JP6287318B2 - Resin composition and method for producing three-dimensional object - Google Patents

Description

  The present invention relates to a resin composition for producing a three-dimensional object by using a laminated deposition system by extrusion, and a method for producing a three-dimensional object by using the laminated deposition system by extrusion using the resin composition as a raw material.

  A laminated deposition system by extrusion (for example, the system manufactured by Stratasys Incorporated in the United States) is a three-dimensional object based on a computer-aided design (CAD) model by extruding a fluid material from a nozzle portion provided in an extrusion head. Is used to build a layer. The raw material is continuously deposited on the XY plane substrate in the chamber from the nozzle, and the extruded raw material is fused with the already deposited laminate and solidifies as it cools. Usually, a three-dimensional object similar to a CAD model is constructed by repeating the extrusion process while the nozzle position with respect to the substrate is raised in the Z-axis direction perpendicular to the XY plane.

  When manufacturing the target three-dimensional object by depositing the laminated raw material, a support material to be removed after completion of the extrusion process is deposited under the projecting part or cavity of the three-dimensional object being constructed, It is common to install a support structure in advance. It is preferable to use a raw material that can be easily peeled and removed from the target three-dimensional object, or a raw material that easily dissolves in a specific solvent (including decomposition and swelling in a broad sense). In some cases, a design is left with some design features and functions without removing a part from the target three-dimensional object.

  Conventionally, an acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as “ABS resin”) has been exclusively used as a lamination raw material from the viewpoint of processability and fluidity (Patent Document 1). However, the ABS resin has a large shrinkage rate and it is difficult to obtain an object with high dimensional accuracy. Also, in applications that require heat resistance, transparency, and surface hardness, practical characteristics cannot be satisfied from the viewpoint of material properties.

  As an attempt to solve the above-mentioned problems by substituting materials, acrylic resins (Patent Documents 2 and 3) having methyl methacrylate as a main monomer, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “bisphenol-A”) Studies have been made using aromatic polycarbonate resins having a main monomer as a raw material.

Special table 2010-521339 Special table 2008-507619 Special table 2012-509777 gazette

  However, since the above-mentioned conventional raw material resin has a high temperature for obtaining fluidity suitable for extrusion, the extrusion temperature must be set to a high temperature of, for example, 300 ° C. or higher, and the base temperature is also high because the cooling and solidification temperature is high. For example, the temperature had to be higher than 100 ° C.

  As an alternative material that does not require excessively high processing temperatures, polylactic acid resin containing lactic acid as the main monomer has been studied, but the extrusion process is completed because polylactic acid resin is a hard and brittle material. When the target object is later peeled off from the substrate or the support material is removed, the target three-dimensional object is often damaged.

  An object of the present invention is a resin composition that can be suitably used in a laminated deposition system by extrusion in view of the above circumstances, can be molded without excessively increasing the extrusion temperature, and has low shrinkage, high heat resistance, The object is to provide a resin composition excellent in material property balance such as high transparency and high surface hardness.

  As a result of intensive studies to solve the above problems, the present inventor has found that all of the above problems can be solved by the invention disclosed below, and has completed the present invention.

  The present invention comprises the following.

[1] A resin composition for producing a three-dimensional object using a laminated deposition system by extrusion, the structural unit (a) derived from a dihydroxy compound having a structure represented by the following general formula (1): And a polycarbonate resin having a structural unit (b) derived from another dihydroxy compound, and the proportion of the structural unit (a) in the total structural units derived from the dihydroxy compound contained in the polycarbonate resin is 40 The structural unit (b) is any structural unit selected from the group consisting of structural units derived from dihydroxy compounds represented by the following formulas (2) to (5). There, the resin composition was measured in accordance with JIS K7191, bending der deflection temperature under load 70 ° C. or higher 125 ° C. or less at a stress 1.80MPa Resin composition, characterized by.

H 2 O—R ¹ —OH (2)
(In formula (2), R ¹ represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.)
HO—CH ₂ —R ² —CH ₂ —OH (3)
(In formula (3), R ² represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.)
H- (O-R < ³ >) _p- OH (4)
(In Formula (4), R ³ represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, and p is an integer of 2 to 100.)
^HO-R 4 -OH (5)
(In formula (5), R ⁴ represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a group having a substituted or unsubstituted acetal ring.)

[ 2 ] A method for producing a three-dimensional object by using a laminated deposition system by extrusion, wherein the resin composition according to [1 ] is used as a raw material, and the temperature of a heating extrusion head in the laminated deposition system by extrusion is set to 230. A method for producing a three-dimensional object, characterized in that the three-dimensional object is produced at a temperature of not higher than ° C.

[ 3 ] A method for producing a three-dimensional object using a laminated deposition system by extrusion, wherein the substrate composition in the laminated deposition system by extrusion is set to 80 ° C. or less using the resin composition described in [1 ] as a raw material. A method for producing a three-dimensional object, characterized in that the three-dimensional object is produced by setting.

The resin composition of the present invention has a lower temperature for obtaining fluidity suitable for extrusion compared to a resin composition for producing a three-dimensional object using a conventionally proposed layered deposition system by extrusion. In addition, it can be molded without excessively raising the extrusion processing temperature, and is excellent in material property balance such as low shrinkage, high heat resistance, high transparency, and high surface hardness.
For this reason, the resin composition of the present invention is used as a raw material for producing a three-dimensional object by a laminated deposition system by extrusion, and the temperature of the heating extrusion head and the base temperature is set lower than before, and the tertiary that exhibits a good appearance The original object can be manufactured accurately and efficiently.

  Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.

[Resin composition for producing a three-dimensional object using a laminated deposition system by extrusion]
The resin composition of the present invention is a resin composition for producing a three-dimensional object using a laminated deposition system by extrusion, and is a dihydroxy compound having a structure represented by the following general formula (1) (hereinafter, “ A polycarbonate resin having a structural unit (a) derived from a dihydroxy compound (1) ”and a structural unit (b) derived from another dihydroxy compound (hereinafter referred to as“ the polycarbonate resin of the present invention ( A) "or" polycarbonate resin (A) ").

[Polycarbonate resin (A)]
<Dihydroxy compound (1)>
In the polycarbonate resin (A) of the present invention, the structural unit (a) derived from the dihydroxy compound (1) represented by the general formula (1) (hereinafter sometimes referred to as “structural unit (1)”). Is included.

  The proportion of the structural unit (1) (that is, the structural unit (a)) in the total structural units derived from the dihydroxy compound contained in the polycarbonate resin (A) of the present invention is 40 to 85 mol%, particularly 45 to 80%. It is preferable that it is mol%, especially 50-70 mol%. When the proportion of the structural unit (1) in the polycarbonate resin (A) is within this range, a polycarbonate resin (A) having a low coloration, a high molecular weight, a high impact strength, and a high glass transition temperature is obtained. Can do.

  The polycarbonate resin (A) of the present invention may contain a structural unit (1) derived from one dihydroxy compound (1) as the structural unit (1) derived from the dihydroxy compound (1). It may contain a structural unit (1) derived from two types of dihydroxy compounds (1).

  The polycarbonate resin (A) of the present invention containing the structural unit (1) derived from the dihydroxy compound (1) is, for example, 1 of the dihydroxy compound (1) according to the method for producing the polycarbonate resin (A) of the present invention described later. Manufactured using seeds or two or more.

  Examples of the dihydroxy compound (1) include isosorbide, isomannide, and isoide which have a stereoisomeric relationship.

  Among the above-mentioned dihydroxy compounds (1), they are abundant as resources and can be easily obtained, and isosorbide obtained by dehydrating condensation of sorbitol produced from various starches is easy to obtain and produce, Most preferable in terms of optical properties and moldability.

  The dihydroxy compound (1) having a cyclic ether structure such as 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 in, and to use an oxygen scavenger or handle under 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 the polycarbonate resin (A) of the present invention is produced using isosorbide containing these decomposition products, the resulting polycarbonate resin (A) is colored. May occur or the physical properties may be significantly deteriorated. Moreover, it may affect the polymerization reaction, and a high molecular weight polymer may not be obtained.

  Therefore, it is preferable to use a stabilizer for the dihydroxy compound (1). As the stabilizer, it is preferable to use stabilizers such as a reducing agent, an antacid, an antioxidant, an oxygen scavenger, a light stabilizer, a pH stabilizer, a heat stabilizer, and the like, and particularly under acidic conditions, the dihydroxy compound (1) It is preferable that a basic stabilizer is contained because of being easily altered. Among these, examples of the reducing agent include sodium borohydride and lithium borohydride, and examples of the antacid include alkalis such as sodium hydroxide. However, the addition of such an alkali metal salt is not preferable because the added alkali metal may serve as a polymerization catalyst during the production of the polycarbonate resin (A).

  Basic stabilizers include hydroxides, carbonates, phosphates, phosphites, hypophosphorous acids of Group 1 or Group 2 metals in the Long Periodic Periodic Table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). Salts, borates, fatty acid salts, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylpheny Basic ammonium compounds such as ruammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, butyltriphenylammonium hydroxide, 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-methyl Examples include amine compounds such as imidazole and aminoquinoline. Of these, sodium or potassium phosphates and phosphites are preferable, and disodium hydrogen phosphate and disodium hydrogen phosphite are particularly preferable because of their effects and ease of distillation removal described later.

  Although there is no restriction | limiting in particular in content in the dihydroxy compound (1) of these basic stabilizers, if too little, there exists a possibility that the effect which prevents the modification of dihydroxy compound (1) may not be acquired, and if too much, a dihydroxy compound Since the modification of (1) may be caused, it is usually 0.0001% by weight to 1% by weight, preferably 0.001% by weight to 0.1% by weight, based on the dihydroxy compound (1).

When the dihydroxy compound (1) to which these stabilizers are added is used as a raw material for the polycarbonate resin (A), depending on the type of the stabilizer, the resulting polycarbonate resin (A) may be colored or the physical properties may be significantly deteriorated. There is a case. For example, when the dihydroxy compound (1) containing the above basic stabilizer is used as a raw material for producing the polycarbonate resin (A), the basic stabilizer itself becomes a polymerization catalyst, and it becomes difficult to control the polymerization rate and quality. In addition, the initial hue is deteriorated, and the resultant molded article of the polycarbonate resin (A) is deteriorated in light resistance.
For this reason, before using dihydroxy compound (1) as a manufacturing raw material of polycarbonate resin (A), it is preferable to remove stabilizers, such as a basic stabilizer, by ion exchange resin or distillation.
Moreover, as mentioned above, when the dihydroxy compound (1) containing the oxidative decomposition product of the dihydroxy compound (1) is used as a raw material for producing the polycarbonate resin (A), the resulting polycarbonate resin (A) may be colored. In addition, there is a possibility that not only the physical properties may be remarkably deteriorated, but also the polymerization reaction is affected and a high molecular weight polymer may not be obtained.

  For this reason, in order to obtain the dihydroxy compound (1) which does not contain an oxidative decomposition product, and in order to remove the above-mentioned basic stabilizer, it is preferable to perform distillation purification of the dihydroxy compound (1). The distillation in this case may be simple distillation or continuous distillation, and is not particularly limited. As distillation conditions, it is preferable to carry out distillation under reduced pressure in an inert gas atmosphere such as argon or nitrogen. In order to suppress thermal denaturation, it is 250 ° C. or lower, preferably 200 ° C. or lower, particularly 180 °. It is preferable to carry out under the conditions of ℃ or less.

  By such distillation purification, the oxidative decomposition product in the dihydroxy compound (1), for example, formic acid content is 20 ppm by weight or less, preferably 10 ppm by weight or less, particularly preferably 5 ppm by weight or less. The polycarbonate resin (A) excellent in hue and thermal stability can be produced without impairing the polymerization reactivity during the production of the resin (A).

The formic acid content of the dihydroxy compound (1) is measured using ion chromatography according to the following procedure. In the following procedure, isosorbide is taken as an example as a representative dihydroxy compound (1).
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.
The ion chromatograph uses DX-500 type manufactured by Dionex, and an electric conductivity detector is 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.

<Dihydroxy compounds other than dihydroxy compound (1)>
In addition to the structural unit (1), the polycarbonate resin (A) of the present invention contains a structural unit (b) derived from a dihydroxy compound other than the dihydroxy compound (1).
The polycarbonate resin (A) of the present invention containing the structural unit (b) derived from a dihydroxy compound other than the dihydroxy compound (1) can be produced, for example, according to the production method of the polycarbonate resin (A) of the present invention described later. It is produced using one or more dihydroxy compounds other than 1).

The structural unit (b) contained in the polycarbonate resin (A) of the present invention is any structural unit selected from the group consisting of structural units derived from dihydroxy compounds represented by the following formulas (2) to (5). Preferably there is.
In the following, the dihydroxy compounds represented by the formulas (2), (3), (4) and (5) are respectively represented by “dihydroxy compound (2)”, “dihydroxy compound (3)” and “dihydroxy compound (4)”. ”And“ dihydroxy compound (5) ”, the structural units derived from the dihydroxy compounds (2), (3), (4), and (5) are referred to as“ structural unit (2) ”and“ structural unit (3) ”, respectively. ”,“ Structural unit (4) ”, and“ structural unit (5) ”.

HO—R ¹ —OH (2)
(In formula (2), R ¹ represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.)
HO—CH ₂ —R ² —CH ₂ —OH (3)
(In formula (3), R ² represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.)
H- (O-R < ³ >) _p- OH (4)
(In Formula (4), R ³ represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, and p is an integer of 2 to 100.)
^HO-R 4 -OH (5)
(In formula (5), R ⁴ represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a group having a substituted or unsubstituted acetal ring.)

  Among the dihydroxy compounds (2) to (5), the polycarbonate resin (A) of the present invention preferably contains a structural unit derived from an aliphatic dihydroxy compound, and in particular, derived from an alicyclic dihydroxy compound. It is preferable that the structural unit to be included is included. In this case, flexibility can be imparted to the obtained polycarbonate resin (A).

(Aliphatic dihydroxy compound)
Examples of the aliphatic dihydroxy compound include aliphatic dihydroxy compounds in which R ⁴ is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms among the dihydroxy compounds represented by the formula (5). Examples of the aliphatic dihydroxy compound include 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and 2-ethyl. -1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,10-decanediol, hydrogenated dilinoleyl glycol, hydrogenated dioleyl glycol and the like.

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

(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 heat resistance of the obtained polycarbonate resin (A) may be increased. 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 the dihydroxy compounds (2) and (3).

As cyclohexanedimethanol which is an alicyclic dihydroxy compound represented by the above formula (3), in the above formula (3), R ² is the following formula (3a) (wherein R ⁵ is a hydrogen atom or substituted Or an unsubstituted alkyl group having 1 to 12 carbon atoms.). Specific examples thereof include 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and the like.

As tricyclodecane dimethal and pentacyclopentadecane dimethanol, which are alicyclic dihydroxy compounds represented by the formula (3), in the formula (3), R ² is represented by the following formula (3b) (wherein n Represents 0 or 1).

As decalin dimethanol or tricyclotetradecane dimethanol which is an alicyclic dihydroxy compound represented by the formula (3), in the formula (3), R ² is represented by the following formula (3c) (where m is It represents 0 or 1). Specific examples thereof include 2,6-decalin dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, and the like.

Moreover, as norbornanedimethanol which is an alicyclic dihydroxy compound represented by the formula (3), in the formula (3), R ² includes various isomers represented by the following formula (3d). . Specific examples thereof include 2,3-norbornane dimethanol, 2,5-norbornane dimethanol and the like.

The adamantane dimethanol, which is an alicyclic dihydroxy compound represented by the formula (3), includes various isomers in which R ² is represented by the following general formula (3e) in the formula (3). Specific examples of such a material include 1,3-adamantane dimethanol.

In addition, cyclohexanediol, which is an alicyclic dihydroxy compound represented by the formula (2), in the formula (2), R ¹ is represented by the following formula (2a) (wherein R ⁵ is a hydrogen atom, substituted or non-substituted). A substituted alkyl group having 1 to 12 carbon atoms). Specific examples thereof include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, and the like.

As tricyclodecanediol and pentacyclopentadecanediol, which are alicyclic dihydroxy compounds represented by the formula (2), in the formula (2), R ¹ is represented by the following general formula (2b) (where n is It represents 0 or 1).

As decalin diol or tricyclotetradecane diol which is an alicyclic dihydroxy compound represented by the formula (2), in the formula (2), R ¹ is the following general formula (2c) (where m is 0) Or represents 1)). Specifically, 2,6-decalindiol, 1,5-decalindiol, 2,3-decalindiol and the like are used as such.

The norbornanediol which is an alicyclic dihydroxy compound represented by the formula (2) includes various isomers in which R ¹ is represented by the following general formula (2d) in the formula (2). Specifically, 2,3-norbornanediol, 2,5-norbornanediol, and the like are used as such.

The adamantanediol which is an alicyclic dihydroxy compound represented by the above formula (2) includes various isomers in which R ¹ is represented by the following formula (2e) in the above formula (2). Specifically, 1,3-adamantanediol etc. are used as such.

  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.

(Polyoxyalkylene dihydroxy compound)
The polyoxyalkylene dihydroxy compound which is a dihydroxy compound represented by the formula (4) is preferable from the viewpoint of flexibility, flexibility, polymerization reactivity, and hue of the obtained polycarbonate resin. The polyoxyalkylene dihydroxy compound, which is a dihydroxy compound represented by the formula (4), is a compound having a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, preferably 2 to 5 carbon atoms, in R ^3. is there. p is an integer of 2 to 100, preferably 2 to 50, more preferably 6 to 30, and still more preferably 12 to 15.

Since the resin composition containing the polycarbonate resin (A) of the present invention has a small swell of the molten resin extruded from the extrusion head, it is possible to draw down the molten resin to be laminated and deposited as finer strands. It can be said that it is a suitable raw material for this use also from the viewpoint of such resin characteristics.
Specific examples of the polyoxyalkylene dihydroxy compound that is the dihydroxy compound represented by the formula (4) include diethylene glycol, triethylene glycol, polyethylene glycol (molecular weight 150 to 4000), and the like. It is not limited to. The dihydroxy compound represented by the formula (4) is preferably polyethylene glycol having a molecular weight of 300 to 2000, and more preferably polyethylene glycol having a molecular weight of 600 to 1500.
These may be used alone or in combination of two or more depending on the required performance of the polycarbonate resin (A) to be obtained.

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

(Dihydroxy compound having an alkylene group or a group having an acetal ring)
The dihydroxy compound represented by the formula (5) is a group having a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, or a substituted or unsubstituted acetal ring in R ^4. It has a dihydroxy compound. When the alkylene group of R ⁴ has a substituent, examples of the substituent include an alkyl group having 1 to 5 carbon atoms. In addition, when the group having an acetal ring of R ⁴ has a substituent, examples of the substituent include an alkyl group having 1 to 3 carbon atoms.
Among the dihydroxy compounds (5), examples of the dihydroxy compound in which R ⁴ is a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms include propanediols such as 1,3-propanediol and 1,2-propanediol. , Butanediols such as 1,4-butanediol and 1,3-butanediol, heptanediols such as 1,5-heptanediol, hexanediols such as 1,6-hexanediol, etc. It is not limited to these. Of these, hexanediols are preferred.
On the other hand, the dihydroxy compound in which R ⁴ is a group having a substituted or unsubstituted acetal ring is not particularly limited, and among these, spiro as represented by the following formulas (8) and (9): A dihydroxy compound having a structure is preferable, and a dihydroxy compound having a plurality of ring structures as represented by the following formula (8) is particularly preferable.

Among these dihydroxy compounds, from the viewpoint of easy availability, ease of handling, high reactivity during polymerization, and the hue of the polycarbonate resin to be obtained, the dihydroxy compound (5) is 1, 3 -Propanediol and 1,6-hexanediol are preferred. Further, from the viewpoint of heat resistance, dihydroxy compounds having a group having an acetal ring are preferable, and those having a plurality of ring structures represented by the above formula (8) are particularly preferable.
These may be used alone or in combination of two or more depending on the required performance of the polycarbonate resin (A) to be obtained.

  When the polycarbonate resin (A) of the present invention has a structural unit derived from an alicyclic dihydroxy compound, the structural unit (1) in the polycarbonate resin (A) of the present invention and the aforementioned dihydroxy which is the structural unit (b). Although the molar ratio with the structural unit derived from the compounds (2) to (5) can be selected at an arbitrary ratio, impact strength (for example, notched Charpy impact strength) is improved by adjusting the molar ratio. In addition, it is possible to obtain a desired glass transition temperature in the polycarbonate resin (A).

(Other dihydroxy compounds)
In addition to the structural unit (1) and the structural units (2) to (5), the polycarbonate resin (A) of the present invention may further include structural units derived from other dihydroxy compounds. Other dihydroxy compounds include aromatic dihydroxy compounds.

  Examples of the aromatic dihydroxy compound include a substituted or unsubstituted bisphenol compound. Specifically, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1- Bis (4-hydroxyphenyl) propane, 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) hexa 3,3-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis Bisphenol compounds having no substituent on the aromatic ring such as (4-hydroxyphenyl) cyclohexane; bis (3-phenyl-4-hydroxyphenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) Bisphenol having an aryl group as a substituent on an aromatic ring such as ethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane Compound: bis (4-hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydroxy-3-methylphenyl) Nyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) 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-dimethyl) Tilphenyl) 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) Aromatic rings such as phenylmethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) phenylethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) cyclohexane Bisphenol compounds having an alkyl group as a substituent thereon; bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) Bisphenol compounds in which a divalent group connecting aromatic rings such as -1-phenylpropane, bis (4-hydroxyphenyl) diphenylmethane, and bis (4-hydroxyphenyl) dibenzylmethane has an aryl group as a substituent; '-Dihydroxydiphenyl ether, 3,3', 5,5'-tetramethyl-4,4 -Bisphenol compounds in which aromatic rings such as dihydroxydiphenyl ether are connected by an ether bond; Fragrances such as 4,4'-dihydroxydiphenylsulfone and 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenylsulfone Bisphenol compounds in which aromatic rings are linked by sulfone bonds; aromatic rings such as 4,4′-dihydroxydiphenyl sulfide and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide are bonded by sulfide bonds Examples thereof include a linked bisphenol compound, and preferably 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “bisphenol A”). ).

  In the polycarbonate resin (A) of the present invention, the content of the structural unit derived from the aromatic dihydroxy compound is 0 with respect to the structural unit derived from all the dihydroxy compounds contained in the polycarbonate resin (A) of the present invention. It is preferably at least mol% and less than 1 mol%, more preferably at least 0 mol% and less than 0.8 mol%, and even more preferably at least 0 mol% and less than 0.5 mol%. By including the structural unit derived from the aromatic dihydroxy compound in the polycarbonate resin (A), improvement in heat resistance, surface impact resistance, molding processability, etc. can be expected, but the inclusion of the structural unit derived from the aromatic dihydroxy compound When there is too much quantity, there exists a possibility that coloring may become remarkable.

  The above-mentioned other hydroxy compounds may be used alone or in combination of two or more.

<Carbonated diester>
The polycarbonate resin (A) of the present invention can be produced by a generally used polymerization method, and the polymerization method can be any of an interfacial polymerization method using phosgene and a melt polymerization method in which a transesterification reaction with a carbonic acid diester is performed. However, a melt polymerization method in which a dihydroxy compound is reacted with a carbon dioxide diester having lower environmental toxicity in the presence of a polymerization catalyst is preferable.

  In this case, the polycarbonate resin (A) of the present invention can be obtained by a melt polymerization method in which a dihydroxy compound containing the above-described dihydroxy compound (1) and a carbonic acid diester are transesterified.

  As a carbonic acid diester used, what is normally represented by following formula (6) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.

In the above formula (6), 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 above formula (6) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, preferably diphenyl carbonate. Carbonates and substituted diphenyl carbonates, particularly preferably diphenyl carbonate. The carbonic acid diester may contain impurities such as chloride ions, and these impurities may hinder the polymerization reaction or may deteriorate the hue of the resulting polycarbonate resin (A). Accordingly, it is preferable to use a product purified by distillation or the like.

The carbonic acid diester is preferably used in a molar ratio of 0.90 to 1.20, more preferably in a molar ratio of 0.95 to 1.10, based on all dihydroxy compounds used in the melt polymerization. It is even more preferable to use at a molar ratio of .96 to 1.10, and particularly preferable to use at a molar ratio of 0.98 to 1.04.
When this molar ratio is less than 0.90, the terminal hydroxyl group of the produced polycarbonate resin (A) is increased, the thermal stability of the polymer is deteriorated, and coloring occurs when the resin composition of the present invention is molded. Or the rate of transesterification may be reduced, or the desired high molecular weight product may not be obtained.
If this molar ratio is greater than 1.20, the rate of the transesterification reaction decreases under the same conditions, making it difficult to produce a polycarbonate resin (A) having a desired molecular weight. The amount of residual carbonic acid diester in (A) increases, and this residual carbonic acid diester may be unfavorable at the time of molding or the odor of the molded product, increasing the heat history during the polymerization reaction, resulting in The hue and weather resistance of the obtained polycarbonate resin (A) may be deteriorated.

  Furthermore, when the molar ratio of the carbonic acid diester to the total dihydroxy compound increases, the amount of residual carbonic acid diester in the resulting polycarbonate resin (A) increases, and these absorb the ultraviolet rays to increase the light resistance of the polycarbonate resin (A). It may worsen and is not preferable. The concentration of the carbonic acid diester remaining in the polycarbonate resin (A) of the present invention is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, particularly preferably 60 ppm by weight or less, and particularly preferably 30 ppm by weight or less. However, actually, the polycarbonate resin (A) may contain an unreacted carbonic acid diester, and the lower limit value of the unreacted carbonic acid diester concentration in the polycarbonate resin (A) is usually 1 ppm by weight.

<Transesterification reaction catalyst>
The polycarbonate resin (A) of the present invention can be produced by transesterifying the dihydroxy compound containing the dihydroxy compound (1) and the carbonic acid diester represented by the formula (6) 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.

  Examples of the transesterification catalyst (hereinafter sometimes referred to as “catalyst”) that can be used in the production of the polycarbonate resin (A) of the present invention include 1 in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005). A basic compound such as a metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound of a group or group 2 (hereinafter simply referred to as “group 1” or “group 2”) Can be mentioned. Among these, Preferably a group 1 metal compound and / or a group 2 metal compound are used.

It is possible to use a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination with the Group 1 metal compound and / or the Group 2 metal compound. 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 are 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 borohydride, potassium borohydride, lithium phenide boron, cesium phenide boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, 2 sodium hydrogen phosphate 2 potassium potassium phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, Examples include cesium alcoholate, phenolate, disodium salt of bisphenol A, 2 potassium salt, 2 lithium salt, 2 cesium salt, etc. Among them, cesium compound and lithium compound are preferable.

  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, Strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate and the like, among which magnesium compounds, calcium compounds and barium compounds are preferred, magnesium compounds and / or Or a calcium compound is still more preferable.

  Examples of the basic boron compound include tetramethyl boron, tetraethyl boron, tetrapropyl boron, tetrabutyl boron, trimethylethyl boron, trimethylbenzyl boron, trimethylphenyl boron, triethylmethyl boron, triethylbenzyl boron, triethylphenyl boron, tributylbenzyl. Examples include sodium, potassium, lithium, calcium, barium, magnesium, or strontium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc. It is done.

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

  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.

  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.

  Among the above, at least one metal compound selected from the group consisting of a Group 2 metal compound and a lithium compound is used as a catalyst. Various properties such as transparency, hue, and light resistance of the resulting polycarbonate resin (A) are used. It is preferable in order to make the physical properties excellent.

  In order to make the polycarbonate resin (A) particularly excellent in transparency, hue, and light resistance, the catalyst is at least one metal compound selected from the group consisting of magnesium compounds and calcium compounds. preferable.

  In the case of a Group 1 metal compound and / or a Group 2 metal compound, the amount of the catalyst used is preferably 0.1 to 300 μmol, more preferably as a metal equivalent with respect to 1 mol of all dihydroxy compounds subjected to the reaction. It is in the range of 0.1 to 100 μmol, more preferably 0.5 to 50 μmol, and even more preferably 1 to 25 μmol.

  Among the above, when using a compound containing at least one metal selected from the group consisting of lithium and a group 2 metal, particularly when using a magnesium compound and / or a calcium compound, the total amount subjected to the reaction as a metal equivalent amount is used. The amount is preferably 0.1 μmol or more, more preferably 0.5 μmol or more, and particularly preferably 0.7 μmol or more per mole of the dihydroxy compound. The upper limit is preferably 20 μmol, more preferably 10 μmol, particularly preferably 3 μmol, and most preferably 2.0 μmol.

  If the amount of the catalyst used is too small, the polymerization activity necessary for producing the polycarbonate resin (A) having a desired molecular weight cannot 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 will the hue of the resulting polycarbonate resin (A) be deteriorated, but also by-products may be generated, resulting in a decrease in fluidity and the generation of gel, resulting in brittle fracture. This may cause the production of polycarbonate resin (A) having a target quality.

<Production method of polycarbonate resin (A)>
The polycarbonate resin (A) of the present invention is obtained by melt polymerization of a dihydroxy compound containing the dihydroxy compound (1) and a carbonic acid diester by an ester exchange reaction. The raw material dihydroxy compound and the carbonic acid diester are transesterified. It is preferable to mix uniformly before.
The mixing temperature 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. There is a possibility that the hue of the polycarbonate resin (A) obtained will deteriorate and the light resistance will be adversely affected.

  The operation of mixing the dihydroxy compound and the carbonic acid diester is an oxygen concentration of 10% by volume or less, further 0.0001% by volume to 10% by volume, especially 0.0001% by volume to 5% by volume, and particularly 0.0001% by volume. It is preferable to carry out in an atmosphere of 1% to 1% by volume from the viewpoint of preventing hue deterioration of the obtained polycarbonate resin (A).

The polycarbonate resin (A) of the present invention is preferably produced by melt polymerization in multiple stages using a plurality of reactors using a catalyst. The reason for carrying out melt polymerization in multiple reactors is that at the beginning of the melt polymerization reaction, it is important to suppress the volatilization of the monomer while maintaining the required polymerization rate because there are many monomers contained in the reaction solution. In the latter stage of the melt polymerization reaction, 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. As described above, the number of the reactors may be at least two, but from the viewpoint of production efficiency, the number of reactors is three or more, preferably 3 to 5, and particularly preferably four.
The type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.

  Furthermore, it is effective to use a reflux condenser for the polymerization reactor in order to suppress the amount of the monomer to be distilled off, and the effect is particularly great in a reactor at the initial stage of polymerization where there are many unreacted monomer components. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected according to the monomer used, but the temperature of the refrigerant introduced into the reflux condenser is usually 45 to 180 ° C. at the inlet of the reflux condenser. Yes, preferably 80 to 150 ° C, particularly preferably 100 to 130 ° C. If the temperature of the refrigerant introduced into the reflux condenser is too high, the reflux amount is reduced and the effect is reduced. If it is too low, the distillation efficiency of the monohydroxy compound to be originally distilled tends to be reduced. As the refrigerant, hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.

  In order to maintain the polymerization rate appropriately and suppress the distillation of the monomer, while maintaining the hue, thermal stability, light resistance, etc. of the finally obtained polycarbonate resin (A), the above-mentioned catalyst is used. It is important to select the type and amount.

  In the production of the polycarbonate resin (A) of the present invention, if there are two or more reactors, the reactor is further provided with a plurality of reaction stages having different conditions, and the temperature and pressure are continuously changed. You may go.

  In the production of the polycarbonate resin (A) of the present invention, the catalyst can be added to the raw material preparation tank, the raw material storage tank, or can be directly added to the reactor. The catalyst supply line is installed in the middle of the raw material line before being supplied to the reactor, and preferably supplied as an aqueous solution.

  As the polymerization conditions, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum in the initial stage of polymerization and to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum in the late stage of polymerization. Appropriate selection of the jacket temperature and internal temperature at the stage and the pressure in the reaction system is important from the viewpoint of the hue and light resistance of the resulting polycarbonate resin (A). For example, if either the temperature or the pressure is changed too quickly before the polymerization reaction reaches a predetermined value, the unreacted monomer will be distilled, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to change, resulting in a decrease in the polymerization rate. Or a polymer having a predetermined molecular weight or terminal group may not be obtained, and as a result, the object of the present invention may not be achieved.

  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 evaporation of the monomer is caused, but also the decomposition and coloring of the polycarbonate resin (A) can be promoted. There is sex.

In the production of the polycarbonate resin (A) of the present invention, the method of transesterifying the dihydroxy compound containing the dihydroxy compound (1) and the carbonic acid diester in the presence of a catalyst is usually carried out in a multistage process of two or more stages. . Specifically, the first stage transesterification reaction temperature (hereinafter sometimes referred to as “internal temperature”) is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and even more. Preferably it is 200 degreeC or more. Further, the transesterification temperature in the first stage is preferably 270 ° C. or lower, more preferably 240 ° C. or lower, further preferably 230 ° C. or lower, and even more preferably 220 ° C. or lower. The residence time in the first stage transesterification reaction is usually 0.1 to 10 hours, preferably 0.5 to 3 hours, and the first stage transesterification reaction involves removing the generated monohydroxy compound from the reaction system. It is carried out while distilling off. In the second and subsequent stages, the transesterification reaction temperature is increased, and the transesterification reaction is usually performed at a temperature of 210 to 270 ° C., preferably 220 to 250 ° C., while simultaneously removing the monohydroxy compound generated outside the reaction system. The pressure of the reaction system is gradually lowered from the pressure in the first stage, so that the pressure of the reaction system finally becomes 200 Pa or less, usually 0.1 to 10 hours, preferably 0.5 to 6 hours, Particularly preferably, the polycondensation reaction is performed for 1 to 3 hours.
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 too low, the target molecular weight does not increase, the molecular weight distribution becomes wide, and the impact strength may be inferior. Further, if the residence time of the transesterification reaction is excessively long, brittle fracture may easily occur. If the residence time is too short, the target molecular weight may not increase and the impact strength may be inferior.

  The by-produced monohydroxy compound is preferably reused as a raw material for carbonic acid diesters and various bisphenol compounds after purification as necessary from the viewpoint of effective utilization of resources.

  In particular, in order to obtain a good polycarbonate resin (A) having a high impact strength by suppressing the coloring, thermal deterioration or burn of the polycarbonate resin (A), the maximum temperature of the reactor in all reaction stages is less than 255 ° C. Preferably it is 250 degrees C or less, It is especially preferable that it is 225-245 degreeC. In addition, in order to suppress the lowering of the polymerization rate in the latter half of the polymerization reaction and to minimize the thermal deterioration of the polycarbonate resin (A) due to the thermal history, a horizontal reaction excellent in plug flow property and interface renewability at the final stage of the reaction. It is preferable to use a vessel.

  In addition, in order to obtain a polycarbonate resin (A) having a high impact strength and obtaining a polycarbonate resin (A) having a high molecular weight, the polymerization temperature may be increased as much as possible to increase the polymerization time. Foreign matter and burns in the resin (A) are generated and tend to be brittlely broken. Therefore, in order to satisfy both the high impact strength and the difficulty of brittle fracture, the polymerization temperature is kept low, the use of a highly active catalyst for shortening the polymerization time, and the appropriate reaction system pressure setting. Etc. are preferably adjusted. 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 final stage of the reaction in order to prevent brittle fracture.

  In addition, when manufacturing polycarbonate resin (A) using substituted diphenyl carbonates, such as diphenyl carbonate and ditolyl carbonate, as carbonic acid diester represented by said Formula (6), phenol and substituted phenol are by-produced and polycarbonate. Residue in the resin (A) is unavoidable, but phenol and substituted phenol also have an aromatic ring, which absorbs ultraviolet rays and may cause deterioration of light resistance. It may be a cause. The polycarbonate resin (A) contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 ppm by weight or more after a normal batch reaction, but from the viewpoint of light resistance and odor reduction. The content of the aromatic monohydroxy compound in the polycarbonate resin (A) is preferably 700 ppm by weight or less, more preferably 500 ppm by weight, using a horizontal reactor excellent in devolatilization performance or an extruder with a vacuum vent. In the following, it is particularly preferable that the content be 300 ppm by weight or less. However, it is difficult to remove the aromatic monohydroxy compound completely industrially, and the lower limit of the content of the aromatic monohydroxy compound in the polycarbonate resin (A) is usually 1 ppm by weight. In addition, these aromatic monohydroxy compounds may naturally have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.

  In addition, Group 1 metals, especially lithium, sodium, potassium, cesium, especially sodium, potassium, cesium, may be mixed not only from the catalyst used but also from raw materials and reactors. Since it may adversely affect the hue if contained in a large amount in (A), the total content of these compounds in the polycarbonate resin (A) of the present invention is preferably as small as possible, and the polycarbonate resin (A) The amount of the metal is usually 1 ppm by weight or less, preferably 0.8 ppm by weight or less, more preferably 0.7 ppm by weight or less.

  The amount of metal in the polycarbonate resin (A) can be measured by various conventionally known methods. After recovering the metal in the polycarbonate resin (A) by a method such as wet ashing, atomic emission, It can be measured by using a method such as absorption, Inductively Coupled Plasma (ICP).

The polycarbonate resin (A) of the present invention 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. For example, the polycarbonate resin (A) is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand, and pelletized, and melted from the final polymerization reactor. The resin is supplied to a single-screw or twin-screw extruder in a state, melt-extruded, and then cooled and solidified to be pelletized, or extracted from the final polymerization reactor in a molten state, and cooled and solidified in the form of a strand once. Examples of the method include a method of supplying the resin again to the single-screw or twin-screw extruder after being pelletized, melt-extruding, and then cooling and solidifying to pelletize.
At that time, in the extruder, the residual monomer under reduced pressure devolatilization, and generally known heat stabilizers, neutralizers, UV absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, A plasticizer, a compatibilizer, a flame retardant, etc. can be added and kneaded.

  The melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate resin (A), 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 (A) is high, the load on the extruder is increased, and the productivity is lowered. When the temperature is higher than 300 ° C., the thermal degradation of the polycarbonate becomes severe, which causes a decrease in mechanical strength due to a decrease in molecular weight, coloring, generation of gas, generation of foreign matters, and further generation of burns. It is preferable to install a filter for removing the foreign matters and burns in the extruder or at the outlet of the extruder.

The size of the filter for removing foreign matter (aperture) is usually 400 μm or less, preferably 200 μm or less, particularly preferably 100 μm or less, with the goal of filtering accuracy of removing 99% or more of foreign matter. If the opening of the filter is excessively large, leakage may occur in the removal of foreign matters and burns, and when the polycarbonate resin (A) is molded, brittle fracture may occur. Moreover, the opening of the said filter can be adjusted according to the use of the thermoplastic resin composition of this invention. For example, when applied to film applications, the aperture of the filter is preferably 40 μm or less and more preferably 10 μm or less because of the requirement to eliminate defects.
Further, a plurality of the filters may be used in series, or a filtration device in which a plurality of leaf disk polymer filters are stacked may be used.

  Moreover, when cooling and pelletizing the melt-extruded polycarbonate resin (A), it is preferable to use cooling methods, such as air cooling and water cooling. The air to be used for air cooling should be air from which foreign substances in the air have been removed in advance using a HEPA filter (a filter specified in JIS Z8112), etc., to prevent the reattachment of foreign substances in the air. desirable. More preferably, it is preferably carried out in a clean room having a higher degree of cleanliness than class 7, as defined in JIS B 9920 (2002), and more preferably higher than class 6. 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 a filter of 10 to 0.45 μm is preferable.

  When the polycarbonate resin (A) of 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 phosphate and triethyl phosphate are preferably used. These are preferably added in an amount of 0.0001 mol% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol% or less, based on the total hydroxy compounds subjected to the reaction. preferable. When the addition amount of the phosphorus compound is less than the lower limit, the effect of preventing coloring is small, and when the addition amount is more than the upper limit, the transparency is lowered, or 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-tert-butylphenyl) phosphite, bis (2,4-di-tert-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% or more and 0.005 mol% or less, more preferably 0.0003 mol% or more and 0.003 mol%, based on the total hydroxy compounds subjected to the reaction. It is preferable to add below. 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 be reduced, or conversely, the coloring may be promoted or the heat resistance may be reduced. Sometimes.

  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, with respect to all the hydroxy compounds subjected to the reaction, 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 lower limit, the effect of preventing coloring is small, and if it is more than the upper limit, it may cause a decrease in transparency, or conversely promote coloring or reduce heat resistance. .

  In addition, the polycarbonate resin (A) produced in this manner may be blended with one or more thermal stabilizers in order to prevent a decrease in molecular weight and a deterioration in hue at the time of molding or the like. .

  Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof. Specifically, triphenyl phosphite, tris (nonylphenyl) phosphite, tris ( 2,4-di-tert-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-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di) -Tert Butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 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-tert-butylphenyl), dimethylbenzenephosphonate, Examples include diethyl benzenephosphonate and dipropyl benzenephosphonate. Among them, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and dimethyl benzenephosphonate are preferably used.

  Such a heat stabilizer can be further added in addition to the addition amount added at the time of melt polymerization. That is, after blending an appropriate amount of a phosphorous acid compound or phosphoric acid compound to obtain a polycarbonate resin (A), and further blending a phosphorous acid compound by the blending method described later, the transparency during polymerization is improved. More heat stabilizers can be blended while avoiding reduction, coloring, and heat resistance reduction, and hue deterioration can be prevented.

  The content of these heat stabilizers is preferably 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight, with respect to 100 parts by weight of the polycarbonate resin (A), and 0.001 to 0. More preferred is 2 parts by weight.

<Physical properties of polycarbonate resin (A)>
The preferred physical properties of the polycarbonate resin (A) of the present invention are shown below.

(Glass-transition temperature)
The polycarbonate resin (A) of the present invention has a glass transition temperature (Tg) of less than 145 ° C. When the glass transition temperature of the polycarbonate resin (A) is too high beyond this range, the polycarbonate resin (A) is likely to be colored, and it may be difficult to improve the impact strength. In this case, it is necessary to set the mold temperature high when transferring the shape of the mold surface to the molded product during molding. For this reason, the temperature controller that can be selected may be limited, or the transferability of the mold surface may be deteriorated.

The glass transition temperature of the polycarbonate resin (A) of the present invention is more preferably less than 140 ° C, and still more preferably less than 135 ° C.
The glass transition temperature of the polycarbonate resin (A) of the present invention is usually 90 ° C. or higher, preferably 95 ° C. or higher.

As a method of setting the glass transition temperature of the polycarbonate resin (A) of the present invention to less than 145 ° C., the proportion of the structural unit (a) in the polycarbonate resin (A) is reduced or used for the production of the polycarbonate resin (A). Examples of the dihydroxy compound include a method of selecting an alicyclic dihydroxy compound having low heat resistance or reducing the proportion of structural units derived from an aromatic dihydroxy compound such as a bisphenol compound in the polycarbonate resin (A). It is done.
In addition, the glass transition temperature of polycarbonate resin (A) of this invention is measured by the method as described in the below-mentioned Example.

(Reduced viscosity)
The degree of polymerization of the polycarbonate resin (A) of the present invention is such that a mixed solvent of phenol and 1,1,2,2, -tetrachloroethane in a weight ratio of 1: 1 is used as a solvent, and the concentration of the polycarbonate resin (A) is 1.00 g. As a reduced viscosity (hereinafter sometimes simply referred to as “reduced viscosity”), which is precisely adjusted to / dl and measured at a temperature of 30.0 ° C. ± 0.1 ° C., preferably 0.40 dl / g or more, Preferably it is 0.42 dl / g or more, and particularly preferably 0.45 dl / g or more, but 0.60 dl / g or more, further 0.85 dl / g or more may be suitably used. The reduced viscosity of the polycarbonate resin (A) of the present invention is preferably 2.0 dl / g or less, more preferably 1.7 dl / g or less, and particularly preferably 1.4 dl / g or less. If the reduced viscosity of the polycarbonate resin (A) is excessively low, the mechanical strength may be weakened. If the reduced viscosity of the polycarbonate resin (A) is excessively high, the fluidity at the time of molding is lowered, and the cycle characteristics. , The distortion of the molded product becomes large and tends to be deformed by heat.

[Additive for resin composition]
As described above, the polycarbonate resin (A) of the present invention can be made into the resin composition of the present invention by adding other additives within a range not impairing the spirit of the present invention.
Examples of such additives include antioxidants, acidic compounds or derivatives thereof, ultraviolet absorbers, light stabilizers, inorganic fillers, and the like. Furthermore, a nucleating agent, a flame retardant, an impact modifier, a foaming agent, and a dye / pigment that are usually used in the resin composition may be blended within a range that does not impair the spirit of the present invention.

  The antioxidant is preferably at least one selected from the group consisting of phenolic antioxidants, phosphite antioxidants and sulfur antioxidants, and phenolic antioxidants and / or phosphites. More preferred are system antioxidants.

  Examples of the phenolic antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-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-tert-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-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis ( 2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} And compounds such as -2,4,8,10-tetraoxaspiro (5,5) undecane.

  Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable. Specifically, octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and the like, preferably pentaerythritol- Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] A further preferred.

  Examples of the phosphite antioxidant include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-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-) tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaeri Li diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, and distearyl pentaerythritol phosphite.

  Among these, trisnonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and tris (2,4-di-tert-butylphenyl) phosphite is more preferred.

  Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, diester Stearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4- (3 -Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. Among the above, pentaerythritol tetrakis (3-lauryl thiopropionate) is preferable.

  When the resin composition of the present invention contains an antioxidant, the content of the antioxidant in the resin composition of the present invention is preferably 0.001 part by weight with respect to 100 parts by weight of the polycarbonate resin (A). Or more, more preferably 0.01 parts by weight or more, particularly preferably 0.05 parts by weight or more, on the other hand, preferably 1 part by weight or less, more preferably 0.7 parts by weight or less, particularly preferably 0.5 parts by weight. It is as follows. If the content of the antioxidant is excessively small, the coloring suppression effect during molding may be insufficient. In addition, if the content of the antioxidant is excessively large, the surface appearance of the obtained three-dimensional object may be impaired due to an increase in bleed deposits on the cooling roll when forming into a sheet by extrusion molding. is there.

  Examples of acidic compounds or derivatives thereof include hydrochloric acid, nitric acid, boric acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, adipic acid, ascorbic acid, aspartic acid, azelaic acid, and adenosine phosphorus. Acid, benzoic acid, formic acid, valeric acid, citric acid, glycolic acid, glutamic acid, glutaric acid, cinnamic acid, succinic acid, acetic acid, tartaric acid, oxalic acid, p-toluenesulfinic acid, p-toluenesulfonic acid, naphthalenesulfonic acid Bronsted acids such as nicotinic acid, picric acid, picolinic acid, phthalic acid, terephthalic acid, propionic acid, benzenesulfinic acid, benzenesulfonic acid, malonic acid, maleic acid, and esters thereof.

Among these acidic compounds or derivatives thereof, sulfonic acids or esters thereof are preferable, and p-toluenesulfonic acid, methyl p-toluenesulfonate, and butyl p-toluenesulfonate are particularly preferable.
These acidic compounds or derivatives thereof can be added in the resin composition production process as compounds that neutralize the basic transesterification catalyst used in the polycondensation reaction of the polycarbonate resin (A) of the present invention.

  When the acidic compound or derivative thereof is blended in the resin composition of the present invention, the blending amount of the acidic compound or derivative thereof in the resin composition is 0.00001 part by weight or more with respect to 100 parts by weight of the polycarbonate resin (A). .1 part by weight or less, preferably 0.0001 part by weight or more and 0.1 part by weight or less. If the amount of the acidic compound or derivative thereof is excessively small, coloring may not be sufficiently suppressed during extrusion molding. Moreover, when there are too many compounding quantities of an acidic compound or its derivative (s), a resin composition may become easy to hydrolyze.

  When an ultraviolet absorber or a light stabilizer is used in the resin composition of the present invention, an additive capable of absorbing light having a wavelength to be absorbed is appropriately selected, and the content thereof is 100 parts by weight of the polycarbonate resin (A). In general, it is preferably 0.01 to 5 parts by weight.

  Examples of inorganic fillers include glass cut fibers, glass milled fibers, glass flakes, silicon carbide, silicon nitride, calcium silicates, gypsum, gypsum whisker and other reinforcing materials, glass powder, silica, crosslinked acrylic powder, zeolite, and firing. Anti-blocking agents such as kaolin, metal powder, metal oxide powder and metal-coated glass powder made of aluminum, titanium, iron, copper, brass, etc., carbonaceous filler such as carbon fiber, activated carbon, carbon black, graphite, pigment, dye And the like. Conventionally known aromatic polycarbonate resins containing bisphenol A as a main monomer often have a problem that decomposition of the resin under heating and melting is accelerated when a part of a metal filler or a basic filler is mixed. The polycarbonate resin (A) of the invention is extremely unlikely to cause such problems, and has an advantage that a richer design can be imparted.

  When the inorganic filler is blended in the resin composition of the present invention, the blending amount varies greatly depending on the type and required performance, but usually 0.01 parts by weight or more and 100 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A). Part or less, preferably 0.01 part by weight or more and 50 parts by weight or less. When the blending amount of the inorganic filler is excessively small, the reinforcing effect is small, and when it is excessively large, the appearance tends to deteriorate.

  In addition, the resin composition of the present invention is, for example, an aromatic polycarbonate other than the polycarbonate resin (A), an aromatic polyester, an aliphatic polyester, a polyamide, as long as the gist of the present invention such as processability and transparency is not significantly impaired. Kneaded with one or more of polystyrene, polyolefin, acrylic resin, amorphous polyolefin, cyclic olefin resin, synthetic resin such as ABS, AS, biodegradable resin such as polylactic acid, polybutylene succinate, rubber, etc. It can also be used as a polymer alloy.

  Moreover, the resin composition of the present invention preferably contains at least one metal compound selected from the group consisting of a lithium compound and a metal of Group 2 of the long-period periodic table, and the content of the metal compound is The amount of metal is preferably 0.1 ppm by weight or more, more preferably 0.5 ppm by weight or more, and particularly preferably 0.7 ppm by weight or more. Further, the upper limit is preferably 20 ppm by weight, more preferably 10 ppm by weight, particularly preferably 3 ppm by weight, most preferably 1.5 ppm by weight, and most preferably 1.0 ppm by weight.

[Method for Producing Resin Composition]
The resin composition of the present invention comprises the polycarbonate resin (A) of the present invention and other ingredients such as other additives used as necessary at the same time or in any order in a tumbler, V-type blender, Nauter mixer, Banbury. It can manufacture by mixing with mixers, such as a mixer, a kneading roll, and an extruder.

[Physical properties of resin composition]
The resin composition of the present invention preferably has a deflection temperature under load at a bending stress of 1.80 MPa as measured in accordance with JIS K7191 of 70 ° C. or higher for applications requiring heat resistance such as containers. Moreover, it is preferable that it is 130 degrees C or less from the point that processing temperature conditions, such as a board | substrate, do not become high too much. As a minimum of this deflection temperature under load, 75 ° C or more is more preferred, and 80 ° C or more is still more preferred. Moreover, as an upper limit, 125 degrees C or less is more preferable, and 120 degrees C or less is further more preferable.

[Method of manufacturing a three-dimensional object]
A method for producing a three-dimensional object using the laminated deposition system by extrusion using the resin composition of the present invention as a raw material will be described in detail below.

[Raw material supply form]
The means for continuously supplying the raw material to the extrusion head of the laminated deposition system by extrusion is a method of supplying filaments or fibers by feeding, a method of supplying powder or liquid from a tank or the like via a quantitative feeder, pellets or granules Examples of the method include extruding and supplying the plasticized material with an extruder or the like, but from the viewpoint of the simplicity of the process and the supply stability, the method of feeding and supplying the monofilament is most preferable.

  When the raw material is supplied with a filament, it is preferable that it is housed in a cartridge wound in a bobbin shape from the viewpoint of stable feeding, protection from environmental factors such as moisture, and prevention of twisting and kinking. The cartridge preferably has a structure in which a moisture-proof material or a moisture-absorbing material is used inside, and at least a portion other than the orifice portion for feeding out the filament is sealed.

  The filament diameter depends on the ability of the system to be used, but is usually preferably 1.0 mm or more and 3.0 mm or less, and particularly preferably 1.5 mm or more and 2.0 mm or less. Further, it is preferable that the accuracy of the diameter is within an error of ± 5% with respect to an arbitrary measurement point of the filament from the viewpoint of the stability of the raw material supply.

  In general, when a filamentary raw material is supplied to a laminated deposition system by extrusion, the filament is often engaged with a driving roll such as a nip roll or a gear roll and supplied to the extrusion head while being pulled. Here, in order to stabilize the supply of raw materials by strengthening the grip by engagement between the filament and the drive roll, a minute uneven shape is transferred on the surface of the filament, or the frictional resistance with the engaging portion is reduced. The addition of an inorganic additive, a spreading agent, a pressure-sensitive adhesive, rubber or the like for increasing the size can also be preferably exemplified.

[Manufacture of three-dimensional objects]
In general, a laminated deposition system by extrusion is provided with a raw material supply unit such as a heatable base, an extrusion head installed in a gantry structure, a heating melter, a filament guide, and a filament cartridge installation unit in the chamber. In some cases, the heating and melting device is integrated.

  Since the extrusion head is installed in the gantry structure, it can be arbitrarily moved on the XY plane of the base. The platform is a platform that builds the target 3D object and support material, etc., and has specifications that can obtain adhesion to the laminate by heating and keeping warm, and improve the dimensional stability of the target 3D object preferable. At least one of the extrusion head and the base is movable in the Z-axis direction perpendicular to the XY plane.

  The raw material is fed out from the raw material supply unit and supplied to the extrusion head in a heated and melted state. In response to a signal transmitted based on the CAD model, the extrusion head feeds the raw material onto the substrate while moving its position, and deposits the layers. After this step is completed, the laminated deposit is taken out from the substrate, and a support material or the like is peeled off as necessary, or an excess portion is cut away to obtain a target three-dimensional object.

  The resin composition of the present invention has a temperature for obtaining fluidity suitable for extrusion, usually about 200 to 210 ° C., and a resin composition for producing a three-dimensional object using a conventional layered deposition system by extrusion. Therefore, in the method for producing a three-dimensional object of the present invention, the temperature of the heating extrusion head in the laminated deposition system by extrusion is 230 ° C. or less, for example, 200 to 210 ° C., and the base temperature is 80 ° C. or less. For example, a three-dimensional object can be stably produced at 60 to 70 ° C.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by the following examples unless the gist of the present invention is exceeded.

  The abbreviations of the compounds used in the description of the following examples are as follows.

<Raw material of polycarbonate resin (A)>
(Dihydroxy compound)
・ ISB: Isosorbide (Rocket Fleure)
CHDM: 1,4-cyclohexanedimethanol (manufactured by Shin Nippon Chemical Co., Ltd.)
(Carbonated diester)
・ DPC: Diphenyl carbonate (Mitsubishi Chemical Corporation)

<Additive of resin composition>
(Phosphite antioxidant)
AS2112: Tris (2,4-di-t-butylphenyl) phosphite (manufactured by ADEKA)
(Phenolic antioxidant)
IRGANOX 1010: Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan)

<Aromatic polycarbonate resin>
NOVAREX 7022R: Aromatic polycarbonate resin having a structure derived only from bisphenol A (manufactured by Mitsubishi Engineering Plastics)
<Acrylic resin>
・ ACRYPET VH (Mitsubishi Rayon Co., Ltd.)
<ABS resin>
-1.75 mm diameter filament (XYZ Printing Inc.)
<Polylactic acid resin>
・ A filament with a diameter of 1.75 mm (manufactured by 3Dom Filament)

[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 = 0.40 / 0.60 / 1.00 / 1.3 × 10 ⁻⁶ , and sufficiently purged with nitrogen (oxygen concentration 0.0005 vol% -0.001 vol%). 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 content thus oligomerized is 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 228 ° C. and the pressure was set to 133 Pa or less over 20 minutes. When the predetermined stirring power was reached, the pressure was restored, and a molten polycarbonate resin (A) was obtained from the outlet of the polymerization reactor.

Further, the polycarbonate resin (A) in the molten state is continuously supplied to a twin-screw extruder equipped with 3 vents and water injection equipment, and 0.1 parts by weight of “IRGANOX1010” and 0.05 parts by weight of “AS2112” In addition, the low-molecular weight product such as phenol is devolatilized under reduced pressure at each vent section provided in the twin-screw extruder, and then pelletized by a pelletizer to obtain the resin composition of the present invention. Pellets were obtained.
The obtained resin composition had a deflection temperature under load at a bending stress of 1.80 MPa, measured according to JIS K7191, of 78 ° C.

  Using a twin screw extruder equipped with a suction vent pump, the resulting resin composition pellets are melt extruded and taken so that the diameter of the strand (filament) having a substantially circular cross section is approximately 1.75 mm, and then cooled and solidified. After that, it was wound on a bobbin.

  As a laminated deposition system by extrusion, “da Vinci 1.0” manufactured by XYZ Printing Inc. of Taiwan was used to form a cup-shaped molded product having an opening above as a three-dimensional object. The manufacturing conditions were standard mode, and the temperature conditions of the extrusion head and substrate were as shown in Table 1. The moldability at this time and the appearance of the obtained three-dimensional object were evaluated, and the results are shown in Table 1.

[Example 2]
In Example 1, the charged composition at the time of producing the polycarbonate resin (A) is ISB / CHDM / DPC / calcium acetate monohydrate = 0.50 / 0.50 / 1.00 / 1.3 × 10 ⁻⁶ . Except for the above changes, pellets of the resin composition were obtained in the same manner as in Example 1.
Table 1 shows the deflection temperature under load at a bending stress of 1.80 MPa, measured according to JIS K7191.
Using the resin composition pellets, molding was performed in the same manner as in Example 1 under the temperature conditions shown in Table 1, and the evaluation results of moldability and appearance are shown in Table 1.

[Example 3]
In Example 1, the charged composition at the time of producing the polycarbonate resin (A) is ISB / CHDM / DPC / calcium acetate monohydrate = 0.70 / 0.30 / 1.00 / 1.3 × 10 ⁻⁶ . Except for the above changes, pellets of the resin composition were obtained in the same manner as in Example 1.
Table 1 shows the deflection temperature under load at a bending stress of 1.80 MPa, measured according to JIS K7191.
Using the resin composition pellets, molding was performed in the same manner as in Example 1 under the temperature conditions shown in Table 1, and the evaluation results of moldability and appearance are shown in Table 1.

[ Reference Example 4]
In Example 1, the charged composition at the time of producing the polycarbonate resin (A) is ISB / CHDM / DPC / calcium acetate monohydrate = 0.85 / 0.15 / 1.00 / 1.3 × 10 ⁻⁶ . Except for the above changes, pellets of the resin composition were obtained in the same manner as in Example 1.
Table 1 shows the deflection temperature under load at a bending stress of 1.80 MPa, measured according to JIS K7191.
Using the resin composition pellets, molding was performed in the same manner as in Example 1 under the temperature conditions shown in Table 1, and the evaluation results of moldability and appearance are shown in Table 1.

[Comparative Example 1]
In Example 1, NOVAREX 7022R (manufactured by Mitsubishi Engineering Plastics) was used in place of the resin composition pellets, and molding was performed under the temperature conditions shown in Table 1, and the evaluation results of moldability and appearance are shown in Table 1. .
Table 1 shows the deflection temperature under load at a bending stress of 1.80 MPa, measured according to JIS K 7191 of NOVAREX 7022R.

[Comparative Example 2]
In Example 1, ACRYPET VH (manufactured by Mitsubishi Rayon Co., Ltd.) was used in place of the resin composition pellets, and molding was performed under the temperature conditions shown in Table 1. Table 1 shows the evaluation results of moldability and appearance.
The deflection temperature under load at a bending stress of 1.80 MPa, measured according to JIS K7191 of ACRYPET VH, is as shown in Table 1.

[Comparative Example 3]
In Example 1, instead of the filament produced from the pellet of the resin composition, an ABS resin filament having a diameter of 1.75 mm (manufactured by XYZ Printing Incorporated) was used as it was, and molding was performed under the temperature conditions shown in Table 1. Table 1 shows the evaluation results of properties and appearance.
Table 1 shows the deflection temperature under load at a bending stress of 1.80 MPa, measured according to JIS K7191 for this ABS resin.

[Comparative Example 4]
In Example 1, a polylactic acid resin filament (manufactured by 3Dom Filament) having a diameter of 1.75 mm was used as it was instead of the filament produced from the pellet of the resin composition, and molding was performed under the temperature conditions shown in Table 1. Table 1 shows the evaluation results of the appearance.
In addition, the deflection temperature under load at a bending stress of 1.80 MPa, measured according to JIS K7191 for this polylactic acid resin, is as shown in Table 1.

Table 1 shows the following.
When the resin compositions of the present invention of Examples 1 to 3 are used, not only moldability but also an excellent appearance can be obtained with a relatively low heating extrusion head and base temperature. In Reference Example 4, the obtained molded product was somewhat hard and brittle.

Comparative Example 1 is an example using a commercially available aromatic polycarbonate resin, but the temperature of the extrusion head and the substrate must be set to a very high temperature, which requires not only equipment modification but also a support material. When molding in combination, there is a high risk of problems such as peeling failure due to extreme temperature differences.
Comparative Example 2 is an example using a commercially available acrylic resin, but it must be set at a relatively high temperature compared to the current ABS resin and polylactic acid resin, although it can be expected for transparency and color development, It does not lead to improvement of workability.

Comparative Example 3 is an example of a filament made of a commercially available ABS resin. However, since it shrinks greatly upon cooling, the molded product is deformed, and an object requiring dimensional accuracy or a relatively large object is obtained. Inappropriate.
Comparative Example 4 is an example of a filament made of a commercially available polylactic acid resin. Although it has the advantage of lowering the processing temperature, it is easy to break when peeled off from the substrate after molding or after handling because of its hard and brittle material. There was a bug. Moreover, the point which is hard to grind | polish and the point whose coating adhesiveness is inadequate are also known as a malfunction.

  The resin composition for producing a three-dimensional object using the laminated deposition system by extrusion of the present invention is excellent not only in moldability but also in the balance of material properties such as low shrinkage, high heat resistance, high transparency, and high surface hardness. By substituting from the conventionally used raw materials such as ABS resin, it contributes to various functions and improvement of defects.

Claims (3)

A resin composition for producing a three-dimensional object using a laminated deposition system by extrusion,
A structural unit (a) derived from a dihydroxy compound having a structure represented by the following general formula (1);
Containing a polycarbonate resin having a structural unit (b) derived from another dihydroxy compound ,
The proportion of the structural unit (a) in the total structural units derived from the dihydroxy compound contained in the polycarbonate resin is 40 mol% or more and 80 mol% or less,
The structural unit (b) is any structural unit selected from the group consisting of structural units derived from dihydroxy compounds represented by the following formulas (2) to (5),
It said resin composition, JIS K7191 was measured according to a resin composition deflection temperature under load of the bending stress 1.80MPa is characterized der Rukoto 70 ° C. or higher 125 ° C. or less.

HO—R ¹ —OH (2)
(In formula (2), R ¹ represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.)
HO—CH ₂ —R ² —CH ₂ —OH (3)
(In formula (3), R ² represents a substituted or unsubstituted cycloalkylene group having 4 to 20 carbon atoms.)
H- (O-R < ³ > ) _p- OH (4)
(In Formula (4), R ³ represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, and p is an integer of 2 to 100.)
^HO-R 4 -OH (5)
(In formula (5), R ⁴ represents a substituted or unsubstituted alkylene group having 2 to 20 carbon atoms, or a group having a substituted or unsubstituted acetal ring.) A method for producing a three-dimensional object using a laminate deposition system by extrusion, wherein the resin composition according to claim 1 is used as a raw material, and a temperature of a heating extrusion head in the laminate deposition system by extrusion is set to 230 ° C. A method for producing a three-dimensional object, characterized in that the three-dimensional object is produced by setting. A method for producing a three-dimensional object using a laminated deposition system by extrusion, wherein the resin composition according to claim 1 is used as a raw material, and a base temperature in the laminated deposition system by extrusion is set to 80 ° C or lower. A method for producing a three-dimensional object, comprising producing a three-dimensional object.