range of 0.0005 to 0.5 parts by mass per 100 parts by mass of the polymerizable composition (X). Examples of the electrolyte include sodium carbonate, sodium sulfate, manganese sulfate, etc. The amount of the electrolyte added is, for example, in the range of 0.01 to 1.0 part by mass relative to 100 parts by mass of the polymerizable composition (X).

[0130] I) Syrup preparation process The polymerizable composition (X) is prepared by adding a solution containing a monomer (a2) to a bead-like macromonomer (a1) produced by suspension polymerization dispersed in an aqueous solution. The temperature at which the macromonomer (a1) is dissolved in the solution containing the monomer (a2) is preferably in the range of 20°C to 100°C, more preferably in the range of 40°C to 90°C, and even more preferably in the range of 50°C to 80°C.

[0131] II) Radical polymerization initiator dissolution process When the radical polymerization initiator reacts at the temperature at which the polymerizable composition (X) obtained in step I) is prepared, the polymerizable composition (X) is first cooled to room temperature or below, and then the radical polymerization initiator is added and dissolved uniformly to obtain a polymerizable mixture. The temperature of the polymerizable composition (X) when the radical polymerization initiator is added is preferably set to a temperature equal to or lower than the 10-hour half-life temperature of the radical polymerization initiator minus 15°C.

[0132] When the polymerization reaction is carried out in the presence of a radical polymerization initiator, known organic peroxides such as 2,4-dichlorobenzoyl peroxide and t-butyl peroxypivalate, and known azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile) can be used as the radical polymerization initiator. The amount of the radical polymerization initiator to be added can be appropriately selected by a person skilled in the art according to well-known techniques. The usual amount of the radical polymerization initiator to be added is 0.0001 to 10 parts by mass per 100 parts by mass of the total amount of the polymerizable composition (X).

[0133] iv) Polymerization reaction step The resulting suspension is then heated while being stirred to initiate the polymerization reaction. It is preferable to remove dissolved oxygen from the polymerizable mixture and the aqueous solution before heating by subjecting them to vacuum degassing or nitrogen substitution. The polymerization temperature during the polymerization reaction is an important condition for obtaining a macromonomer copolymer in a high yield. The polymerization temperature here refers to the temperature of the suspension. The polymerization temperature is preferably 50°C to 90°C, more preferably 60°C to 85°C, and even more preferably 65°C to 80°C. If the polymerization temperature is too low, the reaction may proceed slowly, resulting in a long polymerization time. Furthermore, if the polymerization temperature is too high, cleavage of the adduct radical, which is a reaction intermediate, takes precedence, tending to reduce the yield of the macromonomer copolymer. In the latter stage of the polymerization reaction, the suspension can be heated to increase the reaction rate of the polymerizable composition (X) and to eliminate unreacted radical polymerization initiator. The temperature to which the suspension is heated is preferably 80°C or higher, more preferably 85°C or higher. The temperature rise time can be determined by calculating the time required for the radical polymerization initiator to disappear, and is usually about 30 minutes to 2 hours.

[0134] v) Recovery process After the above steps, the suspension is cooled to room temperature or below, and the resulting copolymer in the form of beads is recovered by a known method such as filtration. If necessary, a washing step for removing impurities such as dispersants and electrolytes, a step for removing beads containing air bubbles, a drying step, etc. may be performed.

[0135] [Method for producing (meth)acrylic copolymer (B)] The (meth)acrylic copolymer (B) is produced using the monomer (b1) as a raw material. The (meth)acrylic copolymer (B) is preferably produced by emulsion polymerization. By using the emulsion polymerization method, the (meth)acrylic copolymer (B) is obtained as an emulsion. By obtaining the (meth)acrylic copolymer (B) as an emulsion, it is suitable for use in the surface treatment step of beads described below. When the (meth)acrylic copolymer (B) is produced by emulsion polymerization, a commonly known initiator, monomer dropping method, stirring method, reaction vessel, etc. suitable for emulsion polymerization can be used. Known water-soluble initiators can be used as the initiator. Examples of initiators include redox initiators, azo initiators, and organic peroxide initiators.

[0136] [Bead surface treatment process] The method for producing particles of the present invention preferably includes a step of surface treating beads using a slurry (suspension) containing beads made of a block copolymer and / or a graft copolymer (A) and an emulsion containing a (meth)acrylic copolymer (B). Here, the slurry containing the block copolymer and / or graft copolymer (A) is preferably obtained by suspension polymerization. The slurry containing the block copolymer and / or graft copolymer (A) can also be obtained by redispersing beads in an aqueous solution after washing and recovery. The emulsion containing the (meth)acrylic copolymer (B) is preferably obtained by emulsion polymerization. In this bead surface treatment step, an emulsion containing a (meth)acrylic copolymer (B) is added to a slurry containing a block copolymer and / or a graft copolymer (A), and then the emulsion is solidified under certain conditions, thereby coating the surface of the block copolymer and / or graft copolymer (A) with the (meth)acrylic copolymer (B).

[0137] In the step of adding an emulsion containing a (meth)acrylic copolymer (B) to a slurry containing a block copolymer and / or a graft copolymer (A), the temperature of the slurry is preferably 20°C to 90°C, more preferably 25°C to 70°C, and even more preferably 30°C to 60°C. By keeping the slurry temperature at 90°C or less, it is possible to prevent rapid solidification of the (meth)acrylic copolymer (B) when the emulsion containing the (meth)acrylic copolymer (B) is added, which would otherwise result in a non-uniform processing state. Furthermore, if the slurry temperature is 20°C or higher, the energy cost required for cooling the slurry can be kept low. Furthermore, when an emulsion of the (meth)acrylic copolymer (B) is added to a slurry containing the block copolymer and / or graft copolymer (A), the temperature of the slurry is preferably lower than the glass transition temperature (Tg) of the (meth)acrylic copolymer (B). By having the temperature of the slurry lower than the Tg of the (meth)acrylic copolymer (B), it is possible to prevent rapid solidification of the (meth)acrylic copolymer (B) when the emulsion is added to the slurry, thereby preventing a non-uniform processing state.

[0138] Various acids and salts can be used as the coagulant. Examples of the various acids and salts that can be used include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, organic acids such as acetic acid, and salts of inorganic and organic acids with sodium, potassium, calcium, magnesium, and aluminum. These coagulants can be used alone or in combination of two or more. These acids and salts are added to a slurry containing the (meth)acrylic copolymer (A) after preparing an appropriate aqueous solution. The timing of adding the coagulant during the bead surface treatment process can be appropriately selected. The coagulant may be added before adding the emulsion containing the (meth)acrylic copolymer (B) to the slurry containing the block copolymer and / or graft copolymer (A), or after adding the emulsion containing the (meth)acrylic copolymer (B) to the slurry containing the block copolymer and / or graft copolymer (A). To prevent uneven coagulation of the (meth)acrylic copolymer (B), it is preferable to add the coagulant before adding the emulsion containing the (meth)acrylic copolymer (B) to the slurry containing the block copolymer and / or graft copolymer (A).

[0139] The mixture of the slurry containing the block copolymer and / or graft copolymer (A) and the emulsion containing the (meth)acrylic copolymer (B) is preferably heated to a temperature equal to or higher than the glass transition temperature (Tg) of the (meth)acrylic copolymer (B). By heating the mixture at a temperature equal to or higher than the Tg of the (meth)acrylic copolymer (B), solidification of the (meth)acrylic copolymer (B) proceeds, and the surfaces of the beads containing the block copolymer and / or graft copolymer (A) can be coated with the (meth)acrylic copolymer (B). After the heat treatment is completed, the slurry is cooled, washed, and dried to obtain particles.

[0140] <Particle uses> The particles of the present invention have excellent powder fluidity and blocking resistance, making them suitable for use as raw materials for various resin compositions. Specifically, the excellent powder fluidity and blocking resistance improve the processability of the particles in the packaging process after washing and drying. Furthermore, fewer particles remain in pipes, hoppers, and drying furnaces, reducing product loss and improving workability. Furthermore, in the process for producing a resin composition using the particles of the present invention, since the particles have high blocking resistance, problems due to blocking are unlikely to occur during mixing as a powder or during transportation and storage.

[0141] [Resin composition] The resin composition of the present invention contains the particles of the present invention (particles (P)) and a polycarbonate resin (C). The polycarbonate resin (C) used in the present invention will be described in detail later.

[0142] The resin composition of the present invention may contain only one type of particles (P) or two or more types thereof, and may also contain only one type of polycarbonate resin (C) or two or more types thereof.

[0143] The content of particles (P) in the resin composition of the present invention is preferably 1 to 25 parts by mass, particularly 2 to 10 parts by mass, and especially 3 to 15 parts by mass, per 100 parts by mass of polycarbonate resin (C). When the content of particles (P) is equal to or greater than the above-mentioned lower limit, the impact resistance improving effect of particles (P) can be sufficiently obtained. On the other hand, when the content of particles (P) is equal to or less than the above-mentioned upper limit, the properties of polycarbonate resin (C), such as heat resistance, are not impaired.

[0144] [Polycarbonate resin (C)] The polycarbonate resin (C) contained in the resin composition of the present invention will be described below. There is no particular limitation on the type of polycarbonate resin (C) used in the present invention. The polycarbonate resin may be used alone or in any combination of two or more types in any ratio.

[0145] Polycarbonate resins are polymers with carbonate bonds represented by the general formula -[-OXOC(=O)-]-, where X is generally a hydrocarbon group but may contain heteroatoms to impart various properties.

[0146] Polycarbonate resins can be classified into aromatic polycarbonate resins, in which the carbons directly bonded to the carbonate bonds are aromatic carbons, and aliphatic polycarbonate resins, in which the carbons directly bonded to the carbonate bonds are aliphatic carbons, and either can be used.From the viewpoint of weather resistance, aliphatic polycarbonate resins are preferred, and aliphatic polycarbonate resins containing alicyclic dihydroxy compounds are more preferred.Furthermore, from the viewpoints of heat resistance, mechanical properties, electrical properties, etc., aromatic polycarbonate resins are preferred.

[0147] There is no specific limitation on the type of polycarbonate resin, but examples include polycarbonate polymers obtained by reacting a dihydroxy compound such as an aromatic dihydroxy compound or an aliphatic dihydroxy compound, or a cyclic ether with a carbonate precursor. In this case, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound may also be reacted. Alternatively, a method of reacting carbon dioxide as a carbonate precursor with a cyclic ether may be used. The polycarbonate polymer may be linear or branched. Furthermore, the polycarbonate polymer may be a homopolymer consisting of one type of repeating unit, or a copolymer having two or more types of repeating units. In this case, the copolymer may be selected from various copolymer forms such as a random copolymer or a block copolymer. Generally, such a polycarbonate polymer is a thermoplastic resin.

[0148] Examples of aromatic dihydroxy compounds that can be used as raw materials for aromatic polycarbonate resins include the following compounds.

[0149] Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,2-benzenedimethanol, 1,3-dihydroxybenzene (i.e., resorcinol), 1,3-benzenedimethanol, 1,4-dihydroxybenzene, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis(2-hydroxyethoxy)benzene, 1,4-bis(2-hydroxyethoxy)benzene; 4,4'-biphenyldimethanol, 4,4'-biphenyldiethanol, 1,4-bis(2-hydroxyethoxy)biphenyl, 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydro dihydroxybiphenyls such as 2,2'-dihydroxy-1,1'-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,3-bis(hydroxymethyl)naphthalene, 1,6-dihydroxynaphthalene, 1,6-bis(hydroxyethoxy)naphthalene, 2,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and other dihydroxynaphthalenes; bisphenols such as bisphenol A bis(2-hydroxyethyl) ether and bisphenol S bis(2-hydroxyethyl) ether.

[0150] Dihydroxydiaryl ethers such as 2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis(3-hydroxyphenoxy)benzene, and 1,3-bis(4-hydroxyphenoxy)benzene.

[0151] 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A), 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C), 2,2-bis(3-methoxy-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-methoxy-4-hydroxyphenyl)propane, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane phenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(3-cyclohexyl-4-hydroxyphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)cyclohexylmethane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl) 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-naphthylethan, 1,1-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)ethane Bis(hydroxyaryl)alkanes such as hexane, 2,2-bis(4-hydroxyphenyl)hexane, 1,1-bis(4-hydroxyphenyl)octane, 2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)hexane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-bis(4-hydroxyphenyl)nonane, 1,1-bis(4-hydroxyphenyl)decane, and 1,1-bis(4-hydroxyphenyl)dodecane.

[0152] 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,4-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5-dimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl) Bis(hydroxyaryl)cycloalkanes such as 3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-propyl-5-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-tert-butyl-cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-phenylcyclohexane, and 1,1-bis(4-hydroxyphenyl)-4-phenylcyclohexane.

[0153] Cardo structure-containing bisphenols such as 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene.

[0154] Dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide.

[0155] Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide.

[0156] Dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone.

[0157] Among these, bis(hydroxyaryl)alkanes are preferred, and bis(4-hydroxyphenyl)alkanes are particularly preferred, with 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol A) and 2,2-bis(3-methyl-4-hydroxyphenyl)propane (i.e., bisphenol C) being particularly preferred from the standpoints of impact resistance and heat resistance. The aromatic dihydroxy compounds may be used alone or in any combination of two or more in any ratio.

[0158] Examples of aliphatic dihydroxy compounds and cyclic ethers that serve as raw materials for aliphatic polycarbonate resins include the following compounds: In the present invention, an aliphatic dihydroxy compound refers to a dihydroxy compound having a saturated hydrocarbon group, and does not include cyclic ethers in which a portion of the cyclic hydrocarbon is substituted with a hetero atom.

[0159] Examples of the aliphatic dihydroxy compound include alkanediols such as ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol, 2,2'-oxydiethanol (i.e., diethylene glycol), and triethylene glycol spiroglycol; and cycloalkanediols such as cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4-(2-hydroxyethyl)cyclohexanol, and 2,2,4,4-tetramethyl-cyclobutane-1,3-diol.

[0160] Examples of cyclic ethers include 1,2-epoxyethane (i.e., ethylene oxide), 1,2-epoxypropane (i.e., propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl-1,2-epoxycyclohexane, 2,3-epoxynorbornane, 1,3-epoxypropane; isosorbide, isomannide, and isoidet (stereoisomers of the compound represented by the following formula (4)).

[0161] [ka]

[0162] The aliphatic dihydroxy compounds and cyclic ethers may be used alone or in any combination of two or more in any ratio, and may also be used in combination with aromatic dihydroxy compounds.

[0163] In the present invention, the method for producing the polycarbonate resin is not particularly limited, and any method may be adopted using the above-mentioned raw materials as appropriate, such as interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of a cyclic carbonate compound, or solid-phase transesterification of a prepolymer.

[0164] As described above, the polycarbonate resin (C) used in the present invention can use, as structural units, an appropriate combination of monomer units such as aliphatic dihydroxy compounds and aromatic dihydro compounds, but it is preferable that the dihydroxy compound contains a structural unit derived from the compound represented by the above formula (4) (this will be referred to as "structural unit (c1)" as appropriate).

[0165] When the polycarbonate resin (C) used in the present invention is a polycarbonate resin having a structural unit derived from the compound represented by the formula (4), the polycarbonate resin may be a homopolycarbonate resin of the structural unit (c1) or a copolymer polycarbonate resin containing a structural unit other than the structural unit (c1). From the viewpoint of achieving better impact resistance, a copolymer polycarbonate resin is preferred.

[0166] The dihydroxy compound represented by the formula (4) includes isosorbide (ISB), isomannide, and isoidet, which are stereoisomers. These may be used alone or in combination of two or more.

[0167] Among the dihydroxy compounds represented by the formula (4), isosorbide (ISB), which is obtained by dehydration condensation of sorbitol produced from various starches that are abundantly present as plant-derived resources and are readily available, is most preferred in terms of availability and ease of production, weather resistance, optical properties, moldability, heat resistance, and carbon neutrality.

[0168] The dihydroxy compound represented by the formula (4) is easily oxidized by oxygen, and therefore, during storage or handling during production, it is preferable to avoid the inclusion of moisture, use an oxygen scavenger, or store under a nitrogen atmosphere to prevent decomposition by oxygen.

[0169] Furthermore, the polycarbonate resin (C) is preferably a copolymer polycarbonate resin containing a structural unit (c1) derived from a dihydroxy compound represented by formula (4) and a structural unit derived from a dihydroxy compound other than the dihydroxy compound represented by formula (4). The dihydroxy compound into which the structural unit (c2) is introduced is not particularly limited, but is preferably one or more dihydroxy compounds selected from the group consisting of aliphatic hydrocarbon dihydroxy compounds, alicyclic hydrocarbon dihydroxy compounds, ether-containing dihydroxy compounds, and dihydroxy compounds containing an aromatic group. A structural unit derived from one or more dihydroxy compounds selected from the group consisting of aliphatic hydrocarbon dihydroxy compounds, alicyclic hydrocarbon dihydroxy compounds, ether-containing dihydroxy compounds, and dihydroxy compounds containing an aromatic group is referred to as "structural unit (c2)" as appropriate. In particular, one or more dihydroxy compounds selected from the group consisting of aliphatic hydrocarbon dihydroxy compounds, alicyclic hydrocarbon dihydroxy compounds, and ether-containing dihydroxy compounds are preferred. These dihydroxy compounds have flexible molecular structures, and therefore, by using these dihydroxy compounds as raw materials, the impact resistance of the resulting polycarbonate resin can be improved. Among these, it is more preferable to use aliphatic hydrocarbon dihydroxy compounds and alicyclic hydrocarbon dihydroxy compounds, which are highly effective in improving impact resistance, and it is most preferable to use alicyclic hydrocarbon dihydroxy compounds. Specific examples of aliphatic hydrocarbon dihydroxy compounds, alicyclic hydrocarbon dihydroxy compounds, ether-containing dihydroxy compounds, and aromatic group-containing dihydroxy compounds are as follows:

[0170] Examples of aliphatic hydrocarbon dihydroxy compounds that can be used include the following: straight-chain aliphatic dihydroxy compounds such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; and branched-chain aliphatic dihydroxy compounds such as 1,3-butanediol, 1,2-butanediol, neopentyl glycol, and hexylene glycol.

[0171] Examples of dihydroxy compounds of alicyclic hydrocarbons that can be used include the following dihydroxy compounds: dihydroxy compounds which are primary alcohols of alicyclic hydrocarbons, exemplified by dihydroxy compounds derived from terpene compounds such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecanedimethanol, 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantanedimethanol, and limonene; and dihydroxy compounds which are secondary or tertiary alcohols of alicyclic hydrocarbons, exemplified by 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, and 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

[0172] Examples of the ether-containing dihydroxy compound include oxyalkylene glycols and dihydroxy compounds containing an acetal ring. As the oxyalkylene glycol, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, etc. can be used.

[0173] As the dihydroxy compound containing an acetal ring, for example, spiro glycol represented by the following structural formula (5) or dioxane glycol represented by the following structural formula (6) can be used.

[0174] [ka]

[0175] As the dihydroxy compound containing an aromatic group, for example, the following dihydroxy compounds can be used, but dihydroxy compounds other than these can also be used. 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3-phenyl)phenyl)propane, 2,2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-2 aromatic bisphenol compounds such as -ethylhexane, 1,1-bis(4-hydroxyphenyl)decane, bis(4-hydroxy-3-nitrophenyl)methane, 3,3-bis(4-hydroxyphenyl)pentane, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxy-3-methylphenyl)sulfide, bis(4-hydroxyphenyl)disulfide, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxy-3,3'-dichlorodiphenyl ether;Dihydroxy compounds having an ether group bonded to an aromatic group, such as 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 2,2-bis(4-(2-hydroxypropoxy)phenyl)propane, 1,3-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, and bis(4-(2-hydroxyethoxy)phenyl)sulfone; 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 9,9-bis(4-(2-hydroxypropoxy)phenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)fluorene, and 9,9-bis(4-(2-hydroxypropoxy)-3-methylphenyl)fluorene; Dihydroxy compounds having a fluorene ring, such as fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-cyclohexylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylphenyl)fluorene, and 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)fluorene;

[0176] In the polycarbonate resin (C), the content of the structural unit (c1) relative to 100 mol% of all structural units derived from dihydroxy compounds is not particularly limited, but the lower limit is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, particularly preferably 55 mol% or more, and most preferably 60 mol% or more. The upper limit is more preferably 95 mol% or less, even more preferably 90 mol% or less, and particularly preferably 85 mol% or less. In these cases, the content of biogenic substances can be further increased, and heat resistance can be further improved. Note that the content of the structural unit (c1) in the polycarbonate may be 100 mol%, but from the perspective of further increasing the molecular weight and further improving impact resistance, it is preferable that a structural unit other than the structural unit (c1) be copolymerized.

[0177] When the polycarbonate resin (C) is a copolymer polycarbonate having the structural unit (c2) in addition to the structural unit (c1), the content of the structural unit (c2) is not particularly limited, but the lower limit is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more. The upper limit is preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, particularly preferably 45 mol% or less, and most preferably 40 mol% or less. In these cases, a flexible structure is introduced into the polymer chain, which can further increase the toughness of the resin and further improve its impact resistance.

[0178] The polycarbonate resin (C) may further contain structural units (other dihydroxy compounds) other than the structural units (c1) and (c2). However, in order for the present invention to exhibit favorable effects, the content of structural units derived from other dihydroxy compounds is preferably 10 mol % or less, and more preferably 5 mol % or less, relative to 100 mol % of all structural units derived from dihydroxy compounds.

[0179] The other dihydroxy compounds can be appropriately selected depending on the properties required for the polycarbonate resin. The other dihydroxy compounds may be used alone or in combination. The use of the other dihydroxy compounds in combination with the dihydroxy compound represented by formula (4) can improve the flexibility and mechanical properties of the polycarbonate resin, as well as the moldability.

[0180] The dihydroxy compound used as a raw material for polycarbonate resin may contain a stabilizer such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer, or heat stabilizer. In particular, the dihydroxy compound represented by formula (4) has the property of being easily degraded under acidic conditions. Therefore, by using a basic stabilizer in the synthesis process of polycarbonate resin, it is possible to suppress the degrada- tion of the dihydroxy compound represented by formula (4), thereby further improving the quality of the obtained polycarbonate resin composition.

[0181] Examples of the basic stabilizer that can be used include the following compounds: hydroxides, carbonates, phosphates, phosphites, hypophosphites, borates, and fatty acid salts of metals of Group 1 or 2 of the long-form periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005); tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, and methyltriphenylammonium hydroxide. and basic ammonium compounds such as butyltriphenylammonium hydroxide; amine compounds such as diethylamine, dibutylamine, triethylamine, morpholine, N-methylmorpholine, pyrrolidine, piperidine, 3-amino-1-propanol, ethylenediamine, N-methyldiethanolamine, diethylethanolamine, diethanolamine, triethanolamine, 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, and aminoquinoline; and hindered amine compounds such as di-(tert-butyl)amine and 2,2,6,6-tetramethylpiperidine.

[0182] The content of the basic stabilizer in the dihydroxy compound is not particularly limited. However, since the dihydroxy compound represented by formula (4) is unstable in an acidic state, it is preferable to set the content of the basic stabilizer so that the pH of an aqueous solution of the dihydroxy compound containing the basic stabilizer is around 7.

[0183] The content of the basic stabilizer relative to the dihydroxy compound represented by formula (4) is preferably 0.0001 to 1% by weight. In this case, the effect of preventing the deterioration of the dihydroxy compound represented by formula (2) is sufficiently obtained. From the viewpoint of further enhancing this effect, the content of the basic stabilizer is more preferably 0.001 to 0.1% by weight.

[0184] Examples of carbonate precursors that are raw materials for polycarbonate resins include carbonyl halides, carbonic acid diesters, etc. The carbonate precursors may be used alone or in any combination and ratio of two or more.

[0185] Examples of carbonyl halides include phosgene; and haloformates such as bischloroformates of dihydroxy compounds and monochloroformates of dihydroxy compounds.

[0186] As the carbonic acid diester used as a raw material for the polycarbonate resin, a compound represented by the following formula (7) can usually be used: These carbonic acid diesters may be used alone or in combination of two or more.

[0187] [ka]

[0188] In the formula (7), A 1 and A 2 are each a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group, and A 1 and A 2 A may be the same or different. 1 and A 2 As the alkyl group, it is preferable to adopt a substituted or unsubstituted aromatic hydrocarbon group, and it is more preferable to adopt an unsubstituted aromatic hydrocarbon group.

[0189] Examples of the carbonate diester represented by formula (7) that can be used include diphenyl carbonate (DPC), substituted diphenyl carbonates such as ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate. Among these carbonate diesters, it is preferable to use diphenyl carbonate or a substituted diphenyl carbonate, and it is particularly preferable to use diphenyl carbonate. Note that the carbonate diester may contain impurities such as chloride ions, which may inhibit the polycondensation reaction or deteriorate the color tone of the resulting polycarbonate resin. Therefore, it is preferable to use a diester purified by distillation or the like, as necessary.

[0190] In the present invention, the method for producing the polycarbonate resin is not particularly limited, and any method may be adopted using the above-mentioned raw materials as appropriate, such as interfacial polymerization, melt transesterification, pyridine method, ring-opening polymerization of a cyclic carbonate compound, or solid-phase transesterification of a prepolymer.

[0191] For example, polycarbonate resins can be synthesized by polycondensing the dihydroxy compound and the carbonic acid diester through a transesterification reaction. More specifically, polycarbonate resins can be obtained by removing from the system, during polycondensation, the monohydroxy compound and other by-products produced in the transesterification reaction.

[0192] The transesterification reaction proceeds in the presence of a transesterification catalyst (hereinafter, the transesterification catalyst will be referred to as a "polymerization catalyst.") The type of polymerization catalyst can have a significant effect on the reaction rate of the transesterification reaction and the quality of the resulting polycarbonate resin.

[0193] The polymerization catalyst is not limited as long as it can satisfy the transparency, color tone, heat resistance, weather resistance, and mechanical strength of the resulting polycarbonate resin. Examples of the polymerization catalyst that can be used include metal compounds of Group I or Group II (hereinafter simply referred to as "Group 1" and "Group 2") in the long-form periodic table, as well as basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds. Among these, Group 1 metal compounds and / or Group 2 metal compounds are preferred, and Group 2 metal compounds are particularly preferred.

[0194] Examples of the Group 1 metal compound that can be used include the following compounds: sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium phenylborohydride, and boron phenylide. Potassium, lithium phenylborate, cesium phenylborate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenylphosphate, dipotassium phenylphosphate, dilithium phenylphosphate, dicesium phenylphosphate, sodium, potassium, lithium, and cesium alcoholates and phenolates, disodium, dipotassium, dilithium, and dicesium salts of bisphenol A, etc. As the Group 1 metal compound, a lithium compound is preferred from the viewpoint of polymerization activity and the color tone of the resulting polycarbonate resin.

[0195] Examples of the Group 2 metal compound that can be used include the following compounds: calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate. As the Group 2 metal compound, magnesium compounds, calcium compounds, or barium compounds are preferred, and from the viewpoints of polymerization activity and the color tone of the resulting polycarbonate resin, magnesium compounds and / or calcium compounds are more preferred, and calcium compounds are most preferred.

[0196] It is also possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound in combination with the Group 1 metal compound and / or Group 2 metal compound as an auxiliary. However, it is particularly preferable to use only the Group 1 metal compound and / or Group 2 metal compound.

[0197] As the basic phosphorus compound, for example, the following compounds can be used: triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.

[0198] Examples of the basic ammonium compound that can be used include the following compounds: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.

[0199] Examples of the amine compound that can be used include the following compounds: 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, and guanidine.

[0200] The amount of the polymerization catalyst used is preferably 0.1 to 300 μmol, more preferably 0.5 to 100 μmol, and particularly preferably 1 to 50 μmol, per mol of the total dihydroxy compounds used in the reaction.

[0201] When a compound containing at least one metal selected from the group consisting of Group 2 metals in the long periodic table and lithium is used as the polymerization catalyst, for example, when a compound containing at least one metal selected from the group consisting of magnesium compounds, calcium compounds, and barium compounds is used, particularly when a magnesium compound and / or a calcium compound is used, the amount of polymerization catalyst used is preferably 0.1 μmol or more, more preferably 0.3 μmol or more, and particularly preferably 0.5 μmol or more, in terms of the metal atomic weight of the compound containing the metal, per mol of all dihydroxy compounds used in the reaction. The upper limit is preferably 10 μmol or less, more preferably 5 μmol or less, and particularly preferably 3 μmol or less.

[0202] By adjusting the amount of polymerization catalyst used within the above range, the polymerization rate can be increased, making it possible to obtain a polycarbonate resin of the desired molecular weight without necessarily increasing the polymerization temperature, thereby suppressing deterioration in the color tone of the polycarbonate resin. Furthermore, it is possible to prevent unreacted raw materials from volatilizing during the polymerization, which would cause the molar ratio of the dihydroxy compound to the carbonate diester to be disrupted, thereby more reliably obtaining a resin of the desired molecular weight. Furthermore, it is possible to suppress the occurrence of side reactions, thereby further preventing deterioration in the color tone of the polycarbonate resin or discoloration during molding.

[0203] Considering the adverse effects of sodium, potassium, or cesium, among the Group 1 metals, on the color tone of the polycarbonate resin, and the adverse effects of iron on the color tone of the polycarbonate resin, the total content of sodium, potassium, cesium, and iron in the polycarbonate resin is preferably 1 ppm by weight or less. In this case, deterioration of the color tone of the polycarbonate resin can be further prevented, and the color tone of the polycarbonate resin can be further improved. From the same perspective, the total content of sodium, potassium, cesium, and iron in the polycarbonate resin is more preferably 0.5 ppm by weight or less. Note that these metals may be mixed in not only from the catalyst used but also from raw materials or reaction equipment. Regardless of their origin, the total amount of compounds of these metals in the polycarbonate resin, as the total content of sodium, potassium, cesium, and iron, is preferably within the above-mentioned range.

[0204] (Synthesis of polycarbonate resin (C)) The polycarbonate resin (C) is preferably obtained by polycondensing a dihydroxy compound used as a raw material, such as the dihydroxy compound represented by the above formula (4), with a carbonic acid diester through an ester exchange reaction in the presence of a polymerization catalyst.

[0205] The dihydroxy compound and carbonate diester raw materials are preferably mixed uniformly before the transesterification reaction. The mixing temperature is usually 80°C or higher, preferably 90°C or higher, and usually 250°C or lower, preferably 200°C or lower, and more preferably 150°C or lower, with 100°C or higher and 120°C or lower being preferred. In this case, the dissolution rate can be increased, the solubility can be sufficiently improved, and problems such as solidification can be sufficiently avoided. Furthermore, in this case, thermal degradation of the dihydroxy compound can be sufficiently suppressed, resulting in a polycarbonate resin with a better color tone and improved weather resistance.

[0206] The operation of mixing the raw material dihydroxy compound and carbonic acid diester is preferably carried out in an atmosphere with an oxygen concentration of 10 vol% or less, more preferably 0.0001 to 10 vol%, even more preferably 0.0001 to 5 vol%, and particularly preferably 0.0001 to 1 vol%, which can improve the color tone and increase the reactivity.

[0207] To obtain a polycarbonate resin, it is preferable to use a carbonic acid diester in a molar ratio of 0.90 to 1.20 relative to the total dihydroxy compounds used in the reaction. In this case, an increase in the number of hydroxyl terminal groups in the polycarbonate resin can be suppressed, thereby improving the thermal stability of the polymer. This can further prevent coloration during molding and increase the rate of the transesterification reaction. It also makes it possible to more reliably obtain a desired high molecular weight polymer. Furthermore, by adjusting the amount of carbonic acid diester used within the above range, a decrease in the rate of the transesterification reaction can be suppressed, enabling more reliable production of a polycarbonate resin with a desired molecular weight. Furthermore, this can suppress an increase in thermal history during the reaction, thereby further improving the color tone and weather resistance of the polycarbonate resin. Furthermore, this can reduce the amount of residual carbonic acid diester in the polycarbonate resin, thereby avoiding or mitigating the generation of stains and odors during molding. From the same perspectives as above, it is more preferable that the amount of carbonic acid diester used relative to the total dihydroxy compounds is 0.95 to 1.10 in molar ratio.

[0208] The polycondensation of a dihydroxy compound and a carbonate diester is carried out in multiple stages using multiple reactors in the presence of the above-mentioned catalyst. The reaction may be carried out in a batchwise manner, a continuous manner, or a combination of a batchwise manner and a continuous manner, but it is preferable to adopt a continuous manner, which allows the production of a polycarbonate resin with less thermal history and is therefore excellent in productivity.

[0209] From the viewpoint of controlling the polymerization rate and the quality of the resulting polycarbonate resin, it is important to appropriately select the jacket temperature, internal temperature, and pressure in the reaction system according to the reaction stage. Specifically, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum in the early stage of the polycondensation reaction, and to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum in the later stage of the reaction. In this case, distillation of unreacted monomers is suppressed, and it becomes easier to adjust the molar ratio of the dihydroxy compound to the carbonate diester to the desired ratio. As a result, a decrease in the polymerization rate can be suppressed. Furthermore, it becomes possible to more reliably obtain a polymer with the desired molecular weight and terminal groups.

[0210] Furthermore, the polymerization rate in a polycondensation reaction is controlled by the balance between hydroxyl and carbonate terminal groups. Therefore, if the balance of terminal groups fluctuates due to the distillation of unreacted monomers, it becomes difficult to maintain a constant polymerization rate, which can lead to significant fluctuations in the molecular weight of the resulting resin. Because the molecular weight of a resin correlates with its melt viscosity, fluctuations in melt viscosity can occur during melt processing of the resulting resin, making it difficult to maintain consistent molded product quality. This problem is particularly likely to occur when polycondensation reactions are performed continuously.

[0211] The use of a reflux condenser in a polymerization reactor is effective in suppressing the amount of unreacted monomer distilled off, and is particularly effective in the early stages of the reaction when a large amount of unreacted monomer is present. The temperature of the refrigerant introduced into the reflux condenser can be selected appropriately depending on the monomer used. Typically, the temperature of the refrigerant introduced into the reflux condenser at the inlet of the reflux condenser is 45 to 180°C, preferably 80 to 150°C, and particularly preferably 100 to 130°C. By adjusting the refrigerant temperature within these ranges, the reflux amount can be sufficiently increased, its effects can be fully achieved, and the efficiency of distillation of the monohydroxy compound to be distilled off can be sufficiently improved. As a result, a decrease in the reaction rate can be prevented, and discoloration of the resulting resin can be further prevented. Examples of refrigerants that can be used include hot water, steam, and heat transfer oil, with steam and heat transfer oil being preferred.

[0212] In order to maintain an appropriate polymerization rate, suppress distillation of monomers, and improve the color tone of the resulting polycarbonate resin, it is important to select the type and amount of the polymerization catalyst described above.

[0213] Polycarbonate resins are usually produced through two or more steps using a polymerization catalyst. The polycondensation reaction may be carried out in two or more steps using one polycondensation reactor, with conditions sequentially changed, but from the viewpoint of production efficiency, it is preferable to carry out the reaction in multiple steps using multiple reactors, with conditions changed for each step.

[0214] From the viewpoint of efficiently carrying out the polycondensation reaction, in the early stage of the reaction when the reaction solution contains a large amount of monomer, it is important to maintain the required polymerization rate while suppressing the evaporation of the monomer. Furthermore, in the later stage of the reaction, it is important to shift the equilibrium toward the polycondensation reaction by sufficiently distilling off the by-product monohydroxy compound. Therefore, the reaction conditions suitable for the early stage of the reaction are usually different from those suitable for the later stage of the reaction. Therefore, by using multiple reactors arranged in series, the respective conditions can be easily changed, thereby improving production efficiency.

[0215] As described above, the number of polymerization reactors used in the production of polycarbonate resins may be at least two, but from the viewpoint of production efficiency, the number is three or more, preferably 3 to 5, and particularly preferably 4. When there are two or more polymerization reactors, each polymerization reactor may further carry out a plurality of reaction stages under different conditions, or the temperature and pressure may be changed continuously.

[0216] The polymerization catalyst can be added to a raw material preparation tank or a raw material storage tank, or can be added directly to a polymerization reactor. From the viewpoint of supply stability and control of the polycondensation reaction, it is preferable to install a catalyst supply line in the raw material line before supplying the raw materials to the polymerization reactor, and supply the polymerization catalyst in the form of an aqueous solution.

[0217] Adjusting the temperature of the polycondensation reaction can improve productivity and prevent the product from being subjected to increased heat history. Furthermore, it is possible to further prevent volatilization of the monomer and decomposition and discoloration of the polycarbonate resin. Specifically, the following reaction conditions can be adopted for the first-stage reaction. The maximum internal temperature of the polymerization reactor is set within the range of usually 150 to 250°C, preferably 160 to 240°C, and more preferably 170 to 230°C. The pressure of the polymerization reactor (hereinafter, "pressure" refers to absolute pressure) is set within the range of usually 1 to 110 kPa, preferably 5 to 70 kPa, and more preferably 7 to 30 kPa. The reaction time is set within the range of usually 0.1 to 10 hours, preferably 0.5 to 3 hours. The first-stage reaction is preferably carried out while distilling off the generated monohydroxy compound from the reaction system.

[0218] From the second stage onwards, it is preferable to gradually reduce the pressure of the reaction system from the pressure of the first stage, and ultimately reduce the pressure (absolute pressure) of the reaction system to 1 kPa or less while continuously removing the generated monohydroxy compound from the reaction system. The maximum internal temperature of the polymerization reactor is usually set in the range of 200 to 260°C, preferably 210 to 250°C. The reaction time is usually set in the range of 0.1 to 10 hours, preferably 0.3 to 6 hours, and particularly preferably 0.5 to 3 hours.

[0219] From the viewpoint of further suppressing coloration and thermal degradation of the polycarbonate resin and obtaining a polycarbonate resin (C) with a better color tone, it is preferable to set the maximum internal temperature of the polymerization reactor in all reaction stages to 210 to 240° C. In addition, in order to prevent a decrease in the polymerization rate in the latter half of the reaction and to minimize deterioration due to thermal history, it is preferable to use a horizontal reactor, which has excellent plug flow properties and interface renewal properties, in the final stage of the polycondensation reaction.

[0220] In continuous polymerization, in order to control the molecular weight of the polycarbonate resin finally obtained at a constant level, it is preferable to adjust the polymerization rate as necessary. In this case, a method with good operability is to adjust the pressure of the polymerization reactor in the final stage.

[0221] Furthermore, as mentioned above, the polymerization rate varies depending on the ratio of hydroxyl group terminals to carbonate group terminals. Therefore, by deliberately reducing one of the terminal groups to suppress the polymerization rate and maintaining a high vacuum in the final-stage polymerization reactor, the amount of remaining low-molecular-weight components in the resin, including monohydroxy compounds, can be reduced. However, in this case, if the amount of one terminal is too small, even a slight change in the terminal group balance can drastically reduce the reactivity, and the molecular weight of the resulting polycarbonate resin may not reach the desired molecular weight. To avoid this problem, it is preferable that the polycarbonate resin obtained in the final-stage polymerization reactor contain at least 10 mol / ton of both hydroxyl group terminals and carbonate group terminals. On the other hand, if both terminal groups are too large, the polymerization rate will be too fast and the molecular weight will be too high, so it is preferable that the amount of one terminal group be 60 mol / ton or less.

[0222] In this way, by adjusting the amount of terminal groups and the pressure of the final-stage polymerization reactor within preferred ranges, the amount of monohydroxy compounds remaining in the resin at the outlet of the polymerization reactor can be reduced. The amount of monohydroxy compounds remaining in the resin at the outlet of the polymerization reactor is preferably 2000 ppm by weight or less, more preferably 1500 ppm by weight or less, and even more preferably 1000 ppm by weight or less. By reducing the content of monohydroxy compounds at the outlet of the polymerization reactor in this way, volatilization of monohydroxy compounds and the like can be easily carried out in a subsequent step.

[0223] Although it is preferable that the amount of remaining monohydroxy compounds is small, in order to reduce it to less than 100 ppm by weight, it is necessary to extremely reduce the amount of one of the terminal groups and adopt operating conditions such as maintaining the pressure of the polymerization reactor at a high vacuum. In this case, as mentioned above, it becomes difficult to maintain the molecular weight of the obtained polycarbonate resin at a constant level, so the amount of remaining monohydroxy compounds is usually 100 ppm by weight or more, preferably 150 ppm by weight or more.

[0224] From the viewpoint of effective resource utilization, it is preferable to reuse the by-produced monohydroxy compound as a raw material for other compounds after purifying it as necessary. For example, when the monohydroxy compound is phenol, it can be used as a raw material for diphenyl carbonate, bisphenol A, etc.

[0225] The glass transition temperature of the polycarbonate resin (C) is preferably 90°C or higher. In this case, the heat resistance and impact resistance of the polycarbonate resin (C) can be improved in a well-balanced manner. From the same viewpoint, the glass transition temperature of the polycarbonate resin (C) is more preferably 100°C or higher, even more preferably 110°C or higher, and particularly preferably 120°C or higher. On the other hand, the glass transition temperature of the polycarbonate resin (C) is preferably 250°C or lower, more preferably 200°C or lower, and particularly preferably 170°C or lower. In this case, the melt viscosity can be reduced by the above-mentioned melt polymerization, and a polymer with a sufficient molecular weight can be obtained. Furthermore, when an attempt is made to increase the molecular weight by increasing the polymerization temperature and decreasing the melt viscosity, the structural unit (c1) may have insufficient heat resistance, which may result in the polymer being more susceptible to discoloration. From the viewpoint of achieving a better balance between improving the molecular weight and preventing coloration, the glass transition temperature of the polycarbonate resin (C) is more preferably 165° C. or lower, further preferably 160° C. or lower, and particularly preferably 150° C. or lower. The glass transition temperature of the polycarbonate resin (C) can be adjusted, for example, by selecting the structural units of the resin or changing the ratio.

[0226] The refractive index of the polycarbonate resin (C) is preferably 1.480 or more and 1.620 or less, more preferably 1.490 or more and 1.600 or less. When it is in this range, the composition has excellent transparency when combined with the block copolymer and / or graft copolymer (A). The refractive index of the polycarbonate resin (C) can be adjusted, for example, by selecting the structural units of the resin or changing the ratio. The refractive index can be measured by the method described below.

[0227] The polycarbonate resin (C) preferably contains a catalyst deactivator. The catalyst deactivator is not particularly limited as long as it is an acidic substance that has the function of deactivating the polymerization catalyst, but examples thereof include phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, phosphonium salts such as octylsulfonate tetrabutylphosphonium salt, benzenesulfonate tetramethylphosphonium salt, benzenesulfonate tetrabutylphosphonium salt, dodecylbenzenesulfonate tetrabutylphosphonium salt, and p-toluenesulfonate tetrabutylphosphonium salt; ammonium salts such as decylsulfonate tetramethylammonium salt, and dodecylbenzenesulfonate tetrabutylammonium salt; and alkyl esters such as benzenesulfonate methyl, p-toluenesulfonate butyl, and hexadecylsulfonate ethyl.

[0228] The catalyst deactivator preferably contains a phosphorus-based compound (hereinafter referred to as the "specific phosphorus-based compound") containing either the partial structure represented by the following structural formula (8) or the following structural formula (9). The specific phosphorus-based compound can be added after the polycondensation reaction is completed, i.e., during the kneading process, pelletization process, or the like, to deactivate the polymerization catalyst described below and inhibit the subsequent unnecessary progression of the polycondensation reaction. As a result, the progression of polycondensation when the polycarbonate resin is heated in a molding process, etc., can be inhibited, and thus the elimination of the monohydroxy compound can be inhibited. Furthermore, by deactivating the polymerization catalyst, discoloration of the polycarbonate resin at high temperatures can be further inhibited.

[0229] [ka]

[0230] The specific phosphorus-based compound containing the partial structure represented by the structural formula (8) or (9) may be phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, phosphonate ester, acidic phosphate ester, etc. Among the specific phosphorus-based compounds, phosphorous acid, phosphonic acid, and phosphonate ester are more effective in deactivating the catalyst and inhibiting coloration, and phosphorous acid is particularly preferred.

[0231] As the phosphonic acid, for example, the following compounds can be used: phosphonic acid (phosphorous acid), methylphosphonic acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 4-methoxyphenylphosphonic acid, nitrilotris(methylenephosphonic acid), propylphosphonic anhydride, etc.

[0232] As the phosphonate ester, for example, the following compounds can be used: dimethyl phosphonate, diethyl phosphonate, bis(2-ethylhexyl) phosphonate, dilauryl phosphonate, dioleyl phosphonate, diphenyl phosphonate, dibenzyl phosphonate, dimethyl methylphosphonate, diphenyl methylphosphonate, diethyl ethylphosphonate, diethyl benzylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, diethyl (methoxymethyl)phosphonate, diethyl vinylphosphonate, hydroxymethylphosphonic acid, diethyl phosphonate, dimethyl (2-hydroxyethyl)phosphonate, diethyl p-methylbenzylphosphonate, diethyl phosphonoacetic acid, ethyl diethylphosphonoacetate, tert-butyl diethylphosphonoacetate, diethyl (4-chlorobenzyl)phosphonate, diethyl cyanophosphonate, diethyl cyanomethylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl phosphonoacetaldehyde diethyl acetal, diethyl (methylthiomethyl)phosphonate, and the like.

[0233] Examples of acidic phosphate esters that can be used include the following compounds: phosphate diesters such as dimethyl phosphate, diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, bis(butoxyethyl) phosphate, bis(2-ethylhexyl) phosphate, diisotridecyl phosphate, dioleyl phosphate, distearyl phosphate, diphenyl phosphate, and dibenzyl phosphate, or mixtures of diesters and monoesters, diethyl chlorophosphate, and zinc stearyl phosphate.

[0234] The specific phosphorus-based compounds may be used singly or in any combination and ratio of two or more.

[0235] The content of the specific phosphorus compound in the polycarbonate resin is preferably 0.1 ppm by weight or more and 5 ppm by weight or less in terms of phosphorus atoms. In this case, the specific phosphorus compound can sufficiently suppress catalyst deactivation and coloration. In addition, in this case, coloration of the polycarbonate resin can be further prevented, particularly in durability tests under high temperature and high humidity.

[0236] Furthermore, by adjusting the content of the specific phosphorus-based compound according to the amount of the polymerization catalyst, the effect of suppressing catalyst deactivation and coloration can be more reliably obtained. The content of the specific phosphorus-based compound is preferably 0.5 to 5 times the molar amount of phosphorus atoms per 1 mol of metal atoms in the polymerization catalyst, more preferably 0.7 to 4 times the molar amount, and particularly preferably 0.8 to 3 times the molar amount of phosphorus atoms per 1 mol of metal atoms in the polymerization catalyst.

[0237] [Additive (D)] The resin composition of the present invention may contain an additive (D) as needed. Examples of the additive (D) include various stabilizers such as antioxidants, ultraviolet absorbers, and heat stabilizers; colorants such as inorganic pigments, organic pigments, and dyes; conductivity-imparting agents such as carbon black and ferrite; inorganic fillers; lubricants; mold release agents; plasticizers; organic peroxides; neutralizing agents; crosslinking agents; and reinforcing agents. The proportion of the additive (D) is preferably 0 to 20 parts by mass, more preferably 0 to 10 parts by mass, based on 100 parts by mass of the resin composition.

[0238] [Physical properties of resin composition] Charpy impact strength The Charpy impact strength of the resin composition of the present invention is 3 kJ / m compared to the Charpy impact strength of the polycarbonate resin (C) alone. 2 It is preferable that the Charpy impact strength is greater than 5kJ / m 2 More preferably, the Charpy impact strength is 8kJ / m or greater. 2 It is even more preferable that the Charpy impact strength is greater than or equal to 10 kJ / m 2 It is particularly preferable that the Charpy impact strength is greater than or equal to this value. The larger this value, the more excellent the impact resistance of the resin composition. The Charpy impact strength is specifically measured by the method described in the Examples section below.

[0239] Flexural modulus The flexural modulus of the resin composition of the present invention is preferably 2400 MPa or more, more preferably 2500 MPa or more, and even more preferably 2600 MPa or more. When the flexural modulus is above the lower limit, the resin composition has excellent rigidity. The upper limit of the flexural modulus is usually about 10000 MPa. Specifically, the flexural modulus is measured by the method described in the Examples section below.

[0240] ·Transparency The haze of a 2 mm thick plate-shaped molded product of the resin composition of the present invention at room temperature (23°C) is preferably less than 5.0%, more preferably less than 1.5%. The haze at 80°C is preferably less than 7.0%, more preferably less than 2.0%. When the haze is less than the above upper limit, the transparency of the resin composition is excellent. Furthermore, the absolute value of the difference between the haze of a 2 mm thick plate-shaped molded product of the resin composition at room temperature (23°C) and the haze at 80°C is preferably 7.0 or less, more preferably 2.0 or less. When the absolute value of the haze difference is less than the above upper limit, the resin composition is excellent in suppressing changes in transparency due to temperature. Specifically, the haze is measured by the method described in the Examples section below.

[0241] [Method of producing resin composition] The resin composition of the present invention can be produced, for example, by mechanically melt-kneading the above-mentioned components, i.e., the polycarbonate resin (C), the particles (P), and the optional additive (D). Examples of melt-kneading machines that can be used here include single-screw extruders, twin-screw extruders, Brabender mixers, Banbury mixers, kneader blenders, and roll mills. The lower limit of the kneading temperature is usually 100°C or higher, preferably 145°C or higher, and more preferably 160°C or higher. The upper limit of the kneading temperature is usually 350°C, preferably 300°C, and more preferably 250°C. During kneading, the components may be kneaded all at once, or a multi-stage division kneading method may be used in which any component is kneaded and then the remaining components are added and kneaded.

[0242] [Method of manufacturing molded body] The resin composition of the present invention can be processed into various molded articles by molding methods such as injection molding (insert molding, two-color molding, sandwich molding, gas injection molding, etc.), extrusion molding, inflation molding, T-die film molding, lamination molding, blow molding, hollow molding, compression molding, and calendar molding. The shape of the molded article is not particularly limited, and examples include sheets, films, plates, particles, blocks, fibers, rods, porous bodies, and foams, with sheets, films, and plates being preferred. The molded film can also be uniaxially or biaxially stretched. Examples of stretching methods include rolls, tentering, and tubular methods. Furthermore, surface treatments commonly used in industry, such as corona discharge treatment, flame treatment, plasma treatment, and ozone treatment, can also be applied.

[0243] [Application] The uses of the molded article containing the resin composition of the present invention are not particularly limited, but examples thereof include the following uses. In the field of electrical and electronic components, these products include covering materials for electric wires, cords, wire harnesses, etc., insulating sheets, displays and touch panels for office automation equipment, membrane switches, photo covers, relay parts, coil bobbins, IC sockets, fuse cases, camera pressure plates, FDD collets, and floppy hubs. In the field of optical components, these products include optical disc substrates, optical disc pickup lenses, optical lenses, LCD substrates, PDP substrates, television screens for projection televisions, phase difference films, fog lamp lenses, illuminated switch lenses, sensor switch lenses, Fresnel lenses, protective glasses, projection lenses, camera lenses, sunglasses, light guide plates, camera strobe reflectors, and LED reflectors. In the field of automotive components, these products include headlamp lenses, turn signal lamp lenses, tail lamp lenses, plastic window glass, meter covers, outer panels, door handles, rear panels, wheel caps, visors, roof rails, sunroofs, instrument panels, panels, in-car displays, control cable covering materials, airbag covers, mudguards, bumpers, boots, airbags, etc. Hoses, lamp packings, gaskets, various moldings such as window moldings, sight shields, weather strips, glass run channels, grommets, vibration control and sound insulation materials, joint materials in the building materials field, handrails, windows, table edge materials, sashes, bathtubs, window frames, signs, lighting covers, water tanks, staircase wainscoting, carports, highway sound insulation walls, multi-wall sheets, steel wire coating materials, lighting globes, switch breakers, protective covers for machine tools, industrial deep-drawn vacuum formed containers, pump housings, home appliances, various packings in the light electrical field, grease Cups, belts, rubber feet, rollers, protectors, suction cups, gaskets for refrigerators, switches, connector covers, game machine covers, pachinko machines, OA housings, notebook PC housings, HDD head trays, instrument windows, transparent housings, OA gear rollers, switch case sliders, gas cock knobs, watch frames, watch wheel train center pieces, amber caps, various rolls for OA equipment, tubular molded products such as hoses and tubes, irregular extrusion products, leather-like products, interlocking devices, toys such as soft-touch dolls, pen grips,Examples of applications include straps, suction cups, watches, umbrella bones, cosmetic cases, toothbrush handles and other general goods, housewares, Tupperware and other containers, cable ties, blow-molded infusion bottles, food bottles, water bottles, various bottles for personal care such as cosmetic bottles, catheters in medical parts, syringes, syringe gaskets, drip tubes, tubes, ports, caps, rubber stoppers, dialyzers, blood connectors, dentures, disposable containers, and the like, and foam molding applications are also possible.

[0244] The applications of the molded article containing the resin composition of the present invention in the film and sheet field are not particularly limited, but examples include the following applications. Namely, stretch film for packaging, wrap film for commercial or household use, pallet stretch film, stretch label, shrink film, shrink label, sealant film, retort film, retort sealant film, aroma-retaining heat seal film, A-PET sealant, frozen food containers and lids, cap seals, heat welding film, heat adhesive film, heat sealing film, bag-in-box sealant film, retort pouches, stand-up pouches, spout pouches, laminated tubes, heavy-duty bags, textile packaging film and other food and miscellaneous goods packaging fields, greenhouse films, mulch films and other agricultural films, infusion bags, multi-chamber containers for high-calorie infusions, peritoneal dialysis (CAPD), antibiotic kit bags and other such products, peritoneal dialysis drainage bags, blood bags, urine bags, surgical bags, ice pillows, ampoule cases, PTP packaging and other medical films and sheets, civil engineering waterproof sheets, waterproof materials, mats, joint materials, flooring materials, roofing leather, ceiling materials, trunk linings, interior skin materials, vibration control sheets, sound insulation sheets, etc. in the automotive parts field; display covers, battery cases, mouse pads, mobile phone cases, IC card holders, floppy disk cases, CD-ROM cases, etc. in the low-voltage field; toothbrush cases, puff cases, cosmetic cases, eye drop and other medicine cases, tissue cases, face masks, etc. in the toiletry and sanitary field; stationery films and sheets, clear files, pen cases, notebook covers, desk mats, keyboard covers, book covers, binders, etc. in the office supplies field; leather for furniture, toys such as beach balls, umbrellas, raincoats, etc. in the general household and miscellaneous goods field such as tablecloths, blister packages, bathtub covers, towel cases, fancy cases, tag cases, pouches, amulet bags, insurance card covers, bankbook cases, passport cases, knife cases, etc.; retroreflective sheets, synthetic paper, etc.Furthermore, examples of adhesive compositions or films and sheets to which adhesive properties have been imparted by applying an adhesive to a substrate include carrier tape, adhesive tape, marking film, dicing film for semiconductors or glass, surface protection film, steel plate and plywood protection film, automobile protection film, adhesive tape for packaging and binding, adhesive tape for office and household use, adhesive tape for joining, adhesive tape for paint masking, adhesive tape for surface protection, adhesive tape for sealing, adhesive tape for corrosion prevention and waterproofing, adhesive tape for electrical insulation, adhesive tape for electronic devices, adhesive film for clothing, adhesive tape for medical and sanitary materials such as adhesive tape base film, adhesive tape for identification and decoration, tape for display, packaging tape, surgical tape, adhesive tape for labels, etc.

[0245] [film] The resin composition of the present invention is particularly useful as a film-forming material, among the various applications mentioned above, because of its excellent transparency, color tone, mechanical properties, heat resistance, moist heat resistance, and dry heat resistance. The film containing the resin composition of the present invention may be a single-layer film made of the resin composition of the present invention, or may be a laminated film of two or more layers formed by co-extrusion with another resin composition. Such a film is useful as a raw film for processing and molding into the containers described below, or as a protective film for the display surfaces of electronic devices, mobile phones, smartphones, etc. Its excellent transparency does not impair the visibility of the display surface underneath the film, and its excellent impact resistance provides excellent protection for devices. Furthermore, its excellent long-term wet heat resistance and long-term dry heat resistance enable it to withstand long-term use in a variety of environments. [Example]

[0246] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following, "parts" means "parts by mass."

[0247] The evaluations in the examples and comparative examples were carried out by the following methods.

[0248] (Mass average molecular weight (Mw) and number average molecular weight (Mn) of macromonomer (a1)) The mass average molecular weight (Mw) and number average molecular weight (Mn) of the macromonomer (a1) obtained in the examples and comparative examples were measured by gel permeation chromatography (GPC). 10 mg of the copolymer obtained was dissolved in 10 mL of tetrahydrofuran, and the solution was filtered through a 0.45 μm filter to prepare a sample for GPC measurement. A polymer measurement guard column (manufactured by Tosoh Corporation, product name: TSK-GUARD COLUMN SUPER HH) and two polymer measurement columns (manufactured by Tosoh Corporation, product name: TSK-GEL SUPER HM-H) were connected in series to a gel permeation chromatography measurement device (manufactured by Tosoh Corporation, model name: HLC-8320). A differential refractometer (RI) was used as the detector. Measurements were performed under the following conditions: separation column temperature: 40°C, mobile phase: tetrahydrofuran, mobile phase flow rate: 0.6 mL / min, and sample injection volume: 10 μL. A calibration curve was created using several types of polymethyl methacrylate with known molecular weights (Polymer Laboratories, peak molecular weight (Mp) 1,560 to 19,500,000) as standard polymers, and Mw and Mn were determined.

[0249] (Mass average molecular weight (Mw) and number average molecular weight (Mn) of macromonomer copolymer) The mass average molecular weight (Mw) and number average molecular weight (Mn) of the macromonomer copolymers, which are block copolymers and / or graft copolymers (A) obtained in the examples and comparative examples, were measured using gel permeation chromatography (GPC). 10 mg of the copolymer obtained was dissolved in 10 mL of tetrahydrofuran, and the solution was filtered through a 0.45 μm filter to prepare a sample for GPC measurement. For GPC measurement of the copolymer, a high-performance liquid chromatography analyzer (Tosoh Corporation, model name: HLC-8320) was used, connected in series with a polymer measurement guard column (Tosoh Corporation, product name: TSK-GEL SUPER HM-H) and one ultra-polymer measurement column (Tosoh Corporation, product name: TSK-GEL GMH HR-H). A differential refractometer (RI) was used as the detector. Measurements were performed under the following conditions: separation column temperature: 40°C, mobile phase: tetrahydrofuran, mobile phase flow rate: 0.6 mL / min, and sample injection volume: 10 μL. A calibration curve was created using several types of polymethyl methacrylate with known molecular weights (Polymer Laboratories, peak molecular weights (Mp) 1,560 to 19,500,000) as standard polymers, and the mass-average molecular weight (Mw) and number-average molecular weight (Mn), which are relative molecular weights converted to polymethyl methacrylate, were determined.

[0250] (Mass Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn) of (Meth)acrylic Copolymer (B)) The mass average molecular weight (Mw) of the (meth)acrylic copolymer (B) in the particles of the present invention was measured using gel permeation chromatography (GPC). 10 mg of the obtained copolymer was dissolved in 10 mL of tetrahydrofuran, and the solution was filtered through a 0.45 μm filter to prepare a sample for GPC measurement. For GPC measurement of the copolymer, a high-performance liquid chromatography measuring device (manufactured by Tosoh Corporation, model name: HLC-8320) was used, connected in series with a polymer measurement guard column (manufactured by Tosoh Corporation, product name: TSK-GEL SUPER HM-H) and one ultra-polymer measurement column (manufactured by Tosoh Corporation, product name: TSK-GEL GMH HR-H). A differential refractometer (RI) was used as the detector. Measurements were performed under the following conditions: separation column temperature: 40°C, mobile phase: tetrahydrofuran, mobile phase flow rate: 0.6 mL / min, and sample injection volume: 10 μL. A calibration curve was created using several types of polymethyl methacrylate with known molecular weights (Polymer Laboratories, peak molecular weights (Mp) 1,560 to 19,500,000) as standard polymers, and the mass-average molecular weight (Mw) and number-average molecular weight (Mn), which are relative molecular weights converted to polymethyl methacrylate, were determined.

[0251] (Measurement of angle of repose) The angle of repose of the particles obtained in the examples and comparative examples was measured using an A, B, D powder property measuring instrument (Model A, B, D-72) manufactured by Tsutsui Scientific Instruments Co., Ltd. The powder was gently poured onto a disk to form a mound. The angle of the left base of the mound formed on the disk was measured. The above procedure was performed three times, and the average value was taken as the angle of repose. The angle of repose was measured using a disk with a diameter of 80 mm. The angle of repose was evaluated in three stages according to the following criteria. ◎: Angle of repose is less than 40° ○: Angle of repose is 40° or more but less than 50° ×: Angle of repose is 50° or more

[0252] (blocking resistance) Figure 1 shows the equipment used to prepare samples for evaluating blocking resistance. 20 g of sample was placed in a cylindrical case 2 with a bottom lid 1, and a top lid 3 was placed on top of the sample. A 5 kg weight 5 was placed on top of the case 2 with a weight stand 4, and the load (pressure: 20 kPa / cm) of the weight 5 was applied to the sample. 2 The sample preparation equipment was placed in a gear oven at 50°C and heated for 6 hours while applying a pressure of 1.4 mm to create a block-shaped sample. After the sample was prepared, it was cooled to room temperature and then placed on a #12 mesh (1.4 mm opening) sieve using a shaker and shaken at regular intervals. The sample block was broken down by shaking, and the time and amount of broken block (amount of powder in the tray) were measured at regular intervals. The time until 60% of the block (12 g) was broken was defined as the 60% crushing time, and blocking resistance was evaluated. The blocking resistance was evaluated on a three-level scale according to the following criteria. ◎: 60% crushing time is less than 100 seconds 〇: 60% crushing time is between 100 seconds and 600 seconds ×: 60% crushing time is 600 seconds or more

[0253] (Charpy impact test) As an index of impact resistance of the molded body, the Charpy impact strength (unit: kJ / m) was measured in accordance with JIS K7111-1 / 1eA (with V-notch, notch tip diameter r = 0.25) using a Charpy impact tester (manufactured by Toyo Seiki Co., Ltd., product name: DG-CP). 2 Five pieces were tested using a 15J hammer, and the average value was calculated. The Charpy impact strength was evaluated in three stages according to the following criteria. ◎: Charpy impact strength is 10kJ / m 2 End ○: Charpy impact strength is 5kJ / m 2 More than 10kJ / m 2 less than ×: Charpy impact strength is 5kJ / m 2 less than

[0254] (Bending elasticity test) As an index of the rigidity of the molded article, the flexural modulus (unit: MPa) of the test piece of the rod-shaped molded article was measured using a Tensilon universal testing machine (manufactured by Orientec Co., Ltd., product name: RTC-1250A) in accordance with JIS K 7171. The flexural modulus was determined from a stress-strain curve obtained under conditions of room temperature 23°C and a test speed of 2 mm / min. The flexural modulus was evaluated in three stages according to the following criteria. ◎: Flexural modulus of elasticity is 2600 MPa or more ○: Flexural modulus is 2500 MPa or more but less than 2600 MPa ×: Flexural modulus less than 2500 MPa

[0255] (Hayes) As an index of transparency of the 2 mm thick plate-shaped molded product, the haze (unit: %) of a 2 mm thick plate-shaped molded product test piece was measured at room temperature of 23°C and 80°C in accordance with JIS K7316 using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., device name: NDH2020). For the 80°C measurement, the plate-shaped molded product was left to stand in an 80°C environment for 1 hour, and then the measurement was carried out immediately. The haze value at room temperature of 23°C was evaluated in three stages according to the following criteria. ◎: Haze is 0.0 or more and less than 1.5% ○: Haze is 1.5% or more and less than 5.0% ×: Haze is 5% or more The haze value at room temperature of 80° C. was evaluated in three stages according to the following criteria. ◎: Haze is 0.0% or more and less than 2.0% ○: Haze is 2.0% or more and less than 7.0% ×: Haze is 7.0% or more The absolute value of the difference between the haze value at room temperature of 23°C and the haze value at room temperature of 80°C was evaluated in three stages according to the following criteria. ◎: The absolute value of the difference in haze is 0.0% or more and less than 2.0% ○: The absolute value of the difference in haze is 2.0% or more and less than 7.0% ×: The absolute value of the difference in haze is 7.0% or more

[0256] (refractive index) The refractive index of the polymer was measured using an Abbe refractometer at the D line of the sodium spectrum at a temperature of 20°C. The refractive index measured under the above conditions is expressed as nD20. The refractive index of the homopolymer of the comonomer was measured using a model polymer of the same monomer composition prepared separately by polymerizing only the comonomer.

[0257] (raw materials) The abbreviations for the compounds used in the examples and comparative examples are as follows. MMA: Methyl methacrylate (Mitsubishi Chemical Corporation) MA: Methyl acrylate (Mitsubishi Chemical Corporation) PHMA: Phenyl methacrylate (Mitsubishi Chemical Corporation) BA: n-butyl acrylate (Mitsubishi Chemical Corporation) BzA: Benzyl acrylate (Osaka Organic Co., Ltd.) St: Styrene (Fujifilm Wako Pure Chemical Industries, Ltd.) Dispersant (1): Dispersant prepared in Preparation Example 1 Chain transfer agent (1): The chain transfer catalyst prepared in Preparation Example 2 Polymerization initiator (1): 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (manufactured by NOF Corporation, trade name: Perocta O) Polymerization initiator (2): 2,2'-azobis(2-methylbutyronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: V-59)

[0258] [Production Example 1: Synthesis of Dispersant (1)] A reactor equipped with a stirrer, a condenser, and a thermometer was charged with 61.6 parts of a 17% by mass aqueous potassium hydroxide solution, 19.1 parts of MMA, and 19.3 parts of deionized water. The liquid in the reactor was then stirred at room temperature, and after confirming the exothermic peak, the mixture was stirred for 4 hours. After this, the reaction liquid in the reactor was cooled to room temperature to obtain an aqueous potassium methacrylate solution.

[0259] Next, 900 parts of deionized water, 70 parts of a 42% by weight aqueous solution of sodium 2-sulfoethyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester SEM-Na), 16 parts of the above potassium methacrylate aqueous solution, and 7 parts of MMA were added to a polymerization apparatus equipped with a stirrer, condenser, and thermometer, and the mixture was stirred. While the atmosphere inside the polymerization apparatus was replaced with nitrogen, the temperature of the liquid in the reaction apparatus was raised to 50°C. 0.053 parts of V-50 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: 2,2'-azobis(2-methylpropionamidine) dihydrochloride) was added as a polymerization initiator to the polymerization apparatus, and the temperature of the liquid in the reaction apparatus was raised to 60°C. After adding the polymerization initiator, 1.4 parts of MMA was added in five instalments every 15 minutes (total amount of MMA: 7 parts). Thereafter, the liquid in the polymerization apparatus was kept at 60° C. for 6 hours while being stirred, and then cooled to room temperature to obtain a dispersant (1) in the form of a transparent aqueous solution with a solid content of 8% by mass.

[0260] [Production Example 2: Synthesis of Chain Transfer Agent (1)] In a synthesis apparatus equipped with a stirrer, 2.00 g (8.03 mmol) of cobalt (II) acetate tetrahydrate (Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade), 3.86 g (16.1 mmol) of diphenylglyoxime (Tokyo Chemical Industry Co., Ltd., EP Grade), and 100 mL of diethyl ether that had been deoxygenated in advance by nitrogen bubbling were placed under a nitrogen atmosphere, and the mixture was stirred at room temperature for 2 hours.

[0261] Next, 20 mL of boron trifluoride diethyl ether complex (manufactured by Tokyo Chemical Industry Co., Ltd., EP grade) was added, and the mixture was stirred for another 6 hours. The obtained mixture was filtered, and the solid was washed with diethyl ether and dried at 100 MPa or less at 20°C for 12 hours to obtain 5.02 g (7.93 mmol, yield 99% by mass) of chain transfer agent (1) as a brown solid.

[0262] [Production Example 3: Synthesis of Macromonomer (a1-1)] In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 parts of deionized water, 0.1 parts of sodium sulfate (Na2SO4), and 0.26 parts of dispersant (1) (solid content 8 mass%) produced in Production Example 1 were added and stirred to form a uniform aqueous solution. Next, 81 parts of MMA (Tg of the homopolymer is 100°C), 5 parts of MA, 14 parts of PHMA (refractive index of the homopolymer is 1.56), 0.0015 parts of the chain transfer agent (1) produced in Production Example 2, and 0.3 parts of polymerization initiator (1) were added to form an aqueous dispersion.

[0263] The inside of the polymerization reactor was then thoroughly purged with nitrogen, and the aqueous dispersion was heated to 75°C and held there for 3 hours, then heated to 90°C and held there for 2 hours. The reaction solution was then cooled to 40°C to obtain an aqueous suspension of the macromonomer. This aqueous suspension was filtered through a filter cloth, and the filtrate was washed with deionized water and dried at 40°C for 16 hours to obtain a bead-like macromonomer (a1-1). The resulting macromonomer (a1-1) had a number-average molecular weight (Mn) of 20,700 and a mass-average molecular weight (Mw) of 38,000. The charging and polymerization results are shown in Table 1.

[0264] [Production Example 4: Synthesis of Macromonomer (a1-2)] In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate (NaSO), and 0.26 parts of dispersant (1) (solid content 8% by mass) produced in Production Example 1 were added and stirred to form a uniform aqueous solution. Next, 81 parts of MMA, 5 parts of MA, 14 parts of PHMA, 0.001 part of chain transfer agent (1) produced in Production Example 2, and 0.3 parts of polymerization initiator (1) were added to form an aqueous dispersion.

[0265] The inside of the polymerization reactor was then thoroughly purged with nitrogen, and the aqueous dispersion was heated to 75°C and held there for 3 hours, then heated to 90°C and held there for 2 hours. The reaction solution was then cooled to 40°C to obtain an aqueous suspension of the macromonomer. This aqueous suspension was filtered through a filter cloth, and the filtrate was washed with deionized water and dried at 40°C for 16 hours to obtain macromonomer (a1-2) in the form of beads. The obtained macromonomer (a1-2) had a number-average molecular weight (Mn) of 38,200 and a mass-average molecular weight (Mw) of 65,500. The charging and polymerization results are shown in Table 1.

[0266] [Production Example 5: Synthesis of (meth)acrylic copolymer (B-1)] A reaction vessel equipped with a stirrer, condenser, and thermometer was charged with a mixture of 280 parts deionized water, 1 part dipotassium alkenyl succinate, 0.12 parts potassium persulfate, 40 parts methyl methacrylate, 2 parts butyl acrylate, and 0.0057 parts n-octyl mercaptan. After purging the atmosphere with nitrogen, the reaction vessel was heated to 65°C with stirring and polymerized for 2 hours. A mixture of 44 parts methyl methacrylate and 14 parts butyl acrylate was then added to the reaction vessel over 1 hour. After the addition was completed, the mixture was stirred for 2 hours to complete the polymerization, yielding a latex of (meth)acrylic copolymer (B-1). The resulting (meth)acrylic copolymer (B-1) had an Mw of 1,500,000, a median diameter of 100 nm, and a Tg of 67°C.

[0267] [Example 1] In a polymerization apparatus equipped with a stirrer, a cooling tube, and a thermometer, 40.0 parts of the macromonomer (a1-1) obtained in Production Example 3, 200 parts of deionized water, 0.5 parts of dispersant (1), and 0.3 parts of sodium sulfate were added and stirred to obtain an aqueous suspension. Next, the temperature inside the polymerization apparatus was raised to 70 ° C, and 42.6 parts of BA and 17.4 parts of St were slowly added. The mixture was then stirred and maintained at 70 ° C for 1 hour to dissolve the macromonomer (a1-1) in the BA and St, obtaining a dispersion. Next, the polymerization apparatus was cooled to 40 ° C, and 0.5 parts of polymerization initiator (2) was added and stirred for 30 minutes to dissolve. Next, the atmosphere inside the polymerization apparatus was thoroughly purged with nitrogen, and the aqueous dispersion was heated to 78 ° C and maintained for 3 hours, then heated to 90 ° C and maintained for 1 hour. By cooling to 40 ° C, a block copolymer and / or graft copolymer (A-1) dispersed in water was obtained. To the block copolymer and / or graft copolymer (A-1) dispersed in water, 0.5 parts of magnesium sulfate and 3.8 parts of the (meth)acrylic copolymer (B-1) obtained in Production Example 5 were added and stirred, and the temperature inside the polymerization reactor was raised to 80°C. The mixture was then maintained at 80°C for 10 minutes with stirring. After cooling to below 40°C, the mixture was filtered through a filter cloth, and the filtrate was washed with deionized water. The filtrate was then dried at 40°C for 12 hours using a hot air circulation dryer to obtain particles (P-1) containing the block copolymer and / or graft copolymer (A-1) and the (meth)acrylic copolymer (B-1). The block copolymer and / or graft copolymer (A-1) contained in the obtained particles (P-1) had a number average molecular weight (Mn) of 77,700 and a mass average molecular weight (Mw) of 576,100. The angle of repose of the obtained particles (P-1) was 43° on an 80 mm diameter disk, indicating good processability. The 60% crushing time in a blocking test for the obtained particles (P-1) was 125 seconds, indicating sufficiently high blocking resistance. The charging and polymerization results are shown in Table 2. The Tg of the homopolymer of styrene (St) is 100°C (POLYMER HANDBOOK FOURTH EDITION 2003), and the Tg of the homopolymer of n-butyl acrylate (BA) is -54°C (POLYMER HANDBOOK FOURTH EDITION 2003). The Tg of the homopolymer of the (meth)acrylic polymer (A2) contained in the (meth)acrylic copolymer (A) was calculated to be -24°C using the Fox equation.

[0268] [Examples 2 to 3] Particles (P-2) to (P-3) of Examples 2 to 3 were obtained in the same manner as in Example 1, except that the types and amounts of macromonomer (a1), monomer (a2), and (meth)acrylic copolymer (B-1) were changed as shown in Table 2. The block copolymer and / or graft copolymer (A-2) contained in the particles (P-2) obtained in Example 2 had a number average molecular weight (Mn) of 97,800 and a mass average molecular weight (Mw) of 1,452,100. The angle of repose of the particles (P-2) was 33° on an 80 mm diameter disk, indicating good processability. The 60% crushing time in a blocking test for the obtained particles (P-2) was 17 seconds, indicating sufficiently high blocking resistance. The charging and polymerization results are shown in Table 2. The block copolymer and / or graft copolymer (A-3) contained in the particles (P-3) obtained in Example 3 had a number average molecular weight (Mn) of 99,200 and a mass average molecular weight (Mw) of 3,752,700. The angle of repose of the particles (P-3) was 33° on an 80 mm diameter disk, indicating good processability. The 60% crushing time in a blocking test for the obtained particles (P-3) was 12 seconds, indicating sufficiently high blocking resistance. The charging and polymerization results are shown in Table 2.

[0269] [Comparative Example 1] The block copolymer and / or graft copolymer (A-3) dispersed in water was filtered through a filter cloth, and the filtrate was washed with deionized water and then dried at 40°C for 12 hours using a hot air circulation dryer to obtain particles (P-4) containing the block copolymer and / or graft copolymer (A-3). The block copolymer and / or graft copolymer (A-3) contained in the obtained particles (P-4) had a number average molecular weight (Mn) of 99,200 and a mass average molecular weight (Mw) of 3,752,700. The angle of repose of particles (P-4) on an 80 mm diameter disk was 52°, indicating poor processability. The 60% crushing time in a blocking test for the resulting particles (P-4) was over 1200 seconds, indicating poor blocking resistance. The charging and polymerization results are shown in Table 2.

[0270] [Table 1]

[0271] [Table 2]

[0272] [Production Example 6: Polycarbonate Resin (C-1)] Polycarbonate resin polymerization was carried out using a continuous polymerization system consisting of three vertical stirred reactors, one horizontal stirred reactor, and a twin-screw extruder. Specifically, ISB, CHDM, and DPC were melted in tanks and continuously fed into the first vertical stirred reactor at flow rates of 35.2 kg / hr for ISB, 14.9 kg / hr for CHDM, and 74.5 kg / hr for DPC (molar ratio ISB / CHDM / DPC = 0.700 / 0.300 / 1.010). Simultaneously, an aqueous solution of calcium acetate monohydrate was fed into the first vertical stirred reactor at a catalyst concentration of 1.5 μmol of calcium acetate monohydrate per mol of total dihydroxy compounds. The reaction temperature, internal pressure, and residence time of each reactor were as follows: first vertical stirred reactor: 190°C, 25 kPa, 90 minutes; second vertical stirred reactor: 195°C, 10 kPa, 45 minutes; third vertical stirred reactor: 210°C, 3 kPa, 45 minutes; and fourth horizontal stirred reactor: 225°C, 0.5 kPa, 90 minutes. The internal pressure of the fourth horizontal stirred reactor was finely adjusted during operation so that the reduced viscosity of the resulting polycarbonate resin would be 0.41 dL / g to 0.43 dL / g.

[0273] Polycarbonate resin was extracted from the fourth horizontal stirred reactor at a rate of 60 kg / hr and then fed in a molten state into a vented twin-screw extruder [TEX30α, manufactured by The Japan Steel Works, Ltd., L / D: 42.0, L (mm): screw length, D (mm): screw diameter]. The extruder had three vacuum vents, where residual low-molecular-weight components in the resin were removed by volatilization. Just before the second vent, 2000 ppm of water was added to the resin, and water volatilization was performed. Just before the third vent, 0.1 parts by weight of Irganox 1010, 0.05 parts by weight of AS2112, and 0.3 parts by weight of E-275 were added, respectively, per 100 parts by weight of polycarbonate resin. The polycarbonate resin that had passed through the extruder was passed through a candle-type filter (made of SUS316) with 10 μm openings while still in the molten state to filter out foreign matter. The polycarbonate resin was then discharged from the die in the form of strands, water-cooled, solidified, and pelletized using a rotary cutter to obtain a polycarbonate resin with an ISB / CHDM molar ratio of 70 / 30 mol%. To the resulting polycarbonate resin, 0.65 ppm by weight of phosphorous acid (0.24 ppm by weight in terms of phosphorus atoms) was added as a catalyst deactivator. The phosphorous acid was added as follows: A masterbatch was prepared by sprinkling an ethanol solution of phosphorous acid onto the resulting polycarbonate resin pellets and mixing them. This masterbatch was then fed into the extruder just before the first vent port (on the resin supply port side of the extruder) so that 1 part by weight of the masterbatch was added per 100 parts by weight of the polycarbonate resin in the extruder. In Table 3, the obtained polycarbonate resin is represented as "(C-1)".

[0274] The refractive index of the polycarbonate resin (C-1) was measured using an Abbe refractometer and found to be 1.502 (nD20). Furthermore, when the polycarbonate resin (C-1) alone was subjected to a Charpy impact test using the method described above, the result was 7 kJ / m 2 It was.

[0275] [Example 4] 93 parts of pellets of polycarbonate resin (C-1) obtained in Production Example 6 and 7 parts of particles (P-1) obtained in Example 1 were melt-kneaded using a 35 mm twin-screw extruder (TEM-35B, manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 240°C to obtain a pelletized resin composition. The obtained pelletized resin composition was molded using a 100-ton injection molding machine (IS-100, manufactured by Toshiba Machine Co., Ltd.) to obtain a 2 mm thick molded body for haze measurement, a bending modulus test piece, and a Charpy impact test piece. The haze value, Charpy impact strength, and bending modulus were measured from the obtained test pieces at 23°C and 80°C. The results are shown in Table 3.

[0276] [Examples 5 to 6, Comparative Example 2] The resin compositions were changed as shown in Table 3, and other procedures were the same as in Example 4, in which melt-kneading, injection molding, and evaluation of the prepared test specimens were carried out. The results are summarized in Table 3.

[0277] [Table 3]

[0278] <Consideration> Comparing Examples 1 to 3 with Comparative Example 1, it was found that mixing the block copolymer and / or graft copolymer (A) with the (meth)acrylic copolymer (B) improved the powder flowability, blocking resistance, and processability of the particles (P). This result demonstrated that the storage stability, handling during molding, and processability of the particles (P) of the present invention were significantly improved. Furthermore, as shown in Examples 4 to 6 and Comparative Example 2, it is clear that the physical properties exhibited when particles of block copolymer and / or graft copolymer (A) coated with (meth)acrylic copolymer (B) are melt-kneaded with polycarbonate resin (C) do not impair the physical properties exhibited when the block copolymer and / or graft copolymer (A) and polycarbonate resin (C) are melt-kneaded.

[0279] The particles of the present invention, which have excellent blocking resistance and powder flowability, can provide resin compositions and molded articles therefrom that have both impact resistance and transparency over a wide temperature range, with excellent processability. Therefore, the present invention has extremely high industrial applicability in the fields of particles, resin compositions, and molded articles therefrom. [Explanation of symbols]

[0280] 1 Bottom lid 2 cases 3 Top lid 4 weight rack 5 weights< / z>

Claims

1. Particles containing a block copolymer and / or a graft copolymer (A), the block copolymer and / or graft copolymer (A) contains a (meth)acrylic polymer (A1) and a (meth)acrylic polymer (A2); the (meth)acrylic polymer (A1) contains a structural unit derived from a methacrylate having a homopolymer glass transition temperature (Tg) of higher than 80°C and a structural unit derived from a (meth)acrylate having a homopolymer refractive index (nD20) of 1.50 or higher, Particles having an angle of repose of 50° or less as measured by the following method. <Method for measuring angle of repose> Using a Tsutsui A, B, D powder property measuring instrument (Model A, B, D-72) manufactured by Rikagaku Kikaisha, the particles are gently poured onto a circular plate with a diameter of 80 mm to form a mound. The angle of the left base of the mound formed on the circular plate is measured as the angle of repose.

2. The particles according to claim 1, wherein the (meth)acrylic polymer (A2) contains a structural unit derived from an alkyl acrylate having a homopolymer glass transition temperature (Tg) of less than 0°C and a structural unit derived from an aromatic vinyl.

3. 2. The particle according to claim 1, further comprising a (meth)acrylic copolymer (B) different from the block copolymer and / or graft copolymer (A), wherein the (meth)acrylic copolymer (B) has a glass transition temperature (Tg) of 40°C or higher and 75°C or lower.

4. 2. The particles according to claim 1, wherein the mass average molecular weight (Mw) of the block copolymer and / or graft copolymer (A) is 20,000 or more and 10,000,000 or less.

5. The particles according to claim 1 or 2, wherein the (meth)acrylic polymer (A2) further contains a structural unit derived from an aromatic acrylate unit.

6. The particle according to claim 1 , wherein the (meth)acrylic polymer (A1) contains a structural unit derived from a macromonomer (a1) represented by the following general formula (1): 【Chemical 1】 (In formula (1), R ０ ~R ｎ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. １ ~X ｎ are each independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10,000.

7. A method for producing particles according to any one of claims 1 to 6, comprising: a step of obtaining the block copolymer and / or graft copolymer (A) by polymerizing a polymerizable composition (X) containing the (meth)acrylic polymer (A1) and the (meth)acrylic polymer (A2) by suspension polymerization; a step of mixing the block copolymer and / or graft copolymer (A) with the (meth)acrylic copolymer (B), and then heat-treating the mixture at a temperature equal to or higher than the glass transition temperature (Tg) of the (meth)acrylic copolymer (B).

8. The method for producing particles according to claim 7 , further comprising the step of producing the (meth)acrylic copolymer (B) by emulsion polymerization.

9. The method for producing particles according to claim 7 , wherein the polymerizable composition (X) contains a macromonomer (a1) represented by the following general formula (1): 【Chemistry 2】 (In formula (1), R ０ ~R ｎ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. １ ~X ｎ are each independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10,000.

10. 8. The method for producing particles according to claim 7, wherein the polymerizable composition (X) contains a monomer (a2), and the monomer (a2) contains an alkyl acrylate having a glass transition temperature (Tg) of a homopolymer of less than 0°C and an aromatic vinyl.

11. A resin composition comprising a polycarbonate resin (C) and the particles according to any one of claims 1 to 6.

12. the (meth)acrylic polymer (A2) has a glass transition temperature (Tg) of less than 0°C; The resin composition according to claim 11, wherein a difference in refractive index (nD20) between the polycarbonate resin (C) and the (meth)acrylic polymer (A2) is less than 0.

026.

13. The resin composition according to claim 11, wherein a difference in refractive index (nD20) between the polycarbonate resin (C) and the (meth)acrylic polymer (A1) is less than 0.

030.

14. The method for producing a resin composition according to claim 11, comprising melt-kneading the polycarbonate resin (C) and the particles.

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