JP6260287B2 - Film decorative resin molded body and method for producing the same - Google Patents

Description

  The present invention relates to a resin molded body for film decoration and a method for producing the same.

  Conventionally, an insert injection molding method has been widely adopted as a method for producing a resin molded body having a decorative film on its surface.

In this insert injection molding method, a flat plastic film is produced as a first step. As this film, a plastic single body molded into a film, a printing decorative film printed on one or both sides of the plastic film, and a three-layer in which a binder layer is adhered to the printing decorative film The film for printing decoration which consists of, etc. are mentioned.
Next, as the second step, if necessary, the film obtained in the first step is heated and softened, and drawn by vacuum forming or pressure forming to decorate the desired resin molding. Molded into a surface shape to produce a molded film.
Further, in the third step, after the film obtained in the first step or the molded film obtained in the second step is inserted into the mold of an injection molding machine and the mold is closed, the injection molding machine A method is employed in which a molten resin is injected into a mold from the cylinder and a resin molded body in which the injected resin is integrated with the above-described film or molded film is employed.

  However, such a molding method has a problem that the adhesion strength between the film or the molded film and the resin molded body is not always sufficient.

  In order to solve this, for example, Patent Document 1 discloses a method of strictly controlling the breaking strength and breaking elongation of a film to be decorated to improve the adhesion between the film and the injected resin. Patent Document 2 proposes a method for improving the adhesion between the film and the resin molded body in consideration of the relationship between the softening temperature of the injected resin and the softening temperature of the film.

JP 2003-145574 A JP 2010-149524 A

  However, since the resin molded body provided with a film as in Patent Document 1 does not consider the relationship between the softening temperature of the injection resin and the softening temperature of the film, when the injection resin and the film are integrated, It was difficult to effectively prevent film flow and peeling.

  Moreover, in patent document 2, although the relationship between the softening temperature of an injection resin and the softening temperature of a film is considered, since the component of polycarbonate resin is not prescribed | regulated strictly, an injection resin and a film are integrated. At that time, it was difficult to effectively prevent the flow and peeling of the film.

  Therefore, the present invention has been made in order to solve such problems, and has high adhesion strength between a decorative film made of a polycarbonate-containing resin and an injection resin without losing the advantage of providing a decorative film layer. It aims at providing the resin molding and its manufacturing method.

The present invention has been studied to achieve the above-mentioned goal, and the gist of the present invention resides in the following [1] to [14].
[1] A resin molded body obtained by inserting a decorative film made of a polycarbonate-containing resin into a mold and integrated with a resin injected from a cylinder of an injection molding machine, wherein the injected resin is: The polycarbonate resin composition is a polycarbonate resin composition obtained by melt-mixing a plurality of carbonate copolymers having different copolymerization ratios. The copolymer is composed of structural units derived from two or more dihydroxy compounds, and has a structural unit derived from a dihydroxy compound having at least a site represented by the following formula (1). 1) Carbonate copolymer with the smallest polymerization ratio of structural units derived from dihydroxy compounds having the moiety represented by The content, and wherein the less than the sum of the content of the other polycarbonate copolymer, resin molding of the film decoration.

（ただし、式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈを構成する部位である場合を除く。）

(Unless moiety represented by the formula (1) is a portion constituting a _-CH 2 -O-H.)

[2] The polycarbonate resin composition according to [1], wherein the content of the polycarbonate copolymer having the lowest glass transition temperature is less than the sum of the contents of other polycarbonate copolymers. Resin molded body with film decoration.
[3] The polycarbonate resin composition is characterized in that the content of the polycarbonate copolymer having the highest reduced viscosity is less than the sum of the contents of other polycarbonate copolymers. ] The resin-molding body of the film decoration as described in.

[4] A resin molded body obtained by inserting a decorative film made of a polycarbonate-containing resin into a mold and integrated with a resin injected from a cylinder of an injection molding machine, wherein the injected resin is: The polycarbonate resin composition is a polycarbonate resin composition obtained by melt-mixing a plurality of carbonate copolymers having different copolymer ratios. The carbonate copolymer is composed of structural units derived from two or more dihydroxy compounds, and has structural units derived from a dihydroxy compound having at least a site represented by the following formula (1), and has a glass transition. The content of the polycarbonate copolymer with the lowest temperature is more than the sum of the contents of other polycarbonate copolymers And wherein the small, resin molding of the film decoration.

（ただし、式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈを構成する部位である場合を除く。）

(Unless moiety represented by the formula (1) is a portion constituting a _-CH 2 -O-H.)

[5] The polycarbonate resin composition according to [4], wherein the content of the polycarbonate copolymer having the highest reduced viscosity is less than the sum of the contents of other polycarbonate copolymers. Resin molded body with film decoration.
[6] A resin molded body obtained by inserting a decorative film made of a polycarbonate-containing resin into a mold and integrated with a resin injected from a cylinder of an injection molding machine, wherein the injected resin is: The polycarbonate resin composition is a polycarbonate resin composition obtained by melt-mixing a plurality of carbonate copolymers having different copolymer ratios. The carbonate copolymer is composed of structural units derived from two or more dihydroxy compounds, and has structural units derived from a dihydroxy compound having at least a site represented by the following formula (1). The content of the highest polycarbonate copolymer is less than the sum of the other polycarbonate copolymer contents. Characterized in that, resin molding of the film decoration.

（ただし、式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈを構成する部位である場合を除く。）

(Unless moiety represented by the formula (1) is a portion constituting a _-CH 2 -O-H.)

[7] Any one of [2] to [5], wherein a glass transition temperature of a polycarbonate copolymer having the lowest glass transition temperature among the polycarbonate copolymers of the polycarbonate resin is in a range of 60 ° C to 105 ° C. The resin-molded body of the film decoration according to item 1.
[8] A method for producing a resin molded body in which a decorative film made of a polycarbonate-containing resin is inserted into a mold, and then the resin is injected from a cylinder of an injection molding machine, and both are integrated. The resin obtained is a resin composition containing a polycarbonate resin composition, and this polycarbonate resin composition is a polycarbonate resin composition obtained by melt-mixing a plurality of carbonate copolymers having different copolymer ratios. The plurality of carbonate copolymers are composed of structural units derived from two or more dihydroxy compounds, and have structural units derived from a dihydroxy compound having at least a site represented by the following formula (1). Having the smallest polymerization ratio of structural units derived from the dihydroxy compound having the site represented by the following formula (1) Boneto co content of the polymer The method for producing a resin molded body characterized by less than the sum of the content of the other polycarbonate copolymer.

（ただし、式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈを構成する部位である場合を除く。）

(Unless moiety represented by the formula (1) is a portion constituting a _-CH 2 -O-H.)

[9] The polycarbonate resin composition according to [8], wherein the content of the polycarbonate copolymer having the lowest glass transition temperature is smaller than the sum of the contents of the other polycarbonate copolymers. A method for producing a resin molded article.
[10] The polycarbonate resin composition is characterized in that the content of the polycarbonate copolymer having the highest reduced viscosity is less than the sum of the contents of other polycarbonate copolymers. ] The manufacturing method of the resin molding of description.

[11] A method for producing a resin molded body in which a decorative film made of a polycarbonate-containing resin is inserted into a mold, and then the resin is injected from a cylinder of an injection molding machine to integrate the two. The resin obtained is a resin composition containing a polycarbonate resin composition, and this polycarbonate resin composition is a polycarbonate resin composition obtained by melt-mixing a plurality of carbonate copolymers having different copolymer ratios. The plurality of carbonate copolymers are composed of structural units derived from two or more dihydroxy compounds, and have structural units derived from a dihydroxy compound having at least a site represented by the following formula (1). Polycarbonate copolymer with the lowest glass transition temperature and other polycarbonate copolymer Method for producing a resin molded body characterized by less than the sum of the content of.

（ただし、式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈを構成する部位である場合を除く。）

(Unless moiety represented by the formula (1) is a portion constituting a _-CH 2 -O-H.)

[12] The polycarbonate resin composition according to [11], wherein the content of the polycarbonate copolymer having the highest reduced viscosity is less than the sum of the contents of other polycarbonate copolymers. Manufacturing method of resin molding.
[13] A method for producing a resin molded body in which a decorative film made of a polycarbonate-containing resin is inserted into a mold and then injected from a cylinder of an injection molding machine to integrate the both. The resin obtained is a resin composition containing a polycarbonate resin composition, and this polycarbonate resin composition is a polycarbonate resin composition obtained by melt-mixing a plurality of carbonate copolymers having different copolymer ratios. The plurality of carbonate copolymers are composed of structural units derived from two or more dihydroxy compounds, and have structural units derived from a dihydroxy compound having at least a site represented by the following formula (1). The content of the polycarbonate copolymer having the highest reduced viscosity is the content of other polycarbonate copolymers. Method for producing a resin molded body characterized by less than the sum of the amounts.

（ただし、式（１）で表される部位が−ＣＨ_２−Ｏ−Ｈを構成する部位である場合を除く。）

(Unless moiety represented by the formula (1) is a portion constituting a _-CH 2 -O-H.)

[14] Any one of [9] to [12], wherein among the polycarbonate copolymers of the polycarbonate resin, the glass transition temperature of the polycarbonate copolymer having the lowest glass transition temperature is in the range of 60 ° C to 105 ° C. The manufacturing method of the resin molding of 1 item | term.

  Since this invention uses a resin having specific conditions as an injection resin, a resin molded body having high adhesion strength between a decorative film made of a polycarbonate-containing resin and a polycarbonate resin composition injected in insert molding is obtained. Can do.

Cross section of insert mold (A) Example of decorative film inserted into insert mold, (b) bb cross-sectional view of (a)

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.

  This invention is an invention according to a decorative film and a resin molded body for film decoration obtained by integrating with a specific resin injected in insert molding and a method for producing the same.

[Decorating film]
The decorative film is a film disposed on the surface (design side surface) on which the design of the resin molded body according to the present invention is displayed, and is a flat film or surface depending on the purpose of the decoration. Films such as a film that has been subjected to a decoration treatment such as embossing, a film that has been drawn by vacuum forming or pressure forming, and a film that has been formed in accordance with the shape of the decorative surface of the target resin molding. In addition, this film may be subjected to a decoration process during insert molding described later.
Examples of the resin constituting the decorative film include an ester resin composition, an acrylic resin composition, and a polycarbonate resin composition containing polycarbonate. In addition, you may use the polycarbonate resin similar to injection resin mentioned later for this polycarbonate resin composition. Among the resins constituting these decorative films, an ester resin composition and a polycarbonate resin composition containing polycarbonate are preferable from the viewpoint of impact resistance, and further, heat resistance and self-digestibility are exhibited. Most preferred is a polycarbonate resin composition comprising a polycarbonate.
Further, the outer surface of the decorative film may be hard-coated in order to increase the surface hardness.

[Injected resin]
The resin injected in the insert molding of the present invention is a resin composition containing a polycarbonate resin. In addition to the polycarbonate resin composition, the resin composition includes a styrene resin composition, a styrene / acrylonitrile resin composition, An acrylic resin composition or the like may be included.

The styrene resin composition refers to a homopolymer or copolymer of a styrene compound such as styrene or α-methylstyrene, or a mixed resin thereof.
The styrene / acrylonitrile resin composition refers to a resin composition comprising a copolymer of styrene and acrylonitrile.
Furthermore, the said acrylic resin composition means the homopolymer and copolymer of various acrylic monomers, or those mixed resins.

  The injection resin is a resin composition containing a polycarbonate resin, which will be described later, and containing the above styrene resin composition, styrene / acrylonitrile resin composition, acrylic resin composition and the like as necessary. The content ratio of the polycarbonate resin in the injection resin is not particularly limited, but it is sufficient that the polycarbonate resin is a main component, that is, the content ratio of the polycarbonate resin is the maximum in the injection resin.

[1] Polycarbonate resin composition The polycarbonate resin composition of the present invention is a resin composition comprising a polycarbonate, and a plurality of carbonate copolymers having different copolymerization ratios, that is, composition ratios of structural units constituting the copolymer. It is obtained by melt-mixing a polymer.
The plurality of carbonate copolymers are both composed of structural units derived from two or more types of dihydroxy compounds, and at least structural units derived from dihydroxy compounds having a site represented by formula (1), That is, it has the dihydroxy compound unit which has a site | part of Formula (1).

However, unless moiety represented by the formula (1) is a portion constituting a _-CH 2 -O-H.

  The molar ratio of the dihydroxy compound unit having the site of the formula (1) to all dihydroxy compound units contained in the resin composition of the present invention is preferably 30 mol% or more, more preferably 40 mol% or more, and 50 More preferably, it is at least mol%. If the molar ratio is lower than this, the heat resistance is low and resin molding tends to be difficult. On the other hand, the molar ratio is preferably 95 mol% or less, more preferably 90 mol% or less, and further preferably 80 mol% or less. If the molar ratio is higher than this, the impact resistance tends to decrease.

  Moreover, the copolymerization ratio of the dihydroxy compound unit which has a site | part of Formula (1) is below the minimum of the said molar ratio, and the copolymerization ratio of the dihydroxy compound unit which has a site | part of Formula (1) is the said. It is also preferable that a carbonate copolymer having a molar ratio higher than the lower limit is melt-mixed so that the molar ratio in the resin composition is within the above range.

  On the other hand, the copolymerization ratio of the dihydroxy compound unit having the site of the formula (1) is not less than the upper limit of the molar ratio and the copolymerization rate of the dihydroxy compound unit having the site of the formula (1) is It is also preferable to melt and mix a carbonate copolymer having a molar ratio less than the upper limit so that the molar ratio in the resin composition is within the above range.

  When the polycarbonate resin composition of the present invention is obtained by melt-mixing a plurality of carbonate copolymers, the blending amount of the carbonate copolymer having the smallest blending amount is 10% by mass or more of the total amount of the plurality of carbonate copolymers. Preferably, the content is 20% by mass or more, and more preferably 25% by mass or more. On the other hand, the blending amount of the copolymer having the largest blending amount is preferably 90% by mass or less, more preferably 80% by mass, and 75% by mass with respect to the total amount of the plurality of carbonate copolymers. More preferably. When the blending ratio of the plurality of carbonate copolymers is out of the above range, the physical properties of the carbonate copolymer having the largest blending properties are obtained. Originally, a carbonate copolymer having a single composition tends to have incompatible heat resistance and impact resistance. Therefore, in order to achieve both the heat resistance and impact resistance of the obtained polycarbonate resin composition, a plurality of carbonate copolymers are used. It is preferable to adjust the blending ratio within the above range.

  In addition, the content of the carbonate copolymer having the smallest polymerization ratio of the structural unit derived from the dihydroxy compound having the site represented by the formula (1) is less than the sum of the contents of the other polycarbonate copolymers. Is preferred. By satisfying this condition, it is possible to exhibit the feature that the heat resistance is improved.

<Physical properties of polycarbonate resin composition>
(Melt viscosity)
From the viewpoint of impact resistance, the melt viscosity of the polycarbonate resin composition of the present invention is preferably 300 Pa · s or more, more preferably 500 Pa · s or more, and further preferably 600 Pa · s or more. On the other hand, from the viewpoint of improving fluidity and improving the appearance during molding, 2000 Pa · s or less is preferable, 1500 Pa · s or less is more preferable, and 1000 Pa · s or less is preferable.

Further, the carbonate copolymer having the lowest copolymerization ratio of the dihydroxy compound unit having the moiety of the formula (1) has the highest copolymerization ratio of the dihydroxy compound unit having the moiety of the formula (1). It is preferable that it is below the melt viscosity of a polymer. And the melt viscosity of the carbonate copolymer having the highest copolymerization ratio of the dihydroxy compound unit having the site of the formula (1) and the carbonate copolymer having the lowest copolymerization ratio of the dihydroxy compound unit having the site of the formula (1) The difference from the melt viscosity of the coalescence is preferably 50 Pa · s or more, more preferably 100 Pa · s or more, and further preferably 200 Pa · s or more. On the other hand, the difference is preferably 700 Pa · s or less, and more preferably 500 Pa · s or less. Due to the difference being within the above range, the polycarbonate resin composition obtained by melt-mixing a plurality of carbonate copolymers having different copolymerization ratios has high impact resistance and appearance such as flow mark and tiger mark. An injection molded product with few defects can be obtained.
In the present invention, the melt viscosity is a value measured at a temperature of 240 ° C. and a shear rate of 91.2 sec ⁻¹ using a capillary flow property tester according to JIS K7199: 1999 “Plastic flow property test method”. .

(Glass transition temperature (Tg))
In the resin composition of the present invention, the glass transition temperature of the carbonate copolymer having the lowest copolymerization ratio of the dihydroxy compound unit having the moiety of formula (1) and the copolymerization of the dihydroxy compound unit having the moiety of formula (1) The difference from the glass transition temperature of the carbonate copolymer having the highest ratio is preferably 5 ° C. or more, and more preferably 10 ° C. or more, from the viewpoint of the impact resistance improving effect. On the other hand, the difference is preferably 45 ° C. or less, more preferably 40 ° C. or less, and further preferably 35 ° C. or less from the viewpoint of hardly causing molding defects due to the influence of a carbonate copolymer having a low glass transition temperature. Is more preferable, and most preferably 30 ° C. or lower.

  In the present invention, the glass transition temperature (Tg) is measured using a differential scanning calorimeter (DSC) in accordance with JIS K7121: 2012 “Method for measuring plastic transition temperature”, and about 10 mg of a resin sample is subjected to a nitrogen stream of 50 mL / min. The temperature was raised from room temperature to 250 ° C. at a rate of temperature increase of 20 ° C./minute, held for 3 minutes, then cooled to 30 ° C. at a rate of 20 ° C./minute, held at 30 ° C. for 3 minutes, and again to 200 ° C. The temperature is raised at a rate of 20 ° C./min, and the DDSC peak top value of measurement data obtained by the second temperature rise is used.

  The glass transition temperature exhibited by the polycarbonate resin composition of the present invention is characterized by being different from the glass transition temperatures exhibited by a plurality of carbonate copolymers having different compositions. In general, the glass transition temperature exhibited by the polymer blend is significantly different from the glass transition temperatures exhibited by each of the raw resin, which means that the raw resin is at least in the nanometer order (molecular level) in the polymer blend. It means having a part in a dissolved state, and this state is referred to as a compatible system in the present invention. Therefore, it can be said that the polycarbonate resin composition of the present invention is a system in which a plurality of carbonate copolymers having different compositions are compatible. In addition, the glass transition temperature which the polycarbonate resin composition of this invention shows is the highest glass transition temperature and the lowest glass transition temperature among each glass transition temperature which the some carbonate copolymer from which a copolymerization ratio differs shows. More preferably in between.

  In the present invention, the compatible part of the polymer blend exhibits remarkable physical properties. For example, when a plurality of carbonate copolymers having different compositions are transparent, the obtained polycarbonate resin composition and a molded product obtained therefrom are a system in which the plurality of carbonate copolymers are compatible with each other. Excellent transparency. In addition, in a compatible system, even if there is no lump of undissolved resin, there is very little, so that it is difficult to break starting from this, the impact resistance of the polycarbonate resin composition of the present invention is This is considered to be an improvement factor.

  In general, the polymer blend with the most advanced compatibility is expected to exhibit a single glass transition temperature, but the polycarbonate resin composition of the present invention exhibits a single glass transition temperature. It is not always necessary. In general, when the polymer blend does not exhibit a single glass transition temperature, it means that the raw resin has a portion in the polymer blend that is in an incompatible state at least on the nanometer order. When in this state, the characteristic physical properties of the raw material resin in an incompatible state may remarkably appear and can be used simultaneously with the physical properties exhibited by the compatible portion. In the present invention, for example, when a composition of a plurality of carbonate copolymers exhibits a plurality of glass transition temperatures, the heat resistance is a characteristic property derived from a copolymer present in a portion that is in an incompatible state. Heat resistance that cannot be achieved by adjusting the general monomer ratio by exhibiting impact resistance, which is a characteristic physical property exhibited by a part where multiple carbonate copolymers are compatible at the same time. And impact resistance can be realized.

  In the present invention, there are several methods for measuring the glass transition temperature. One of them is to use a differential scanning calorimeter (DSC) for the polycarbonate resin composition of the present invention at a heating rate of 20 ° C./min. When the polycarbonate resin composition of the present invention is measured by the above method, when the inflection point showing the glass transition appears at a different temperature from the plurality of carbonate copolymers having different compositions, the copolymerization ratio is It can be said that this is a system in which a plurality of different carbonate copolymers are compatible.

The other is that according to the dynamic viscoelasticity measurement of JIS K7198A, the polycarbonate resin composition of the present invention is subjected to a temperature dispersion of the dynamic viscoelasticity at a strain of 0.1%, a frequency of 10 Hz, and a heating rate of 3 ° C./min. When the polycarbonate resin composition of the present invention is measured by the above method, the temperature at which the peak of the main dispersion of loss tangent (tan δ), in other words, the maximum value of loss tangent (tan δ) appears, is called the glass transition temperature. You can also.
Further, when measured in the above dynamic viscoelasticity measurement, the temperature at which the peak of the main dispersion of the loss elastic modulus (E ″), that is, the maximum value of the loss elastic modulus (E ″) appears, can also be referred to as the glass transition temperature.
In a system in which a plurality of carbonate copolymers having different copolymerization ratios are compatible with each other when they appear at different temperatures from a plurality of carbonate copolymers having different compositions depending on the glass transition temperature determined by the dynamic viscoelasticity measurement. It can be said that there is.
In the polycarbonate resin composition of the present invention, the main dispersion peak of loss tangent (tan δ) and the main dispersion peak of loss elastic modulus (E ″) do not need to be single, as in the measurement with a differential scanning calorimeter. Needless to say.

  In the present invention, the measurement of the glass transition temperature of a plurality of carbonate copolymers, and the measurement that the obtained polycarbonate resin composition exhibits a single glass transition temperature are a method using DSC, and dynamic viscoelasticity. Any method of measurement can be used, but the glass transition temperature value obtained by differential scanning calorimeter measurement and the glass transition temperature value obtained by dynamic viscoelasticity measurement are often different. When comparing and evaluating the glass transition temperatures of a plurality of carbonate copolymers having different compositions and the glass transition temperature of a polycarbonate resin composition obtained from them, either one of the measurement methods should be used.

  One or more glass transition temperatures of the polycarbonate resin composition of the present invention are preferably 60 ° C. or higher, and more preferably 75 ° C. or higher. If it is more than the lower limit which requires a glass transition temperature, it is preferable at the point of heat resistance and heat deformation. On the other hand, the glass transition temperature of one or more indicated by the polycarbonate resin composition is preferably 150 ° C. or lower, and more preferably 140 ° C. or lower. If it is below the upper limit which requires a glass transition temperature, it is preferable at the point of moldability and productivity.

  Furthermore, among the polycarbonate copolymers constituting the polycarbonate resin of the present invention, the glass transition temperature of the polycarbonate copolymer having the lowest glass transition temperature is preferably 60 ° C. or higher, and more preferably 75 ° C. or higher. If it is more than the lower limit which requires a glass transition temperature, it is preferable at the point of heat resistance and heat deformation. Further, the upper limit of the glass transition temperature is preferably 105 ° C, more preferably 100 ° C or less. When it is higher than 105 ° C., there is a case in which the problem that the adhesion with the film is lowered may occur.

  In addition, among the plurality of polycarbonate copolymers constituting the polycarbonate resin composition of the present invention, the content of the polycarbonate copolymer having the lowest glass transition temperature is less than the sum of the contents of the other polycarbonate copolymers. It is preferable. By satisfying this condition, it is possible to exhibit the following characteristics.

(Impact resistance)
The value of the notched Charpy impact test of a polycarbonate resin composition was measured according to ISO 179 (2000 years) of the present invention is preferably from 3 kJ / ^{m 2} or more, 5 kJ / ^{m 2} or more is more preferable. When the value of the notched Charpy impact test is within this range, it can be widely used for applications that require impact resistance. Further, the surface impact brittle fracture rate of the polycarbonate resin composition of the present invention measured by the method described in Examples is preferably 20% or less, and more preferably 5% or less. It can be preferably used in applications where impact resistance is required at temperatures within the range where the surface impact brittle fracture rate is required, and the minimum temperature within the range where the surface impact brittle fracture rate is applied is used as an indicator of cold resistance. The lower the temperature, the more preferably it can be used in a lower temperature environment.

(Heat-resistant)
The value of the load deflection temperature measured by the method described in the examples of the polycarbonate resin composition of the present invention is preferably 80 ° C. or higher, more preferably 90 ° C. or higher. The higher the value of the load deflection temperature, the higher the heat resistance, and it can be preferably used in a high temperature environment such as being exposed to direct sunlight or being used near a heating element.

(Reduced viscosity)
Of the plurality of polycarbonate copolymers constituting the polycarbonate resin composition of the present invention, the content of the polycarbonate copolymer having the highest reduced viscosity is preferably less than the sum of the contents of the other polycarbonate copolymers. . By satisfying this condition, it is possible to exhibit the following characteristics.

The reduced viscosity is measured at a temperature of 20.0 ° C. ± 0.1 ° C. using an Ubbelohde viscometer manufactured by Moriyu Rika Kogyo Co., Ltd., and the following formula is obtained from the passage time t _{0 of the} solvent and the passage time t of the polycarbonate solution. The relative viscosity η _rel is obtained from <1>, and the specific viscosity η _sp is obtained from the obtained relative viscosity from the formula <2>. Then, the reduced viscosity η _sp / c can be obtained by dividing this specific viscosity by the concentration c (g / dL). It shows that molecular weight is so large that this value is high.
η _rel = t / t ₀ <1>
[eta] _sp = ([eta]-[eta] ₀ ) / [eta] ₀ = [eta] _rel- 1 <2>.

[2] Carbonate copolymer The polycarbonate resin composition of the present invention is obtained by melting and mixing a plurality of carbonate copolymers having different copolymerization ratios as described above.
Each of the plurality of carbonate copolymers is composed of a structural unit (dihydroxy compound unit) derived from two or more kinds of dihydroxy compounds and has a structure derived from a dihydroxy compound having at least a site represented by formula (1) It has a unit (dihydroxy compound unit having a site of formula (1)).

However, unless moiety represented by the formula (1) is a portion constituting a _-CH 2 -O-H.

Hereinafter, the details of the carbonate copolymer used in the present invention will be described.
<Dihydroxy compound>
(Dihydroxy compound having the moiety of formula (1))
The dihydroxy compound having the moiety of formula (1) is not particularly limited as long as it has a moiety represented by formula (1) in a part of the molecular structure, that is, an ether structure. Among these, those having a cyclic ether structure as part of the molecular structure are preferred. Further, it preferably has no aromatic ring structure. Examples of the compound include anhydrous sugar alcohols typified by dihydroxy compounds represented by formula (2); dihydroxy compounds represented by formula (3); or dioxane glycol.

In formula (3), R ^{1 to} R ⁴ each independently represents an alkyl group having 1 to 3 carbon atoms.

  Examples of the dihydroxy compound represented by the formula (2) include isosorbide, isomannide, and isoide which are in a stereoisomeric relationship. The dihydroxy compound represented by the formula (3) is 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane. (Common name: spiroglycol), 3,9-bis (1,1-diethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, 3,9-bis ( 1,1-dipropyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro (5.5) undecane and the like. Of these dihydroxy compounds, the compound of formula (2), which is abundant as a resource and easily available, is particularly preferred, and isosorbide obtained by dehydration condensation of sorbitol produced from various starches is obtained and produced. Most preferable from the viewpoints of ease of processing, optical properties, and moldability.

  Isosorbide is easily oxidized gradually by oxygen. For this reason, when storing or handling during manufacture, it is important to prevent moisture from being mixed, to use an oxygen scavenger, or to be in a nitrogen atmosphere in order to prevent decomposition by oxygen. When isosorbide is oxidized, decomposition products such as formic acid are generated. For example, when a polycarbonate resin is produced using isosorbide containing these decomposition products, the resulting polycarbonate resin may be colored or the physical properties may be significantly deteriorated. In addition, the polymerization reaction may be affected, and a high molecular weight polymer may not be obtained. In addition, when a stabilizer for preventing the generation of formic acid is added, depending on the type of the stabilizer, coloring may occur in the obtained polycarbonate resin, or the physical properties may be significantly deteriorated. A reducing agent or an antacid is used as the stabilizer. Among these, examples of the reducing agent include sodium borohydride and lithium borohydride, and examples of the antacid include alkali metal salts such as sodium hydroxide. Since the addition of such an alkali metal salt may become a polymerization catalyst, if it is added excessively, the polymerization reaction may not be controlled.

  In order to obtain isosorbide containing no oxidative decomposition product, isosorbide may be distilled as necessary. Also, isosorbide may be distilled if necessary, when a stabilizer is added to prevent the oxidation or decomposition of isosorbide. In this case, the distillation of isosorbide may be simple distillation or continuous distillation, and is not particularly limited. Distillation is carried out under reduced pressure in an inert gas atmosphere such as argon or nitrogen. By performing such distillation of isosorbide, it is possible to use high-purity isosorbide having a formic acid content of 20 ppm by mass or less, particularly 5 ppm by mass or less.

In addition, the measuring method of formic acid content in isosorbide is performed according to the following procedures using an ion chromatograph.
About 0.5 g of isosorbide is precisely weighed and collected in a 50 ml volumetric flask and made up to volume with pure water. A sodium formate aqueous solution is used as a standard sample, and the peak having the same retention time as that of the standard sample is defined as formic acid, and quantified by an absolute calibration curve method from the peak area.
As the ion chromatograph, DX-500 type manufactured by Dionex was used, and an electric conductivity detector was used as a detector. As a measurement column, AG-15 is used for a guard column manufactured by Dionex, and AS-15 is used for a separation column. A measurement sample is injected into a 100 μl sample loop, and 10 mM NaOH is used as an eluent, and the measurement is performed at a flow rate of 1.2 ml / min and a thermostat temperature of 35 ° C. A membrane suppressor is used as the suppressor, and a 12.5 mM-H ₂ SO ₄ aqueous solution is used as the regenerating solution.

  The carbonate copolymer used in the present invention preferably contains an aliphatic dihydroxy compound in addition to the dihydroxy compound unit having the moiety of formula (1), and is a straight chain aliphatic dihydroxy compound unit or an alicyclic dihydroxy compound. Preferably, it contains units and most preferably contains alicyclic dihydroxy compound units. By further including an aliphatic dihydroxy compound unit, the carbonate copolymer has impact resistance superior to that of the conventional carbonate copolymer, and water absorption is reduced, which may be a useful material.

(Alicyclic dihydroxy compound)
Although it does not specifically limit as an alicyclic dihydroxy compound, Usually, the compound containing a 5-membered ring structure or a 6-membered ring structure is mentioned. When the alicyclic dihydroxy compound has a 5-membered ring structure or a 6-membered ring structure, the resulting polycarbonate resin may have high heat resistance. The six-membered ring structure may be fixed in a chair shape or a boat shape by a covalent bond. Carbon number contained in an alicyclic dihydroxy compound is 70 or less normally, Preferably it is 50 or less, More preferably, it is 30 or less. When the number of carbon atoms is excessively large, the heat resistance becomes high, but synthesis tends to be difficult, purification becomes difficult, and cost tends to be high. The smaller the carbon number, the easier it is to purify and the easier it is to obtain.

  Specific examples of the alicyclic dihydroxy compound containing a 5-membered ring structure or a 6-membered ring structure include alicyclic dihydroxy compounds represented by the following formula (I) or (II).

^{_{HOCH 2 -R 5 -CH 2 OH ·····}} (I)
HO—R ⁶ —OH (II)
(However, in formula (I) and formula (II), R ⁵ and R ⁶ each independently represents a substituted or unsubstituted divalent group containing a cycloalkyl structure having 4 to 20 carbon atoms.)

  Examples of the alicyclic dihydroxy compounds represented by the formula (I) include cyclohexanedimethanols, tricyclodecane dimethanols, pentacyclopentadecane dimethanols, decalin dimethanols, tricyclotetradecane dimethanols, norbornane Examples thereof include methanol and adamantane dimethanol.

The cyclohexanedimethanols include various isomers in which R ⁵ is represented by the following formula (Ia) in the formula (I).

In formula (Ia), R ⁷ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.

  Examples of such isomers include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and the like.

The tricyclodecane dimethanols and pentacyclopentadecane dimethanols include various isomers in which R ⁵ is represented by the following formula (Ib) in the formula (I).

In the formula (Ib), m represents 0 or 1.

The decalin dimethanols and tricyclotetradecane dimethanols include various isomers in which R ⁵ is represented by the following formula (Ic) in the formula (I).

In the formula (Ic), n represents 0 or 1.

  Examples of such isomers include 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol and the like.

The norbornanedimethanols include various isomers in which R ⁵ is represented by the following formula (Id) in the formula (I).

  Examples of such isomers include 2,3-norbornane dimethanol, 2,5-norbornane dimethanol and the like.

The adamantanedimethanols include various isomers in which R ⁵ is represented by the following formula (Ie) in the formula (I).

  Examples of such isomers include 1,3-adamantane dimethanol.

  Examples of the alicyclic dihydroxy compound represented by the formula (II) include cyclohexanediols, tricyclodecanediols, pentacyclopentadecanediols, decalindiols, tricyclotetradecanediols, norbornanediols, adamantanediols. And the like.

The cyclohexanediols include various isomers in which R ⁶ is represented by the following formula (IIa) in the formula (II).

In formula (IIa), R ⁸ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms.

  Examples of such isomers include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and the like.

The tricyclodecanediols and pentacyclopentadecanediols include various isomers in which R ⁶ is represented by the following formula (IIb) in the formula (II).

In the formula (IIb), m represents 0 or 1.

The decalindiols and tricyclotetradecanediols include various isomers in which R ⁶ is represented by the following formula (IIc) in the formula (II).

In formula (IIc), n represents 0 or 1.

  Examples of such isomers include 2,6-decalindiol, 1,5-decalindiol, 2,3-decalindiol, and the like.

The norbornanediols include various isomers in which R ⁶ is represented by the following formula (IId) in the formula (II).

  Examples of such isomers include 2,3-norbornanediol, 2,5-norbornanediol, and the like.

The adamantanediols include various isomers in which R ⁶ is represented by the following formula (IIe) in the formula (II).

  Examples of such isomers include 1,3-adamantanediol.

  Among the specific examples of the alicyclic dihydroxy compounds described above, cyclohexane dimethanols, tricyclodecane dimethanols, adamantane diols, and pentacyclopentadecane dimethanols are preferable, and are easily available and easy to handle. From the viewpoint, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, and tricyclodecane dimethanol are particularly preferable.

  In addition, the said exemplary compound is an example of the alicyclic dihydroxy compound which can be used for this invention, Comprising: It is not limited to these at all. These alicyclic dihydroxy compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  In the carbonate copolymer used in the present invention, the molar ratio of the dihydroxy compound unit having the moiety of formula (1) to the alicyclic dihydroxy compound unit is preferably 80:20 to 30:70, and 70:30. More preferably, it is ˜40: 60. When the proportion of the dihydroxy compound unit having the moiety of formula (1) is larger than the above range, coloring tends to occur, and conversely, when the proportion of the dihydroxy compound unit having the moiety of formula (1) is low, it is difficult to obtain a high molecular weight. Thus, the impact resistance is difficult to improve, and the glass transition temperature tends to decrease.

  In the carbonate copolymer used in the present invention, in addition to the dihydroxy compound unit having the moiety of the formula (1) and the alicyclic dihydroxy compound unit, further structural units derived from other dihydroxy compounds (hereinafter referred to as “other dihydroxy compounds”). It may be referred to as “compound unit”). Examples of other dihydroxy compounds include aliphatic dihydroxy compounds and aromatic dihydroxy compounds.

  Examples of the aliphatic dihydroxy compound include 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2- Examples include ethyl 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol, and the like.

  Examples of aromatic dihydroxy compounds include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, and 2,2-bis. (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) pentane, 2,2 -Bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxyphenyl) Hexane, 2,2-bis (4-hydroxyphenyl) hexane, 3,3-bis (4-hydroxyphenyl) hexane, 2, Substituents on aromatic rings such as -bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane Bisphenol compounds not having; bis (3-phenyl-4-hydroxyphenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) ethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) Bisphenol compounds having an aryl group as a substituent on an aromatic ring such as propane and 2,2-bis (3-phenyl-4-hydroxyphenyl) propane; bis (4-hydroxy-3-methylphenyl) methane, 1, 1-bis (4-hydroxy-3-methylphenyl) ethane, 1,1-bis (4-hydroxy-3-methyl) Enyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, bis (4-hydroxy-3-ethylphenyl) methane 1,1-bis (4-hydroxy-3-ethylphenyl) ethane, 1,1-bis (4-hydroxy-3-ethylphenyl) propane, 2,2-bis (4-hydroxy-3-ethylphenyl) Propane, 1,1-bis (4-hydroxy-3-ethylphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (4-hydroxy-3- (sec -Butyl) phenyl) propane, bis (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3, 5-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, bis (4-hydroxy) -3,6-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,6-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,6-dimethylphenyl) propane, bis ( 4-hydroxy-2,3,5-trimethylphenyl) methane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) ethane, 2,2-bis (4-hydroxy-2,3, 5-trimethylphenyl) propane, bis (4-hydroxy-2,3,5-trimethylphenyl) phenylmethane, 1,1-bis (4-hydroxy-2,3, A bisphenol compound having an alkyl group as a substituent on an aromatic ring such as trimethylphenyl) phenylethane or 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) cyclohexane; ) Phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylpropane, bis (4-hydroxyphenyl) diphenylmethane, bis (4 -Hydroxyphenyl) A bisphenol compound having a divalent group connecting aromatic rings such as dibenzylmethane having an aryl group as a substituent; 4,4'-dihydroxydiphenyl ether, 3,3 ', 5,5'-tetramethyl- Aromatic rings such as 4,4'-dihydroxydiphenyl ether Bisphenol compounds linked together by coupling; aromatic rings such as 4,4′-dihydroxydiphenylsulfone and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylsulfone linked by sulfone bonds Bisphenol compounds in which aromatic rings such as 4,4′-dihydroxydiphenyl sulfide and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide are connected by a sulfide bond; Preferably, it may be abbreviated as 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “bisphenol A”). ).

  These other hydroxy compounds may be used alone or in combination of two or more.

  In this invention, although the molar ratio of the dihydroxy compound unit which has a site | part of Formula (1), an alicyclic dihydroxy compound unit, and another dihydroxy compound unit can be selected in arbitrary ratios, it is possible to adjust the said molar ratio. The impact resistance may be improved, and the desired glass transition temperature of the polycarbonate resin can be obtained.

  In at least one of the carbonate copolymers constituting the resin composition of the present invention, among the structural units derived from two or more kinds of dihydroxy compounds constituting the carbonate copolymer, derived from the dihydroxy compound having the smallest molar use amount. The copolymerization ratio of the structural units to be formed is preferably 20 mol% or more, and more preferably 30 mol% or more. On the other hand, the copolymerization ratio of the structural units derived from the dihydroxy compound having the largest molar use amount is preferably 80 mol% or less, and more preferably 70 mol% or less. When the monomer ratio is out of the above range, the compatibility between a plurality of copolymers used for melt-kneading is lowered, transparency and impact resistance may be lowered, and compatibility is deteriorated. There is a possibility that physical properties derived from other dihydroxy compound units constituting the polymer will rise and the resulting polycarbonate resin composition will have undesirable physical properties.

[3] Production Method of Carbonate Copolymer The carbonate copolymer used in the present invention can be produced by a commonly used polymerization method, and the polymerization method includes an interfacial polymerization method using phosgene, a carbonic acid diester and an ester. Although any method of the melt polymerization method in which an exchange reaction is performed may be used, a melt polymerization method in which a dihydroxy compound is reacted with a carbonic diester having lower toxicity to the environment in the presence of a polymerization catalyst is preferable.
The carbonate copolymer used in the present invention is more preferably obtained by a melt polymerization method in which the above-described dihydroxy compound and carbonic acid diester are transesterified.

<Carbonated diester>
As a carbonic acid diester used, what is represented by Formula (4) is mentioned normally. These carbonic acid diesters may be used alone or in combination of two or more.

In formula (4), A ¹ and A ² are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic group.

  Examples of the carbonic acid diester represented by the formula (4) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, preferably diphenyl carbonate. Substituted diphenyl carbonate, particularly preferably diphenyl carbonate. Carbonic acid diesters may contain impurities such as chloride ions, which may hinder the polymerization reaction or worsen the hue of the resulting carbonate copolymer. It is preferable to use a product purified by the above.

  The carbonic acid diester is preferably used in a molar ratio of 0.96 to 1.10, particularly preferably in a molar ratio of 0.98 to 1.04, based on all dihydroxy compounds used in the melt polymerization. When this molar ratio is smaller than 0.96, the terminal hydroxyl group of the obtained carbonate copolymer is increased, the thermal stability of the polymer is deteriorated, and when the molar ratio is larger than 1.10, the same condition is obtained. Below, the rate of the transesterification reaction decreases, making it difficult to produce a carbonate copolymer having a desired molecular weight, and the amount of residual carbonic diester in the produced polycarbonate resin is increased. This is not preferable at the time of molding or causing odor of the molded product.

<Transesterification reaction catalyst>
The carbonate copolymer used in the present invention produces a polycarbonate resin by transesterifying the dihydroxy compound containing the dihydroxy compound of the present invention and the carbonic acid diester represented by the formula (4) as described above. More specifically, it can be obtained by transesterification to remove by-product monohydroxy compounds and the like out of the system. In this case, melt polymerization is usually carried out by transesterification in the presence of a transesterification catalyst.

  As the transesterification catalyst (hereinafter sometimes referred to as “catalyst”) that can be used in the production of the carbonate copolymer, the obtained carbonate copolymer has high impact resistance, low brittle fracture rate, surface As long as the hardness is high and the balance between glass transition temperature and impact resistance is good, it is not limited. However, Group 1 metal compounds, Group 2 metal compounds, basicity in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005) Examples thereof include basic compounds such as boron compounds, basic phosphorus compounds, basic ammonium compounds, phosphines, basic phosphonium compounds, and amine compounds. Preferably, Group 1 metal compounds and / or Group 2 metal compounds are used.

  In addition to the Group 1 metal compound and / or the Group 2 metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, an amine compound, or the like can be used in combination. It is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.

  In addition, the group 1 metal compound and / or the group 2 metal compound is usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt. From the viewpoint of easiness, a hydroxide, carbonate, and acetate are preferable, and acetate is preferable from the viewpoint of hue and polymerization activity.

  Examples of the Group 1 metal compound include 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 tetraphenylborate, potassium tetraphenylborate, lithium tetraphenylborate, cesium tetraphenylborate, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, lithium Disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, disesium phenyl phosphate, sodium, potassium Lithium, cesium alcoholate, phenolate, bisphenol A disodium salt, dipotassium salt, dilithium salt, cesium salt and the like. Of these, cesium compounds and lithium compounds are preferred.

  Examples of the Group 2 metal compound include 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, Examples include strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate. Of these, magnesium compounds, calcium compounds and barium compounds are preferred, and magnesium compounds and / or calcium compounds are more preferred.

  Examples of basic boron compounds include tetramethyl boric acid, tetraethyl boric acid, tetrapropyl boric acid, tetrabutyl boric acid, trimethylethyl boric acid, trimethylbenzyl boric acid, trimethylphenyl boric acid, triethylmethyl boric acid, triethylbenzyl. Sodium salt, potassium salt, lithium salt such as boric acid, triethylphenyl boric acid, tributylbenzyl boric acid, tributylphenyl boric acid, tetraphenyl boric acid, benzyltriphenyl boric acid, methyltriphenyl boric acid, butyltriphenyl boric acid , Calcium salt, barium salt, magnesium salt, or strontium salt.

  Examples of the phosphine and the basic phosphonium compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and a quaternary phosphonium salt.

  Examples of the amine compound include 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 the like.

Examples of the basic ammonium compound include 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 Sid, butyl triphenyl ammonium hydroxide, and the like.
The said catalyst may be used individually by 1 type, and may use 2 or more types together.

  In the case of a group 1 metal compound and / or a group 2 metal compound, the amount of the catalyst used is usually within a range of 0.1 to 100 μmol as a metal conversion amount with respect to 1 mol of all dihydroxy compounds used in the polymerization. Preferably, it exists in the range of 0.5-50 micromol, More preferably, it exists in the range of 1-25 micromol. If the amount of the catalyst used is too small, the polymerization activity necessary for producing a polycarbonate resin having a desired molecular weight may not be obtained, and sufficient breaking energy may not be obtained. On the other hand, if the amount of the catalyst used is too large, not only the hue of the resulting polycarbonate resin will deteriorate, but also by-products will be generated, resulting in a decrease in fluidity and the occurrence of gels, which causes brittle fracture. In some cases, it may be difficult to produce a polycarbonate resin having a target quality.

<Melt polymerization>
As described above, the carbonate copolymer is obtained by subjecting a dihydroxy compound containing the dihydroxy compound of the present invention and a carbonic acid diester to melt polymerization by a transesterification reaction. It is preferable to mix uniformly before.

  The temperature at the time of mixing the raw materials is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Among these, 100 ° C. or higher and 120 ° C. or lower is preferable. If the mixing temperature is too low, the dissolution rate may be slow or the solubility may be insufficient, often causing problems such as solidification, and if the mixing temperature is too high, the dihydroxy compound may be thermally deteriorated. As a result, the hue of the polycarbonate resin obtained is deteriorated, which may adversely affect the light resistance.

  When the melting point of the carbonic acid diester is lower than any of the melting points of the dihydroxy compound, dissolving the solid or liquid dihydroxy compound in the melt of the carbonic acid diester can suppress thermal deterioration of the dihydroxy compound and can dissolve it uniformly. Therefore, it is preferable.

The carbonate copolymer is preferably produced by melt polymerization in a plurality of stages using a plurality of reactors using a catalyst, but the reason for carrying out the melt polymerization in a plurality of reactors is the initial stage of the melt polymerization reaction. Since there are many dihydroxy compounds and carbonic acid diesters contained in the reaction solution, it is important to suppress the volatilization of the dihydroxy compounds and carbonic acid diesters while maintaining the necessary polymerization rate. This is because it is important to sufficiently distill off the by-produced monohydroxy compound in order to shift the equilibrium to the polymerization side. Thus, in order to set different polymerization reaction conditions, it is preferable from the viewpoint of production efficiency to use a plurality of reactors arranged in series and change the reaction conditions in each reactor.
As described above, the number of reactors used may be at least two or more, but from the viewpoint of production efficiency, the number is three or more, preferably 3 to 5, and particularly preferably four. If there are two or more reactors, a plurality of reaction stages with different conditions may be provided in the reactor, or the temperature and pressure may be continuously changed.

  The catalyst can be added to the raw material preparation tank, the raw material storage tank, or directly to the reactor. From the viewpoint of supply stability and control of melt polymerization, the raw material before being supplied to the reactor is used. A catalyst supply line is installed in the middle of the line and is preferably supplied as an aqueous solution. If the temperature of the transesterification reaction is too low, the productivity is lowered and the thermal history of the product is increased. If the temperature is too high, not only the dihydroxy compound and carbonic acid diester are volatilized, but also the decomposition and coloring of the polycarbonate resin is promoted. there is a possibility.

  The method of transesterifying a dihydroxy compound containing at least a dihydroxy compound having a moiety of formula (1) and a carbonic acid diester in the presence of a catalyst is usually carried out in a multistage process of two or more stages. Specifically, the transesterification temperature in the first stage (hereinafter sometimes referred to as “internal temperature”) is usually 140 to 220 ° C., preferably 150 to 200 ° C., and the residence time is usually 0.1. For 10 to 10 hours, preferably 0.5 to 3 hours. In the second and subsequent stages, the transesterification reaction temperature is increased, usually at a temperature of 210 to 270 ° C., while simultaneously removing the phenol generated outside the reaction system, the pressure in the reaction system is changed from the pressure in the first stage. The polycondensation reaction is finally carried out under a pressure of the reaction system of 200 Pa or less while gradually decreasing. When the transesterification reaction temperature is excessively high, the hue is deteriorated when formed into a molded product, which may easily cause brittle fracture. When the transesterification reaction temperature is excessively low, the target molecular weight is not increased, the molecular weight distribution is widened, the impact resistance is inferior, and the brittle fracture rate may be increased. Moreover, when the residence time of the transesterification reaction is excessively long, brittle fracture tends to occur. If the residence time is too short, the target molecular weight may not increase, and the impact resistance may be poor.

  In particular, in order to obtain a good carbonate copolymer which suppresses coloring, thermal deterioration or burns of the carbonate copolymer, has high surface impact resistance, and is difficult to brittle fracture, the maximum internal temperature in all reaction stages is 255 ° C. It is preferable that it is less than 225-250 degreeC especially. In addition, in order to suppress the lowering of the polymerization rate in the second half of the polymerization reaction and minimize the thermal deterioration of the carbonate copolymer due to thermal history, a horizontal reactor with excellent plug flow and interface renewability at the final stage of the reaction. Is preferably used.

  In addition, in order to obtain a carbonate copolymer having a high surface impact resistance and to obtain a carbonate copolymer having a high molecular weight, the polymerization temperature may be increased as much as possible to increase the polymerization time. Foreign matter and burns are generated and tend to cause brittle fracture. Therefore, in order to satisfy both the high impact resistance and the difficulty of brittle fracture, the polymerization temperature is kept low, the use of a highly active catalyst for shortening the polymerization time, the appropriate reaction system It is preferable to set the pressure. Furthermore, it is preferable to remove foreign matters or burns generated in the reaction system by a filter or the like in the middle of the reaction or at the end of the reaction in order to make brittle fracture difficult.

  When the carbonate copolymer used in the present invention is produced by a melt polymerization method, one or more of a phosphoric acid compound and a phosphorous acid compound can be added during polymerization for the purpose of preventing coloring.

  As the phosphoric acid compound, one or more of trialkyl phosphates such as trimethyl phosphite and triethyl phosphite are preferably used. These are preferably added in an amount of 0.0001 mol% to 0.005 mol%, more preferably 0.0003 mol% to 0.003 mol%, based on all hydroxy compound components. When the addition amount of the phosphorus compound is less than the lower limit, the effect of preventing coloring is small, and when it is more than the upper limit, the transparency is lowered, and conversely, the coloring is promoted or the heat resistance is lowered.

  Moreover, as a phosphorous acid compound, the heat stabilizer shown below can be selected arbitrarily and used. In particular, trimethyl phosphite, triethyl phosphite, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) One or more of pentaerythritol diphosphites can be suitably used. These phosphorous acid compounds are preferably added in an amount of 0.0001 mol% to 0.005 mol%, more preferably 0.0003 mol% to 0.003 mol%, based on the total hydroxy compound components. It is preferable to do. If the addition amount of the phosphorous acid compound is less than the lower limit, the effect of preventing coloring is small, and if it is more than the upper limit, the transparency may decrease, or conversely, the coloring may be promoted or the heat resistance may be decreased. There is also.

  The phosphoric acid compound and the phosphorous acid compound can be added in combination, but the addition amount in that case is the total amount of the phosphoric acid compound and the phosphorous acid compound, and the total hydroxy compound component described above, The content is preferably 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less. If this addition amount is less than the above lower limit, the effect of preventing coloring is small, and if it is more than the upper limit, transparency may be reduced, and conversely, coloring may be promoted or heat resistance may be reduced.

The carbonate copolymer is usually cooled and solidified after melt polymerization as described above, and pelletized with a rotary cutter or the like.
The method of pelletization is not limited, but the carbonate copolymer is drawn out from the final polymerization reactor in a molten state, cooled and solidified in the form of strands, pelletized, and uniaxial in the molten state from the final polymerization reactor. Alternatively, the resin is supplied to a twin-screw extruder, melt-extruded, and then cooled and solidified to be pelletized, or extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand, and once pelletized. After that, a method in which the resin is again supplied to a single-screw or twin-screw extruder, melt-extruded, cooled and solidified, and pelletized, or the like can be given.
At that time, in the extruder, the remaining carbonic acid diester or monohydroxy compound is devolatilized under reduced pressure, and generally known heat stabilizers, neutralizers, UV absorbers, mold release agents, colorants, electrification An inhibitor, a lubricant, a lubricant, a plasticizer, a compatibilizer, a flame retardant, and the like can be added and kneaded.

  The melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the carbonate copolymer, but is usually 150 to 300 ° C, preferably 200 to 270 ° C, and more preferably 230 to 260 ° C. When the melt-kneading temperature is lower than 150 ° C., the melt viscosity of the polycarbonate resin is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the polycarbonate is severely thermally deteriorated, and foreign matter and burns are generated. It is preferable to install a filter for removing foreign matters and burns in the extruder or at the exit of the extruder.

The opening of the filter is usually 400 μm or less, preferably 200 μm or less, particularly preferably 100 μm or less. If the opening of the filter is excessively large, leakage may occur in the removal of foreign matters and burns, and when a carbonate copolymer or a composition thereof is molded, brittle fracture may occur.
Further, a plurality of filters may be used in series, or a filtration device in which a plurality of leaf disk polymer filters are stacked may be used.

  When cooling the carbonate copolymer or its composition into chips, it is preferable to use a cooling method such as air cooling or water cooling. The air used for air cooling should be air from which foreign substances in the air have been removed in advance with a HEPA filter (a filter specified in JIS Z8112), etc., to prevent reattachment of foreign substances in the air. desirable. When using water cooling, it is desirable to use water from which metal in water has been removed with an ion exchange resin or the like, and foreign matter in water has been removed with a filter. There are various openings of the filter to be used, but those having a filter of 10 to 0.45 μm are preferable.

<Physical properties of carbonate copolymer>
The copolymer composition of the carbonate copolymer used in the present invention can be determined by cooling a melt-mixed polycarbonate resin into a chip and dissolving it in a predetermined deuterated chloroform solvent and measuring it by ¹ H-NMR.

From the viewpoint of impact resistance, the melt viscosity of the carbonate copolymer used in the present invention is preferably 300 Pa · s or more, more preferably 500 Pa · s or more, and further preferably 600 Pa · s or more. On the other hand, from the viewpoint of improving fluidity and improving the appearance during molding, 2000 Pa · s or less is preferable, 1500 Pa · s or less is more preferable, and 1000 Pa · s or less is preferable.
The method for controlling the melt viscosity of the carbonate copolymer can be achieved, for example, by controlling the intrinsic viscosity of the carbonate copolymer. As an example, there is a method of stopping the melt polycondensation by returning the pressure of the reactor from the reduced pressure state to the atmospheric pressure when a predetermined stirring power is reached during the melt polycondensation of the carbonate copolymer. At this time, if the stirring power at stop is set high, the melt viscosity of the carbonate copolymer can be increased, and if the stirring power at stop is set low, the melt viscosity of the carbonate copolymer can be decreased. .

  Although the glass transition temperature of the carbonate copolymer used for this invention is dependent on the composition, 60 degreeC or more is preferable and 75 degreeC or more is more preferable. When the glass transition temperature is higher than the lower limit, the heat resistance of the polycarbonate resin composition of the present invention tends to be good, and sufficient moldability tends to be obtained. On the other hand, the glass transition temperature of the carbonate copolymer used in the present invention is preferably 155 ° C. or lower, and more preferably 145 ° C. or lower. If the glass transition temperature is lower than the upper limit, the melt viscosity becomes high at the time of polymerization and molding, so that the molecular weight cannot be sufficiently increased at the time of polymerization, or the melt mixing is not sufficiently performed at the time of molding. There is a tendency for the characteristics to deteriorate.

  The carbonate copolymer used in the present invention is molded to a thickness of 3 mm, and the total light transmittance measured based on JIS K7361-1 in the molded product is preferably 80% or more, more preferably 90% or more. preferable. Further, the haze measured based on JIS K7105 is preferably 10% or less, and more preferably 3% or less. If the total light transmittance and haze of the carbonate copolymer are within such ranges, it is preferable because the transparency of the polycarbonate resin composition of the present invention is improved.

[4] Manufacturing method of polycarbonate resin composition <Melt mixing of carbonate copolymer>
The polycarbonate resin composition of the present invention can be produced by melt-mixing a plurality of carbonate copolymers obtained by a melt polymerization method and having different copolymerization ratios.
Various known methods can be applied as the melt mixing method, but a method of supplying a plurality of carbonate copolymers having different compositions to an extruder and melt-kneading can be preferably used.

  In the present invention, when a plurality of carbonate copolymers are melt-mixed, one or more heat stabilizers can be blended in order to prevent coloring due to deterioration of the carbonate copolymers.

  Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tris ( Nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, Diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2 Methylene bis (4,6-di-t-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, distearyl penta Erythritol diphosphate, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, 4,4′-biphenylenediphosphinic acid tetrakis (2,4-di- t-butylphenyl), dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like. Among them, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and dimethyl benzenephosphonate are preferably used.

  In addition to the addition amount added at the time of melt polymerization, the said heat stabilizer can be further mix | blended. That is, after blending an appropriate amount of a phosphorous acid compound or a phosphoric acid compound to obtain a polycarbonate resin, adding a phosphorous acid compound by a blending method described later, a decrease in transparency during polymerization, coloring, and By avoiding a decrease in heat resistance, more heat stabilizers can be blended, and deterioration of hue can be prevented.

  The content of these heat stabilizers is preferably 0.0001 to 1 part by mass, more preferably 0.0005 to 0.5 part by mass, and 0.001 to 0.2 part by mass with respect to 100 parts by mass of the polycarbonate resin. Part is more preferred.

  Moreover, 1 type, or 2 or more types of the antioxidant normally known for the purpose of antioxidant may be mix | blended with the polycarbonate resin composition of this invention.

  Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol bis [3 -(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4,6-tris (3,5-di- -Butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy -Benzylphosphonate-diethyl ester, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-biphenylenediphosphinic acid tetrakis (2,4-di-t-butylphenyl), 3 , 9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro ( 5,5) Undecane and the like can be mentioned.

  The content of these antioxidants is preferably 0.0001 to 0.5 parts by mass with respect to 100 parts by mass of the polycarbonate.

  Further, the polycarbonate resin composition of the present invention does not impair the object of the present invention in order to further improve the releasability from the cooling roll at the time of sheet molding or from the mold at the time of injection molding. You may mix | blend the 1 type (s) or 2 or more types of a mold release agent in the range.

  Such release agents include higher fatty acid esters of monohydric or polyhydric alcohols, higher fatty acids, paraffin wax, beeswax, olefin waxes, olefin waxes containing carboxy groups and / or carboxylic anhydride groups, silicone oils, Examples include organopolysiloxane.

  As the higher fatty acid ester, a partial ester or a total ester of a monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms is preferable. Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbite, stearyl stearate, behenic acid monoglyceride, behenyl behenate, Pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate Sorbitan monostearate, 2-ethylhexyl stearate and the like. Of these, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and behenyl behenate are preferably used.

  As the higher fatty acid, a saturated fatty acid having 10 to 30 carbon atoms is preferable. Such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.

  The content of the release agent is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

  Further, the polycarbonate resin composition of the present invention is significantly less discolored by ultraviolet rays than the conventional polycarbonate resin, but for the purpose of further improvement, it does not impair the purpose of the present invention. You may mix | blend 1 type (s) or 2 or more types.

  Examples of such UV absorbers and light stabilizers include 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole and 2- (3-t-butyl-5-methyl-2-hydroxyphenyl)-. 5-chlorobenzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2 , 2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis3-benzoxazin-4-one) and the like.

  The content of the ultraviolet absorber and the light stabilizer is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of polycarbonate and BR>.

The resin composition used in the present invention may contain a colorant. Examples of the colorant include organic dyes such as inorganic pigments, organic pigments, and organic dyes.
Examples of inorganic pigments include barium yellow (CI pigment Yellow 31), yellow lead (CI pigment Yellow 34), zinc yellow (CI pigment Yellow 36), and nickel titanium yellow (C. I. pigment Yellow 36). 53), chromate such as chromium titanium yellow (CI Pigment Brown 24); ferrocyanide such as bitumen (CI pigment Blue 27); cadmium yellow (CI pigment Yellow 42), cadmium Sulfides such as red (C.I. pigment Red 108); iron black (C.I. pigment Black 11), Bengala (C.I. pigment Red 101), titanium dioxide (C.I. pigment White 6), etc. Acid Silicates such as ultramarine (CI pigment blue 29); or carbon blacks such as channel black, roller black, disk, gas furnace black, oil furnace black, thermal black, and acetylene black (CI pigment) Black 7).

  Examples of organic dyes such as organic pigments and organic dyes include C.I. I. pigmentBlack 1 (condensed aniline type), C.I. I. pigment Yellow 12 (monoazo type), C.I. I. pigment Yellow 23 (anthraquinone series), C.I. I. pigment Yellow 109 (isoindolinone series), C.I. I. pigment Yellow 138 (quinophthalone series), C.I. I. pigment Orange 5 (monoazo type), C.I. I. Vat Orange 3 (perinone series), C.I. I. pigment Red 1 (monoazo type), C.I. I. pigment Red 37 (pyrazolone azo type), C.I. I. pigment Red 87 (thioindigo system), C.I. I. pigment Red 224 (perylene type), C.I. I. pigment Violet 19 (quinacridone series), C.I. I. pigment Violet 3 (azomethine series), C.I. I. pigment Violet 37 (dioxazine type), C.I. I. pigment blue 15 (phthalocyanine series), C.I. I. pigment Green 1 (azomethine type) and the like.

These colorants may be used alone or in combination of two or more.
The amount of the colorant used in the present invention is 0.00001 parts by weight or more and 3 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin. Preferably they are 0.0001 weight part or more and 2 weight parts or less, More preferably, they are 0.0005 weight part or more and 1 weight part or less. If the amount of the colorant is less than 0.00001 parts by weight, it is difficult to obtain a deep and clear color. When the amount is more than 3 parts by weight, the surface roughness of the molded product increases, and it is difficult to obtain a deep and clear color.

Further, the polycarbonate resin composition of the present invention may be a resin composition containing the above-mentioned additives, and in addition to the above-mentioned additives, various known additives as long as the object of the present invention is not impaired. For example, it may be a resin composition containing an impact resistance improver, a flame retardant, a flame retardant aid, a hydrolysis inhibitor, an antistatic agent, a foaming agent, a dye and pigment, and the like. Further, for example, it is a resin composition in which a synthetic resin such as aromatic polycarbonate, aromatic polyester, polyamide, polystyrene, polyolefin, acrylic, and amorphous polyolefin, and a biodegradable resin such as polylactic acid and polybutylene succinate are mixed. May be.

  In the polycarbonate resin composition of the present invention, as a blending method of the above-mentioned carbonate copolymer and various additives as described above, for example, a tumbler, a V-type blender, a super mixer, a nauter mixer, a Banbury mixer, kneading There is a method of mixing and kneading with a roll, an extruder, etc., or a solution blending method of mixing in a state of being dissolved in a common good solvent such as methylene chloride, but this is not particularly limited. Any method may be used as long as it is a blending method used.

  In addition, there is no limitation on the blending timing of the above-mentioned carbonate copolymer and the above-mentioned various additives, etc., and after mixing a plurality of carbonate copolymers having different compositions into pellets, various additives are blended. It is also possible to mix various additives, etc. with each of a plurality of carbonate copolymers having different compositions to mix them as composition pellets, or to mix a plurality of carbonate copolymers having different compositions. At the same time, various additives may be blended at the same time.

[Mold equipment for insert molding]
As shown in FIG. 1, the insert resin molding die apparatus according to the present invention is composed of two molds constituting the insert molding mold apparatus 1, that is, a fixed side mold 2 and a movable side mold 3. Is done. As shown in FIG. 1, a decorative film 4 can be inserted in the fixed mold 2, and a recess for filling the entire surface of the decorative film 4 with a molten resin is formed. By closing these two molds, the resin filling cavity 5 is formed.

Of the two molds, one (fixed side) mold recess is formed with a design surface side cavity surface 5a in close contact with the film, and the other (movable side) mold has no design surface. The design surface side cavity surface 5b is formed.
In FIG. 1, a design surface side cavity surface 5 a that is in close contact with the film is formed on the fixed mold 2, and the non-design surface side cavity surface 5 b that does not have a design surface is formed on the movable mold 3. However, the present invention is not limited to this, and may be reversed.

  The injected resin is supplied to at least one end of the cavity 5 of the fixed mold 2 and between the design surface side cavity surface 5a and the non-design surface side cavity surface 5b of the cavity 5. A side gate 8 is provided. The side gate 8 is fed with the injection resin through the spray 6 and the runner 7 for introducing the injection resin from the outside of the mold apparatus 1 for insert resin molding. The injection resin is supplied to the cavity 5 from the side gate 8.

“Insert injection molding using insert molding die equipment”
Examples of a method for producing an injection-molded body using the insert resin molding die apparatus include the following methods.
First, a decorative film 4 of 100 mm × 100 mm (thickness 0.25 mm), which is a polycarbonate resin main component, is inserted into the cavity 5 of the fixed mold 2, and then the injection resin is poured into a cylinder of an injection molding machine and melted. Let Then, the movable side mold 3 and the fixed side mold 2 are brought into contact with each other, the mold is closed, and the injected resin is cavityd through the spray 6, the runner 7 and the side gate 8 of the mold apparatus for insert resin molding. Pour into 5 and fill and hold the pressure. Thereafter, the resin in the cavity 5 is cooled, the mold is opened, and the resin molded body decorated with the film, in which the decorative film and the injection resin are integrated, is taken out.

  In the above insert resin molding die apparatus, a cooling pipe 9 is arranged in the fixed side mold 2 and the movable side mold 3, and although not shown, the mold can be adjusted so that the mold temperature can be adjusted. Connected from the temperature controller, water can be passed.

  The insert injection molding conditions differ depending on the type of resin used, but when the above-mentioned specific polycarbonate resin composition is used, the cylinder temperature of the injection molding machine is subject to thermal decomposition due to shear heat generation when the resin is plasticized. It is preferable to set it as 220 to 260 degreeC from the point to suppress, and it is more preferable to set it as 230 to 250 degreeC. The mold temperature of the insert resin molding die apparatus is preferably 40 ° C. to 90 ° C., and preferably 50 ° C. to 80 ° C., because there is little deformation after the molded product is released from the mold. It is more preferable.

[Various automotive interior resin panels]
Using the above-described mold apparatus for molding an insert resin, insert resin molding of the specific polycarbonate resin composition is performed to produce a decorated insert resin molded body such as an automobile interior resin panel or a transparent display panel. can do.

  The insert resin molded body produced by the production method of the present invention is a resin panel for various automobile interiors, transparent display, particularly utilizing its weather resistance, colored sharpness due to transparency, and long-term durability of these characteristics. It is suitably used for panels and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited to a following example at all.

[Method for producing isosorbide polycarbonate resin composition (hereinafter sometimes referred to as ISP resin composition)]
(1) Measurement of structural unit ratio (composition ratio) derived from each dihydroxy compound in polycarbonate copolymer or resin composition Structural unit ratio derived from each dihydroxy compound in polycarbonate copolymer or resin composition is polycarbonate. 30 mg of resin is weighed and dissolved in about 0.7 mL of deuterated chloroform to obtain a solution, which is put in an NMR tube having an inner diameter of 5 mm, and ¹ H at room temperature using JNM-AL400 (resonance frequency 400 MHz) manufactured by JEOL. NMR spectrum was measured. The structural unit ratio derived from each dihydroxy compound was determined from the signal intensity ratio based on the structural unit derived from each dihydroxy compound.
The structural unit ratio is sometimes simply referred to as a composition ratio.

(2) Measurement of glass transition temperature (Tg) It measured using the differential scanning calorimeter (SII nanotechnology company make: DSC6220). About 10 mg of a resin sample was sealed in an aluminum pan manufactured by the same company, and the temperature was raised from room temperature to 250 ° C. at a temperature rising rate of 20 ° C./min under a nitrogen stream of 50 mL / min. After maintaining the temperature for 3 minutes, it was cooled to 30 ° C. at a rate of 20 ° C./min. The temperature was maintained at 30 ° C. for 3 minutes, and the temperature was increased again to 200 ° C. at a rate of 20 ° C./min. The value of the peak top of the DDSC in the measurement data obtained by the second temperature increase was defined as Tg.

(3) Measurement of reduced viscosity A polycarbonate copolymer or resin composition sample was dissolved using a mixed solvent of phenol and 1,1,2,2-tetrachloroethane methylene chloride in a mass ratio of 1: 1. A polycarbonate solution with a concentration of 00 g / dL was precisely prepared. Using Moritomo Rika Co. Ubbelohde viscometer tube was measured at a temperature of 20.0 ° C. ± 0.1 ° C., relative viscosity by the following equation from the transit time t of the passing time t ₀ and the polycarbonate solution solvent η _{find rel} ,
η _rel = t / t ₀
Next, the specific viscosity η _sp was determined from the following equation from the relative viscosity.
η _sp = (η−η ₀ ) / η ₀ = η _rel −1
Then, the reduced viscosity η _sp / c was determined by dividing the specific viscosity by the concentration c (g / dL). The higher this value, the higher the molecular weight.

The abbreviations of the compounds used in the description of the following examples are as follows.
ISB: Isosorbide (Rocket Fleure, trade name: POLYSORB)
CHDM: 1,4-cyclohexanedimethanol (manufactured by Shin Nippon Rika Co., Ltd., trade name: SKY CHDM)
・ DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)
AS2112: Compound name, tris (2,4-di-t-butylphenyl) phosphite (manufactured by ADEKA)
IRGANOX 1010: Compound name, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (manufactured by BASF Japan Ltd.)
E-275: Compound name, ethylene glycol distearate (manufactured by NOF Corporation)

(Production Example 1)
In a polymerization reactor equipped with a stirring blade and a reflux condenser controlled at 100 ° C., ISB and CHDM, DPC and calcium acetate monohydrate having a chloride ion concentration of 10 ppb or less by purification by distillation, in a molar ratio. ISB / CHDM / DPC / calcium acetate monohydrate = 0.80 / 0.20 / 1.00 / 1.3 × 10 ⁻⁶ , fully substituted with nitrogen, oxygen concentration 0.0005 The volume was adjusted to 0.001% by volume. Subsequently, heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to be 100 ° C. After that, temperature increase was started, the internal temperature was adjusted to 210 ° C. in 40 minutes, and when the internal temperature reached 210 ° C., control was performed so as to maintain this temperature, and at the same time, pressure reduction was started and the temperature reached 210 ° C. After 90 minutes, the pressure was changed to 13.3 kPa (absolute pressure, the same applies hereinafter), and the pressure was maintained for another 60 minutes.

The phenol vapor produced as a by-product with the polymerization reaction is led to a reflux condenser using a steam controlled at 100 ° C. as the inlet temperature to the reflux condenser, and a monomer component contained in the phenol vapor in a slight amount is introduced into the polymerization reactor. Then, the phenol vapor that did not condense was recovered by guiding it to a condenser using 45 ° C. warm water as a refrigerant. The contents thus oligomerized are once restored to atmospheric pressure, and then transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. The internal temperature was set to 220 ° C. and the pressure was set to 200 Pa in 60 minutes.
Thereafter, the internal temperature was set to 230 ° C. over 20 minutes, the pressure was reduced to 133 Pa or less, the pressure was restored when the predetermined stirring power was reached, the contents were extracted in the form of strands, and the pellets of polycarbonate copolymer were formed with a rotary cutter.

(Production Example 2)
Manufacture except that in Preparation Example 1, the charge composition was changed to ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, polycarbonate copolymer pellets were obtained.

(Production Example 3)
Manufacture except that in Preparation Example 1, the charge composition was changed to ISB / CHDM / DPC / calcium acetate monohydrate = 0.60 / 0.40 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, polycarbonate copolymer pellets were obtained.

(Production Example 4)
Manufacture except that in Preparation Example 1, the charge composition was changed to ISB / CHDM / DPC / calcium acetate monohydrate = 0.50 / 0.50 / 1.00 / 1.3 × 10 ⁻⁶ In the same manner as in Example 1, polycarbonate copolymer pellets were obtained.

(Conbound of resin composition)
The pellets of the polycarbonate copolymer produced in Production Example 1 to Production Example 4 were blended to the constituent ratios shown in Table 2 using a Henschel mixer, and a twin-screw extruder (TEX30HSS-32) manufactured by Nippon Steel Co., Ltd. was used. After extruding at a resin temperature of 250 ° C., cooling and solidifying with water, and pelletizing with a rotary cutter, a polycarbonate resin compound product was produced.

(Compound example 1)
Production Example 1 (Resin 1) was blended with a Henschel mixer at a ratio of 80.3 wt% and Production Example 4 (Resin 4) at a ratio of 19.7 wt%, and a twin screw extruder manufactured by Nippon Steel (TEX30HSS-32). Was extruded at a resin temperature of 250 ° C., cooled and solidified with water, and pelletized with a rotary cutter to produce a polycarbonate resin compound product.

(Compound example 2)
A compound product of polycarbonate resin was produced in the same manner as in Compound Example 1 except that the composition ratio in Compound Example 1 was changed so that Resin 1 / Resin 4 = 71.4 / 28.6.

(Compound example 3)
Production Example 2 (Resin 2) was blended in a ratio of 75.0 wt% and Production Example 4 (Resin 4) was mixed in a Henschel mixer at a ratio of 25.0 wt%. Was extruded at a resin temperature of 250 ° C., cooled and solidified with water, and pelletized with a rotary cutter to produce a polycarbonate resin compound product.

(Compound example 4)
In Compound Example 3, a polycarbonate compound product was produced in the same manner as Compound Example 1 except that the component ratio was changed to be resin 2 / resin 4 = 50/50.

[Decorating film]
As shown in FIG. 2, a product name: Panlite film (hereinafter referred to as “polycarbonate film”), which is mainly composed of polycarbonate of Teijin Chemicals Ltd., has a printing layer 13 and a binder layer on both ends of the polycarbonate film 11. 12 was used.

[Example 1]
The insert molding die shown in FIG. 1 was used as the insert molding die. In this mold, concave portions having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm for inserting a film mainly composed of polycarbonate are formed in the fixed-side mold 2 shown in FIG.
The mold temperature of the fixed mold 2 and the movable mold 3 is adjusted to 70 ° C. by passing hot water of 70 ° C. from the mold temperature controller (not shown) into the cooling pipe 9 shown in FIG. did.
Next, a decorative film having a thickness of 0.3 mm mainly composed of polycarbonate was inserted into the concave portion of the stationary mold 2 and fixed to the cavity surface with a double-sided tape. The molding machine is a NAMEMU2000 molding machine manufactured by Meiki Seisakusho Co., Ltd. The molding machine cylinder melts resin 5 as an injection resin at a cylinder temperature of 250 ° C. The mold was closed and filled into the cavity 5 through the spray 6, runner 7 and side gate 8 of the insert molding die, and the pressure was maintained. Then, the resin in the cavity was cooled, the mold was opened, and the resin-molded body for film decoration, in which the molded body 10 for injection resin (see FIG. 2) was laminated on the film for decoration 4, was taken out.
The obtained resin-decorated resin molded film was subjected to thermal strain for 2 hours in a gear oven with a temperature in the tank of 100 ° C., but the film was not peeled off and the resin was not deformed. The function as a panel was satisfactory, and the resin-molded body decorated with a film had a beautiful appearance over the entire surface.

[Example 2]
Injection molding was performed in the same manner as in Example 1 except that the injected resin was resin 6. The obtained resin-decorated resin molded film was subjected to thermal strain for 2 hours in a gear oven with a temperature in the tank of 100 ° C., but the film was not peeled off and the resin was not deformed. The function as a panel was satisfactory, and the resin-molded body decorated with a film had a beautiful appearance over the entire surface.

[Example 3]
Injection molding was performed in the same manner as in Example 1 except that the injected resin was resin 7. The obtained resin-decorated resin molded film was subjected to thermal strain for 2 hours in a gear oven with a temperature in the tank of 100 ° C., but the film was not peeled off and the resin was not deformed. The function as a panel was satisfactory, and the resin-molded body decorated with a film had a beautiful appearance over the entire surface.

[Example 4]
Injection molding was performed in the same manner as in Example 1 except that the injected resin was changed to resin 8. The obtained resin-decorated resin molded film was subjected to thermal strain for 2 hours in a gear oven with a temperature in the tank of 100 ° C., but the film was not peeled off and the resin was not deformed. The function as a panel was satisfactory, and the resin-molded body decorated with a film had a beautiful appearance over the entire surface.

[Comparative Example 1]
Injection molding was performed in the same manner as in Example 1 except that the injected resin was resin 1. As a result of applying a thermal strain of 2 hours in a gear oven with a temperature in the tank of 100 ° C., the resulting film-laminated resin molded body was not seen in the deformation of the resin, but the film and the resin were peeled off and decorated. The function as a resin panel was not satisfied.

[Comparative Example 2]
Injection molding was performed in the same manner as in Example 1 except that the injected resin was resin 2. As a result of applying a thermal strain of 2 hours in a gear oven with a temperature in the tank of 100 ° C., the resulting film-laminated resin molded body was not seen in the deformation of the resin, but the film and the resin were peeled off and decorated. The function as a resin panel was not satisfied.

[Comparative Example 3]
Injection molding was performed in the same manner as in Example 1 except that the injected resin was resin 3. As a result of applying a thermal strain of 2 hours in a gear oven with a temperature in the tank of 100 ° C., the resulting film-laminated resin molded body was not seen in the deformation of the resin, but the film and the resin were peeled off and decorated. The function as a resin panel was not satisfied.

[Comparative Example 4]
Injection molding was performed in the same manner as in Example 1 except that the injected resin was resin 4. As a result of applying thermal strain for 2 hours in a gear oven with a temperature in the tank of 100 ° C., the film-laminated resin molded body was not peeled off from the film, but was deformed. The function as a decorated resin panel was not satisfied.

DESCRIPTION OF SYMBOLS 1 Insert molding die 2 Fixed side die 3 Movable side die 4 Decorating film 5 Cavity 5a Design side cavity surface 5b Non-design side cavity surface 6 Sprue 7 Runner 8 Side gate 9 Cooling pipe 10 Molding of injection resin Body 11 Polycarbonate film 12 Binder layer 13 Print layer

Claims (14)

Inserting a decorative film made of polycarbonate-containing resin into a mold, and a resin molded body obtained by integrating with a resin injected from a cylinder of an injection molding machine,
The injected resin is a resin composition including a polycarbonate resin composition;
This polycarbonate resin composition is a polycarbonate resin composition obtained by melt mixing a plurality of carbonate copolymers having different copolymerization ratios,
Each of the plurality of carbonate copolymers is composed of structural units derived from two or more dihydroxy compounds, and has at least a structural unit derived from a dihydroxy compound represented by the following formula (2) .
The content of the carbonate copolymer having the smallest polymerization ratio of the structural unit derived from the dihydroxy compound represented by the following formula (2) is less than the sum of the contents of the other polycarbonate copolymers. , Resin-decorated body with film decoration.

  2. The film additive according to claim 1, wherein the polycarbonate resin composition has a content of the polycarbonate copolymer having the lowest glass transition temperature less than the sum of the contents of the other polycarbonate copolymers. Decorated resin molding.   3. The film according to claim 1, wherein the polycarbonate resin composition has a content of the polycarbonate copolymer having the highest reduced viscosity less than the sum of the contents of the other polycarbonate copolymers. 4. Decorated resin molding. Inserting a decorative film made of polycarbonate-containing resin into a mold, and a resin molded body obtained by integrating with a resin injected from a cylinder of an injection molding machine,
The injected resin is a resin composition including a polycarbonate resin composition;
This polycarbonate resin composition is a polycarbonate resin composition obtained by melting and mixing a plurality of carbonate copolymers having different copolymer ratios,
Each of the plurality of carbonate copolymers is composed of structural units derived from two or more dihydroxy compounds, and has at least a structural unit derived from a dihydroxy compound represented by the following formula (2) .
A resin molded product for film decoration, characterized in that the content of the polycarbonate copolymer having the lowest glass transition temperature is less than the sum of the contents of other polycarbonate copolymers.

  5. The film decoration according to claim 4, wherein the polycarbonate resin composition has a content of the polycarbonate copolymer having the highest reduced viscosity less than a sum of the contents of the other polycarbonate copolymers. Resin molded body. Inserting a decorative film made of polycarbonate-containing resin into a mold, and a resin molded body obtained by integrating with a resin injected from a cylinder of an injection molding machine,
The injected resin is a resin composition including a polycarbonate resin composition;
This polycarbonate resin composition is a polycarbonate resin composition obtained by melting and mixing a plurality of carbonate copolymers having different copolymer ratios,
Each of the plurality of carbonate copolymers is composed of structural units derived from two or more dihydroxy compounds, and has at least a structural unit derived from a dihydroxy compound represented by the following formula (2) .
A resin molded product for film decoration, characterized in that the content of the polycarbonate copolymer having the highest reduced viscosity is less than the sum of the contents of other polycarbonate copolymers.

  6. The glass transition temperature of the polycarbonate copolymer having the lowest glass transition temperature among the polycarbonate copolymers of the polycarbonate resin is in a range of 60 ° C. to 105 ° C. 6. Resin molded body with film decoration. Inserting a decorative film made of a polycarbonate-containing resin into a mold, then injecting the resin from a cylinder of an injection molding machine, and integrating the both,
The injected resin is a resin composition including a polycarbonate resin composition;
This polycarbonate resin composition is a polycarbonate resin composition obtained by melting and mixing a plurality of carbonate copolymers having different copolymer ratios,
Each of the plurality of carbonate copolymers is composed of structural units derived from two or more dihydroxy compounds, and has at least a structural unit derived from a dihydroxy compound represented by the following formula (2) .
The content of the carbonate copolymer having the smallest polymerization ratio of the structural unit derived from the dihydroxy compound represented by the following formula (2) is less than the sum of the contents of the other polycarbonate copolymers. Manufacturing method of resin molding.

  9. The resin molding according to claim 8, wherein the polycarbonate resin composition has a content of the polycarbonate copolymer having the lowest glass transition temperature less than the sum of the contents of the other polycarbonate copolymers. Body manufacturing method.   10. The resin according to claim 8, wherein the polycarbonate resin composition has a content of the polycarbonate copolymer having the highest reduced viscosity less than the sum of the contents of the other polycarbonate copolymers. Manufacturing method of a molded object. Inserting a decorative film made of a polycarbonate-containing resin into a mold, then injecting the resin from a cylinder of an injection molding machine, and integrating the both,
The injected resin is a resin composition including a polycarbonate resin composition;
This polycarbonate resin composition is a polycarbonate resin composition obtained by melt mixing a plurality of carbonate copolymers having different copolymerization ratios,
Each of the plurality of carbonate copolymers is composed of structural units derived from two or more dihydroxy compounds, and has at least a structural unit derived from a dihydroxy compound represented by the following formula (2) .
A method for producing a resin molded article, wherein the content of the polycarbonate copolymer having the lowest glass transition temperature is less than the sum of the contents of the other polycarbonate copolymers.

  The resin molded article according to claim 11, wherein the polycarbonate resin composition has a content of the polycarbonate copolymer having the highest reduced viscosity that is less than the sum of the contents of the other polycarbonate copolymers. Manufacturing method. Inserting a decorative film made of a polycarbonate-containing resin into a mold, then injecting the resin from a cylinder of an injection molding machine, and integrating the both,
The injected resin is a resin composition including a polycarbonate resin composition;
This polycarbonate resin composition is a polycarbonate resin composition obtained by melt mixing a plurality of carbonate copolymers having different copolymerization ratios,
Each of the plurality of carbonate copolymers is composed of structural units derived from two or more dihydroxy compounds, and has at least a structural unit derived from a dihydroxy compound represented by the following formula (2) .
A method for producing a resin molded article, wherein the content of the polycarbonate copolymer having the highest reduced viscosity is less than the sum of the contents of the other polycarbonate copolymers.

  13. The glass transition temperature of the polycarbonate copolymer having the lowest glass transition temperature among the polycarbonate copolymers of the polycarbonate resin is in the range of 60 ° C. to 105 ° C. 13. Manufacturing method of resin molding.

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