JP2013018977A - Injection molding material, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an injection molding material having high flowability at the injection molding and obtainable of a molded product having high impact strength, and a method for producing the same.SOLUTION: The injection molding material comprises a resin composition containing 40-90 mass% polycarbonate resin having a branching degree of 0.35-0.55 [nm/(g/mol)] and weight-average molecular weight of 10,000-80,000 and 5-30 mass% thermoplastic polyester resin having weight-average molecular weight of 10,000-50,000. The method for producing the injection molding material is carried out by melt kneading a raw material containing (A) the polycarbonate resin having a branching degree of 0.35-0.55 [nm/(g/mol)] and weight-average molecular weight of 10,000-80,000 and (B) the thermoplastic polyester resin having weight-average molecular weight of 10,000-50,000 and after that, carrying out a gap-passing treatment for passing the raw material through a slit having ≤5 mm gap distance.

Description

  The present invention relates to an injection molding material comprising a resin composition containing a polycarbonate resin and a polyester resin, and a method for producing the same.

  Currently, resins such as polycarbonate resins and thermoplastic polyester resins and their resin compositions are used in containers from the viewpoints of excellent moldability, mechanical properties, heat resistance, weather resistance, appearance, hygiene, and economy. It is used in a wide range of fields as molding materials for packaging films, home appliances, OA equipment, AV equipment, electrical / electronic parts, and automobile parts. Therefore, the amount of the thermoplastic resin and the molded product of the resin composition used is large, and is increasing year by year. Therefore, the amount of molded articles that have been used and discarded is increasing, which is a serious social problem.

  In recent years, laws such as “Act on the Promotion of Separate Collection and Recycling Related to Containers and Packaging (Container and Packaging Recycling Law)” and “Act on Promotion of Procurement of Environmental Goods by the Countries (Green Purchasing Law)” With successive enforcement, interest in material recycling technology for molded articles of such thermoplastic resins and resin compositions has increased. In particular, there is an urgent need to establish a material recycling technology for PET bottles using polyethylene terephthalate (hereinafter also referred to as “PET”) resin, whose usage is rapidly increasing. In addition, with the widespread use of optical recording medium products (optical discs) made of polycarbonate resin such as CD, CD-R, DVD, MD, etc., methods for recycling scraps and wastes generated during these molding processes A method for reusing a polycarbonate resin obtained after peeling off a reflective layer, a recording layer, and the like from an optical disk is now being studied.

  Polycarbonate resin basically has excellent impact resistance, but once it is molded, it is affected by the heat history during molding, resulting in a low molecular weight and sufficient impact strength in the molded product. It may not be possible. Further, when a molded product of such a low molecular weight polycarbonate resin is pulverized and used again as a recycled resin, there is a problem that the impact strength of the molded product is further reduced.

  In addition, the polycarbonate resin has a problem that it does not have good fluidity due to the molding temperature, and good moldability cannot be obtained.

  For example, Patent Document 1 proposes to lower the molecular weight of a polycarbonate resin in order to improve the fluidity of the polycarbonate resin. However, depending on this method, there is a problem that the impact strength of a molded product is lowered. .

  For example, Patent Document 2 proposes that a polyester resin is copolymerized in a polymer alloy of a polycarbonate resin and a polyester resin in order to improve fluidity while maintaining the impact strength of the polycarbonate resin. However, a resin composition having sufficient fluidity has not yet been obtained.

JP-A 62-297319 JP 2011-16950 A

  The present invention has been made in view of the circumstances as described above, and an object thereof is an injection molding material having high fluidity at the time of injection molding, and capable of obtaining high impact strength in a molded product, and It is in providing the manufacturing method.

The injection molding material of the present invention has a degree of branching in the molecule of 0.35 to 0.55 [nm / (g / mol)], and a polycarbonate resin having a weight average molecular weight of 10,000 to 80,000 is 40 to 90. Contained in a proportion of mass%,
It is characterized by comprising a resin composition containing a thermoplastic polyester resin having a weight average molecular weight of 10,000 to 50,000 in a proportion of 5 to 30% by mass.

In the injection molding material of the present invention, the polycarbonate resin preferably has a weight average molecular weight of 12,000 to 50,000.
In the injection molding material of the present invention, the polyester resin preferably has a weight average molecular weight of 15,000 to 40,000.
Furthermore, in the injection molding material of the present invention, the polycarbonate resin preferably has a degree of branching of 0.39 to 0.53 [nm / (g / mol)].

  In the method for producing an injection molding material of the present invention, (A) the degree of branching in the molecule is 0.35 to 0.55 [nm / (g / mol)], and the weight average molecular weight is 10,000 to 80,000. A gap passing treatment is performed in which a raw material containing a polycarbonate resin and (B) a thermoplastic polyester resin having a weight average molecular weight of 10,000 to 50,000 is melted and kneaded and then passed through a slit having a gap distance of 5 mm or less. It is characterized by giving.

According to the injection molding material of the present invention (hereinafter, also simply referred to as “molding material”), the molding material has a branched structure in which the degree of branching is within a specific range, and the weight average molecular weight is within a specific range. Polycarbonate resins (hereinafter also referred to as “specific polycarbonate resins”) and thermoplastic polyester resins having a weight average molecular weight within a specific range (hereinafter also referred to as “specific polyester resins”) have specific ratios. When the resin composition is contained in the resin composition, high fluidity can be obtained at the time of injection molding, and high impact strength can be obtained in the molded product.
Further, even when the molded product molded by the molding material of the present invention is pulverized and used again as a recycled molding material, the initial molding material is a resin composition containing a specific polycarbonate resin and a specific polyester resin. As a result, high fluidity can be obtained at the time of injection molding, and the impact strength in the molded product can be sufficiently maintained.

  According to the method for producing a molding material of the present invention, it is possible to produce a molding material capable of obtaining high impact strength in a molded product by performing a specific gap passage treatment.

It is explanatory drawing which shows one structural example of the apparatus (die | dye) used for the specific clearance passage process in the manufacturing method of the molding material of this invention, (a) is a perspective top view, (b) is PQ It is line sectional drawing.

  Hereinafter, the present invention will be described in detail.

  The molding material of the present invention is for injection molding and comprises a resin composition containing (A) a specific polycarbonate resin and (B) a specific polyester resin as essential components.

[(A) Polycarbonate resin]
A specific polycarbonate resin (hereinafter also referred to as “component (A)”) is a main component constituting the molding material of the present invention.
The specific polycarbonate resin as the component (A) has a branched structure with a degree of branching of 0.35 to 0.55 [nm / (g / mol)], and a weight average molecular weight of 10,000 to 80,000. , 40 to 90% by mass.
In the molding material of the present invention, since a specific polycarbonate resin is contained, the specific polycarbonate resin has a branched structure. Therefore, even if the molecular weight is reduced due to the influence of heat history during injection molding, Compared with the chain structure, it has a higher viscosity, and therefore a high impact strength can be obtained in the molded product.

  As specific polycarbonate resin, what is obtained by reacting dihydric phenol and a carbonate precursor can be used. As a method for producing such a polycarbonate resin, a known method can be employed. For example, a dihydric phenol, such as phosgene, as a raw material, a branching agent or a molecular weight regulator is added and polymerized ( Interfacial polymerization method).

  Examples of the dihydric phenol for forming a specific polycarbonate resin include hydroquinone, resorcin, dihydroxydiphenyl, bis (hydroxyphenyl) alkane, bis (hydroxyphenyl) cycloalkane, bis (hydroxyphenyl) sulfide, and bis (hydroxyphenyl). ) Ether, bis (hydroxyphenyl) ketone, bis (hydroxyphenyl) sulfone, bis (hydroxyphenyl) sulfoxide, bis (hydroxyphenyl) benzene, and derivatives thereof in which the nucleus is substituted with an alkyl group or a halogen atom are used. be able to. Representative examples of particularly suitable dihydric phenols include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2, 2-bis {(3,5-dibromo-4-hydroxy) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfone, bis {(3,5-dimethyl-4-hydroxy) phenyl} sulfone, etc. Two or more kinds can be mixed and used. Among these, it is particularly preferable to use bisphenol A.

  Examples of the carbonate precursor for forming a specific polycarbonate resin include diaryl carbonates such as diphenyl carbonate, ditoluyl carbonate, bis (chlorophenyl) carbonate, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, and carbonyl halides such as phosgene, A haloformate such as dihaloformate of dihydric phenol can be used, but is not limited thereto. Of these, diphenyl carbonate is preferred. These carbonate precursors can also be used alone or in combination of two or more.

Examples of the branching agent for forming a specific polycarbonate resin include trifunctional or higher polyfunctional compounds such as 1,3,5-trihydroxybenzene (phloroglucin), 4,6-dimethyl-2,4, and the like. 6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4- Polyhydroxy compounds such as hydroxyphenyl) heptene-3,1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane; 3,3-bis ( 4-hydroxyaryl) oxyindole, 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred. These branching agents can be used alone or in combination of two or more.
It is preferable that the addition amount of a branching agent is 0.01-10 mass% with respect to a bihydric phenol, More preferably, it is 0.1-3 mass%.

  Examples of the molecular weight modifier for forming a specific polycarbonate resin include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like. Phenol is preferred. For example, alkyl group-substituted phenols such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol; vinyl groups such as isopropanylphenol -Containing phenol; epoxy group-containing phenol; carboxyl group-containing phenol such as 0-oxinebenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; These molecular weight modifiers can be used alone or in combination of two or more.

  Specific examples of the specific polycarbonate resin include “Taflon” (manufactured by Idemitsu Kosan Co., Ltd.), “Iupilon” (manufactured by Mitsubishi Engineering Plastics), and the like.

  In addition, as the specific polycarbonate resin, a polycarbonate resin obtained from a molded product that has been used and discarded (hereinafter also referred to as “recycled polycarbonate resin”) can be used.

(Degree of branching)
The degree of branching of the specific polycarbonate resin is 0.35 to 0.55 [nm / (g / mol)] on average, and more preferably 0.39 to 0.53 [nm / (g / mol)]. It is said.
In the present invention, the degree of branching of a specific polycarbonate resin refers to the radius of rotation (nm) and molecular weight (g / mol) measured using GPC (gel permeation chromatography) -MALS (multi-angle light scattering detector). ) Is a slope of a straight line (hereinafter also referred to as “rotational radius-molecular weight logarithmic straight line”) obtained by plotting on a log-log graph having a radius of rotation on the vertical axis and a molecular weight on the horizontal axis. With this slope, the size of the molecule relative to the molecular weight can be estimated, and this value is taken as the degree of branching. In the present invention, the degree of branching refers to an average value of ten log samples obtained from a logarithmic radius-molecular weight logarithmic straight line.
In the case of using a polycarbonate resin having an excessively low degree of branching, a sufficiently high impact strength cannot be obtained in a molded product. On the other hand, when a polycarbonate resin having an excessive branching degree is used, excellent fluidity cannot be obtained during molding.

In the present invention, the degree of branching (rotation radius—slope of molecular weight logarithmic straight line) is measured and calculated by the following method and conditions.
[GPC conditions]
(apparatus)
Apparatus: GPC HLC-8220 (manufactured by Tosoh Corporation)
Column: TSK guard column + TSK gel SuperHZM-M3 series (manufactured by Tosoh Corporation)
(Measurement condition)
Sample preparation: 1.0 mg of the resin to be measured is dissolved in 1.0 ml of tetrahydrofuran at room temperature Carrier solvent: Tetrahydrofuran (THF)
Column temperature: maintained at 40 ° C. Flow rate: 0.2 ml / min
Sample injection: 10 μL of the solution is injected into the apparatus together with the carrier solvent (molecular weight).
Detection: Refractive index detector (RI detector)
Molecular weight: The molecular weight is calculated using a calibration curve obtained by measuring the molecular weight distribution of the measurement object using monodisperse polystyrene standard particles. As a standard polystyrene sample for preparing a calibration curve, the molecular weight of “Pressure Chemical Co., Ltd.” is 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ^4. 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and measuring at least about 10 standard polystyrene samples, Create a calibration curve.
Under the above GPC conditions, a GPC-MALS measurement is performed using a multi-angle light scattering detector (MALS detector) “DAWN HELEOS II” (manufactured by Wyatt Technology), whereby the inclination of the logarithmic straight line of the radius of rotation and the molecular weight is obtained. Calculated.
Theoretically, a linear molecule has an inclination of the logarithmic straight line of the radius of rotation and molecular weight of 1, and the smaller the inclination, the higher the degree of branching.

(Weight average molecular weight)
The weight average molecular weight of the specific polycarbonate resin is 10,000 to 80,000, and more preferably 12,000 to 50,000.
When a polycarbonate resin having an excessively low weight average molecular weight is used, high impact strength cannot be obtained in a molded product. On the other hand, when a polycarbonate resin having an excessive weight average molecular weight is used, excellent fluidity cannot be obtained during molding.

In the present invention, the weight average molecular weight of the polycarbonate resin is measured by GPC (gel permeation chromatography) under the following methods and conditions.
(apparatus)
Apparatus: GPC HLC-8220 (manufactured by Tosoh Corporation)
Column: TSK guard column + TSK gel SuperHZM-M3 series (manufactured by Tosoh Corporation)
(Measurement condition)
Sample preparation: 1.0 mg of the resin to be measured is dissolved in 1.0 ml of tetrahydrofuran at room temperature Carrier solvent: Tetrahydrofuran (THF)
Column temperature: maintained at 40 ° C. Flow rate: 0.2 ml / min
Sample injection: 10 μL of the solution is injected into the apparatus together with the carrier solvent (molecular weight).
Detection: Refractive index detector (RI detector)
Molecular weight: The molecular weight is calculated using a calibration curve obtained by measuring the molecular weight distribution of the measurement object using monodisperse polystyrene standard particles. As a standard polystyrene sample for preparing a calibration curve, the molecular weight of “Pressure Chemical Co., Ltd.” is 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ^4. 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and measuring at least about 10 standard polystyrene samples, Create a calibration curve.

[(B) Polyester resin]
A specific polyester resin (hereinafter also referred to as “component (B)”) is an essential component constituting the molding material of the present invention.
The specific polyester resin as the component (B) is a thermoplastic having a weight average molecular weight of 10,000 to 50,000.
In the molding material of the present invention, by containing a specific polyester resin as the component (B) together with the component (A), the resin composition has more excellent moldability.

As the specific polyester resin, specifically, a polyester resin obtained from a molded product that has been used and discarded (hereinafter, also referred to as “regenerated polyester resin”) can be used.
Moreover, as a specific polyester resin, what is obtained by polycondensing a derivative having dicarboxylic acid or ester-forming ability and a diol or ester-forming ability by a known method can also be used.

  Specific examples of the dicarboxylic acid for forming a specific polyester resin include, for example, terephthalic acid, isophthalic acid, orthophthalic acid, 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4 ' -Biphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid , Aromatic dicarboxylic acids such as sodium 5-sulfoisophthalate, adipic acid, sebacic acid, succinic acid, azelaic acid, malonic acid, succinic acid, dodecanedioic acid and other aliphatic dicarboxylic acids, 1,3-cyclohexanedicarboxylic acid, 1 Fats such as 1,4-cyclohexanedicarboxylic acid Wherein the dicarboxylic acids and their ester-forming derivatives (e.g. methyl ester, such as lower alkyl esters such as ethyl ester), and dicarboxylic acids derived from such.

  Specific examples of the diol for forming the specific polyester resin include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, Aliphatic diols having 2 to 10 carbon atoms such as 1,3-butanediol, 1,6-hexanediol, 1,10-decanediol, neopentyl glycol, 2-methylpropanediol, 1,5-pentadiol, Derived from alicyclic diols such as 4-cyclohexanedimethanol and 1,4-cyclohexanediol, polyalkylene glycols having a molecular weight of 6000 or less, such as diethylene glycol, polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol. Diol is It is below.

  Both of these dicarboxylic acids and diols can be used alone or in combination of two or more. Furthermore, the polyester resin has a structure derived from a tri- or higher functional monomer such as glycerin, trimethylolpropane, pentaerythritol, trimellitic acid, or pyromellitic acid, as long as it is 1 mol% or less based on the total structural unit. You may have a component.

  The specific polyester resin is obtained by polycondensation of an aromatic dicarboxylic acid or a derivative having an ester forming ability and an aliphatic diol or an ester forming ability from the viewpoint of further improving impact strength and flame retardancy. An aromatic polyester resin is preferred.

  Specific examples of the specific polyester resin include, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate, poly-1,4-cyclohexanedimethylene terephthalate. , Polycaprolactone, p-hydroxybenzoic acid-based polyester, polyarylate-based resin, and the like. Among these, PET and PEN using ethylene glycol as the diol component are particularly preferable from the viewpoint of balance of physical properties such as crystallization behavior, thermal properties, and mechanical properties.

(Weight average molecular weight)
The weight average molecular weight of the specific polyester resin is 10,000 to 50,000, more preferably 15,000 to 40,000.
When a polyester resin having an excessively low weight average molecular weight is used, the impact strength of the molded product may be reduced due to the low viscosity. On the other hand, when a polyester resin having an excessive weight average molecular weight is used, the fluidity may be lowered during molding because the viscosity is high.

In the present invention, the weight average molecular weight of the polyester resin is measured by GPC (gel permeation chromatography) under the following methods and conditions.
(apparatus)
Apparatus: GPC HLC-8220 (manufactured by Tosoh Corporation)
Column: TSK guard column + TSK gel SuperHZM-M3 series (manufactured by Tosoh Corporation)
(Measurement condition)
Sample preparation: 1.0 mg of the resin to be measured is dissolved in 1.0 ml of tetrahydrofuran at room temperature Carrier solvent: Tetrahydrofuran (THF)
Column temperature: maintained at 40 ° C. Flow rate: 0.2 ml / min
Sample injection: 10 μL of the solution is injected into the apparatus together with the carrier solvent (molecular weight).
Detection: Refractive index detector (RI detector)
Molecular weight: The molecular weight is calculated using a calibration curve obtained by measuring the molecular weight distribution of the measurement object using monodisperse polystyrene standard particles. As a standard polystyrene sample for preparing a calibration curve, the molecular weight of “Pressure Chemical Co., Ltd.” is 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ^4. 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and measuring at least about 10 standard polystyrene samples, Create a calibration curve.

The IV value (intrinsic viscosity) of the specific polyester resin is preferably 0.65 to 1.00, more preferably 0.80 to 0.90.
When the IV value of a specific polyester resin is too small, high impact strength cannot be obtained in the molded product, and chemical resistance may be lowered. On the other hand, when the IV value of a specific polyester resin is excessive, the flow viscosity increases at the time of molding, and the kneading temperature is set high in the later-described (I) melting / kneading treatment. In addition, the polyester resin may have a large amount of terminal groups, resulting in a decrease in thermal stability, resulting in a decrease in molecular weight and a decrease in impact strength in the molded product.

  In the present invention, the IV value of the polyester resin is a value when measured at 30 ° C. using a phenol / tetrachloroethane (mass ratio: 1/1) mixed solvent.

(Resin composition)
In the resin composition constituting the molding material of the present invention, the content of the specific polycarbonate resin is 40 to 90% by mass, more preferably 45 to 85% by mass with respect to the total amount of the molding material. Content of a polyester resin is 5-30 mass% with respect to the molding material whole quantity, More preferably, it is 10-30 mass%.
When the content of the specific polycarbonate resin and the specific polyester resin is within the above range, both high fluidity during injection molding and high impact strength in the molded product can be achieved.
When the content of the specific polycarbonate resin is too small, the impact strength in the molded product becomes insufficient.
Moreover, when content of specific polyester resin is excessive, the fluidity | liquidity at the time of injection molding falls.

  In the resin composition in the present invention, the mass ratio of the specific polycarbonate resin as the component (A) and the specific polyester resin as the component (B) is (A) component: (B) component = (15: 1) to (2: 1) are preferable.

In the resin composition constituting the molding material of the present invention, in addition to the component (A) and the component (B), other resin components can be blended within the range in which the object of the present invention is achieved. Examples of other resin components include polyethylene resin and ABS resin. Moreover, arbitrary components can be mix | blended with the molding material of this invention as needed. Optional components include, for example, flame retardants (such as sulfonate compounds), crosslinking agents (such as phenolic resins), pigments, dyes, reinforcing materials (glass fibers, carbon fibers, talc, mica, clay minerals, potassium titanate) Fiber, etc.), filler (titanium oxide, metal powder, wood powder, rice husk, etc.), heat stabilizer, oxidative degradation inhibitor, ultraviolet absorber, lubricant, mold release agent, crystal nucleating agent (eg GMA-MA-PE, etc.) ), Plasticizers, flame retardants, antistatic agents, foaming agents and the like.
The content of the other resin component is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, based on the total amount of the molding material. Moreover, it is preferable that content of an arbitrary component is 1-30 mass% with respect to the molding material whole quantity, More preferably, it is 1-20 mass%.

According to the molding material of the present invention, the molding material has a branched structure having a branching degree within a specific range, and a specific polycarbonate resin having a weight average molecular weight within a specific range and a specific polyester resin, respectively. By comprising the resin composition contained at a specific ratio, high fluidity can be obtained at the time of injection molding, and high impact strength can be obtained in the molded product.
Further, even when the molded product molded by the molding material of the present invention is pulverized and used again as a recycled molding material, the initial molding material is a resin composition containing a specific polycarbonate resin and a specific polyester resin. As a result, high fluidity can be obtained at the time of injection molding, and the impact strength in the molded product can be sufficiently maintained.

[Method of manufacturing molding material]
The method for producing a molding material of the present invention comprises melting and kneading a raw material containing at least a specific polycarbonate resin as the component (A) and a specific polyester resin as the component (B), and then the gap distance is 5 mm or less. A gap passing process for passing through the slit is performed.
Specifically, (I) a raw material containing at least the component (A) and the component (B) is melted and kneaded, (II) the obtained molten raw material is subjected to a gap passing process, III) A molding material is obtained by cooling.
The molding material thus obtained is generally made into a pellet by, for example, cutting with a pelletizer after cooling treatment (III) in order to facilitate processing during molding by injection molding. The

(I) Melting / kneading treatment The melting / kneading treatment is performed, for example, by using an extrusion kneader. Such an extrusion kneader is not particularly limited, and a known extrusion kneader using a shearing force can be used. For example, a twin screw extrusion kneader “KTX30” (manufactured by Kobe Steel), “KTX46” ( Kobe Steel Corporation).
Melting / kneading conditions are not particularly limited. For example, the screw rotation speed is 50 to 1000 rpm, and the melting / kneading temperature is 150 to 500 ° C., for example.

(II) Gap-passing process The gap-passing process is performed by passing the molten raw material through a slit having a gap distance of 5 mm or less after melting and kneading.
In the method for producing a molding material according to the present invention, when the molding material obtained is molded by an injection molding method by performing a gap passage treatment for passing through a slit having a gap distance of 5 mm or less, the impact strength in the molded product Will be improved.

In the method for producing a molding material of the present invention, it is preferable to perform the gap passing treatment once or more, preferably 2 times or more, more preferably 3 times or more.
As the number of times of the gap passing process is increased, the impact strength in the molded product is significantly improved. The upper limit of the number of times of the gap passing process is usually 1000 times. It is possible to reduce the number of times the gap passing process is performed after kneading with a single-screw or twin-screw extruder kneader. For example, the gap passing process is continuously performed with a device attached to the discharge port of the twin-screw extruder kneader. In some cases, the number of times can be reduced from 3 to 10 times.

The gap distance between the slits is 5 mm or less, preferably 1 to 3 mm. For example, in the case of using an apparatus having two or more slits, the gap distances are each independently 5 mm or less, more preferably 1 to 3 mm.
When the gap distance between the slits exceeds 5 mm, the impact strength of the molded product may not be improved.

  Hereinafter, as a specific example of the gap passing process, a method using an apparatus having two slits in series with a gap distance of 5 mm or less will be described.

FIG. 1 is an explanatory view showing one configuration example of an apparatus (die) used for a specific gap passage process in the method for producing a molding material of the present invention, wherein (a) is a perspective plan view, and (b) is a perspective view. It is a PQ line sectional view.
This apparatus 10A includes a substantially rectangular parallelepiped housing, and includes an inflow port 5 for inflowing raw materials and an outflow port 6 for discharging processed material (molding material). In the raw material flow path between the two slits (2a, 2b) formed between two parallel planes.
Immediately before each of the slits 2a and 2b, there are reservoir portions 1a and 1b having a cross-sectional area larger than that of the slits 2a and 2b.

  This apparatus 10A connects the inlet 5 to a discharge port of an extrusion kneader (not shown), thereby using the pushing force of the extrusion kneader as a driving force for moving the raw material in the molten state. As a whole, it can be moved in the movement direction MD and can pass through the slits 2a and 2b. Thus, since apparatus 10A can be used by being connected to the discharge port of an extrusion kneader, it can also be called a die.

  The raw material flows into the pool portion 1a from the inflow port 5 and spreads in the width direction WD. The raw material filled in the reservoir 1a passes through the slit 2a and moves to the reservoir 1b, and then passes through the slit 2b and is discharged from the discharge port 6.

Gap distance x ₁ in the slit 2a is specifically a 3 mm, the gap distance x ₂ in the slit 2b is specifically a 3 mm.

The distances y ₁ and y ₂ in the movement direction MD in the slits 2a and 2b are preferably independently ₂ to 200 mm, more preferably 5 to 50 mm.
The distance y ₁ in the movement direction MD in the slit 2a is specifically 50 mm, and the distance y ₂ in the movement direction MD in the slit 2b is specifically 40 mm.

The distance z ₁ in the width direction WD in the slits 2a and 2b is preferably 10 to 500 mm, more preferably 50 to 300 mm, and specifically 250 mm.

The maximum heights h ₁ and h ₂ in the reservoir portions 1a and 1b are preferably 3 to 150 mm, more preferably 5 to 100 mm, and specifically 50 mm.
In the present invention, the maximum height of the reservoir portion refers to the maximum height in a vertical section with respect to the width direction WD.

The distance m ₁ in the movement direction MD in the pool part 1a and the distance m ₂ in the movement direction MD in the pool part 1b may be 1 mm or more independently, preferably 2 mm or more, more preferably 5 mm from the viewpoint of efficiency. More preferably, it is 10 mm or more, specifically 100 mm. The upper limit of the distance m ₁ and m _2, is not particularly limited, the distance m ₁ and when m ₂ is too large, an extrusion kneading machine efficiency is connected to the inlet 5 with reduced It is necessary to increase the pushing force. Accordingly, the distances m ₁ and m ₂ are each preferably preferably 1 to 300 mm, more preferably 2 to 100 mm, and still more preferably 5 to 50 mm.

Sectional area S _2a of the slit 2a and the cross-sectional area S _2b of the ratio S _1a / S _2a and the slit 2b of the maximum cross-sectional area S _1a of the immediately preceding reservoir 1a and the maximum cross-sectional area S _1b of the immediately preceding reservoir 1b The ratio S _1b / S _2b is usually independently 1.1 or more, particularly 1.1 to 1000. From the viewpoint of more uniform mixing / dispersion, downsizing of the apparatus, and prevention of vent-up, 2 -100 is preferable, More preferably, it is 3-15.

Feedstock slit 2a, the flow rate as it passes through 2b, as long 1 g / min or more in the value of the cross-sectional area 1 cm ² per slit, preferably 10~5000g / min, more preferably 10 to 500 g / min is there.

In the present invention, the cross-sectional area means an area in a vertical cross section with respect to the moving direction MD.
In the present invention, the flow velocity is measured by dividing the discharge amount (g / min) of the raw material discharged from the discharge port by the cross-sectional area (cm ² ) of the gap.

The viscosity of the raw material during the gap passing treatment is not particularly limited as long as the flow velocity during the gap passing is achieved, but is, for example, 1 to 10000 Pa · s, preferably 10 to 8000 Pa · s.
In the present invention, the viscosity of the raw material is measured by a viscoelasticity measuring device “MARS” (manufactured by Harker).

  The pressure for moving the raw material in the movement direction MD is not particularly limited as long as the flow velocity at the time of passing through the gap is achieved, but is preferably 0.1 MPa or more as the resin pressure indicated by the differential pressure from the atmospheric pressure. The resin pressure is the pressure of the raw material measured 1 mm or more inside from the raw material discharge port in the slit, and is measured by directly measuring with a pressure gauge. The higher the pressure, the more effective, but if the resin pressure is too high, significant shearing heat is generated and the resin may be decomposed. Therefore, the resin pressure is preferably 500 MPa or less, more preferably 50 MPa or less.

The temperature of the raw material during the gap passing treatment is not particularly limited as long as the flow velocity during the gap passing is achieved, but is preferably 400 ° C. or lower because the resin is decomposed at a high temperature exceeding 400 ° C. Further, it is preferable that the temperature of the raw material during the gap passing treatment is equal to or higher than the glass transition temperature (Tg) of the raw material because the resin pressure does not increase remarkably.
The temperature of the raw material during the gap passing process can be controlled by adjusting the heating temperature of the apparatus that performs the process.

(III) Cooling treatment The cooling treatment is not particularly limited, for example, a method of immersing in water of 0 to 60 ° C, a method of cooling with a gas of -40 ° C to 60 ° C, or a metal of -40 ° C to 60 ° C. This is done by the method of Further, for example, it may be performed by a method of leaving and cooling as it is.

  The molding material thus obtained is usually cut by a pelletizer in order to facilitate processing during molding by the injection molding method.

In order to obtain the molding material of the present invention, a premixing process in which all components constituting the raw material are mixed in advance may be performed prior to (I) the melting and kneading process.
In addition, after the premixing treatment, it is preferable to sufficiently dry the raw material from the viewpoint of suppressing the hydrolysis reaction of the specific polyester resin before (I) melting and kneading treatment.

  According to the method for producing a molding material of the present invention, it is possible to produce a molding material capable of obtaining high impact strength in a molded product by performing a specific gap passage treatment.

[Production Example 1 of Polycarbonate Resin]
In a container with a stirrer having an internal volume of 50 liters, 0.043 mol of phloroglucinol, 9.2 mol of bisphenol A, 9 liters of a 2.0N aqueous sodium hydroxide solution and 8 liters of dichloromethane were stirred and phosgene was blown into the vessel for 30 minutes. . Next, 0.44 mol of bisphenol A, 0.022 mol of triethylamine and 4.5 liter of 0.2N aqueous sodium hydroxide solution were added and reacted for 40 minutes, and then the aqueous phase and the organic phase were separated. In this way, a dichloromethane solution of polycarbonate oligomer was obtained. In the obtained polycarbonate oligomer, 0.44 mol of tert-butylphenol was dissolved, 335 g of sodium hydroxide and 2.2 mol of bisphenol A were dissolved in 4.5 liter of water, 0.017 mol of triethylamine and 6 liters of dichloromethane were added, The mixture was stirred at a rotation speed of 500 rpm and reacted for 60 minutes. After the reaction, the aqueous phase and the organic phase are separated, and the organic phase is washed with water, 0.03N aqueous sodium hydroxide solution, 0.2N hydrochloric acid and water in this order, and after washing, dichloromethane is removed to obtain a polycarbonate resin [1]. It was. The polycarbonate resin [1] had a branched structure, the degree of branching was 0.47 [nm / (g / mol)], and the weight average molecular weight was 15,000.

[Production Example 2 of Polycarbonate Resin]
Polycarbonate resin [2] was obtained in the same manner as in Production Example 1 for polycarbonate resin, except that the amount of tert-butylphenol added was changed to 0.35 mol. The degree of branching of this polycarbonate resin [2] was 0.47 [nm / (g / mol)]. Table 1 shows the weight average molecular weight of the polycarbonate resin [2].

[Production Example 3 of Polycarbonate Resin]
In polycarbonate resin production example 1, polycarbonate resin [3] was obtained in the same manner except that the addition amount of phloroglucinol was changed to 0.02 mol and the addition amount of tert-butylphenol was changed to 0.40 mol. It was. The degree of branching of this polycarbonate resin [3] was 0.55 [nm / (g / mol)]. Table 1 shows the weight average molecular weight of the polycarbonate resin [3].

[Production Example 4 of Polycarbonate Resin]
Polycarbonate resin [4] was obtained in the same manner except that the addition amount of phloroglucinol was changed to 0.1 mol and the addition amount of tert-butylphenol was changed to 0.30 mol in Production Example 1 of the polycarbonate resin. It was. The degree of branching of this polycarbonate resin [4] was 0.35 [nm / (g / mol)]. Table 1 shows the weight average molecular weight of the polycarbonate resin [4].

[Production Example 5 of polycarbonate resin]
In polycarbonate resin production example 1, polycarbonate resin [5] was obtained in the same manner except that the addition amount of phloroglucinol was changed to 0.03 mol and the addition amount of tert-butylphenol was changed to 0.20 mol. It was. The degree of branching of this polycarbonate resin [5] was 0.47 [nm / (g / mol)]. Table 1 shows the weight average molecular weight of the polycarbonate resin [5].

[Production Example 6 of polycarbonate resin]
In polycarbonate resin production example 1, polycarbonate resin [6] was obtained in the same manner except that the addition amount of phloroglucinol was changed to 0.03 mol and the addition amount of tert-butylphenol was changed to 0.5 mol. It was. The degree of branching of this polycarbonate resin [6] was 0.47 [nm / (g / mol)]. Table 1 shows the weight average molecular weight of the polycarbonate resin [6].

[Production Example 7 of polycarbonate resin]
Polycarbonate resin [7] was obtained in the same manner as in Production Example 1 of polycarbonate resin, except that phloroglucinol was not added and the addition amount of p-butylphenol was changed to 0.4 mol. The weight average molecular weight of this polycarbonate resin [7] is shown in Table 1.

[Production Example 8 of Polycarbonate Resin]
In polycarbonate resin production example 1, polycarbonate resin [8] was obtained in the same manner except that the addition amount of phloroglucinol was changed to 0.02 mol and the addition amount of tert-butylphenol was changed to 0.2 mol. It was. The degree of branching of this polycarbonate resin [8] was 0.34 [nm / (g / mol)]. Table 1 shows the weight average molecular weight of the polycarbonate resin [8].

[Production Example 9 of polycarbonate resin]
Polycarbonate resin [9] was obtained in the same manner as in Production Example 1 of polycarbonate resin, except that phloroglucinol was not added and the addition amount of p-butylphenol was changed to 0.44 mol. The weight average molecular weight of this polycarbonate resin [9] is shown in Table 1.

[Production Example 10 of polycarbonate resin]
In polycarbonate resin production example 1, polycarbonate resin [10] was obtained in the same manner except that the addition amount of phloroglucinol was changed to 0.04 mol and the addition amount of tert-butylphenol was changed to 0.4 mol. It was. The degree of branching of this polycarbonate resin [10] was 0.47 [nm / (g / mol)]. Table 1 shows the weight average molecular weight of the polycarbonate resin [10].

[Production Example 11 of Polycarbonate Resin]
In polycarbonate resin production example 1, polycarbonate resin [11] was obtained in the same manner except that the addition amount of phloroglucinol was changed to 0.04 mol and the addition amount of tert-butylphenol was changed to 0.35 mol. It was. The degree of branching of this polycarbonate resin [11] was 0.47 [nm / (g / mol)]. Table 1 shows the weight average molecular weight of the polycarbonate resin [11].

<Example 1>
The raw materials consisting of the components shown in Table 2 were dry blended at a predetermined content ratio using a V-type mixer, dried at 60 ° C. for 4 hours under reduced pressure using a vacuum dryer, and premixed. The dried raw material is charged from the raw material supply port of a twin screw extrusion kneader “KTX30” (manufactured by Kobe Steel) and melted under the conditions of discharge rate: 30 kg / hour, resin pressure: 4 MPa, and screw rotation speed: 250 rpm. A kneading process was performed. In this twin-screw extrusion kneader, the cylinder part is composed of nine blocks C1 to C9 for each temperature control block, the raw material supply ports are provided in the C1 part, and the rotor and kneader are provided in the C3 part and the C7 part. A combination of screws is arranged, and a vent is installed at C8 part. Then, using a device (die) similar to that shown in FIG. 1 and setting the gap distance of the slit to 5 mm, the raw material in the molten state discharged from the twin-screw extruder kneader is fed into the inlet (5) under the following gap passage processing conditions. After flowing in, a predetermined slit (2a, 2b) was passed through and discharged from the discharge port (6) to perform a gap passing process. What was discharged from the die was cooled by immersing it in water at 30 ° C., and was cut with a pelletizer to obtain a pellet-shaped molding material [1].

-Gap passage processing conditions-
Raw material flow rate: 30 kg / h
Resin pressure of raw material: 10 MPa
Raw material temperature: 270 ° C

<Examples 2-6 and Comparative Examples 1-6>
Molding materials [2] to [12] in the same manner as in Example 1 except that the type of each component constituting the raw material, the content ratio thereof, and the gap distance of the slit in the gap passing treatment were changed according to those shown in Table 2. ] Was obtained.

<Evaluation>
(1) Fluidity After the obtained molding materials [1] to [12] were dried at 80 ° C. for 4 hours, an injection molding machine “J55ELII” (manufactured by Nippon Steel Works) was used, and a rod flow test piece (flow The flow length was evaluated according to the following evaluation criteria at a channel thickness of 1 mm and a channel width of 8 mm. The conditions were a cylinder temperature of 280 ° C., a mold temperature of 40 ° C., and an injection pressure of 40 MPa. The results are shown in Table 2. In addition, it is evaluated that fluidity | liquidity is so good that flow length is large.
A: 100 mm or more B: 60 mm or more and less than 100 mm C: 20 mm or more and less than 60 mm (no problem in practical use)
D: less than 20 mm (practical problem)

(2) Impact strength After the obtained molding materials [1] to [12] were dried at 80 ° C. for 4 hours, the cylinder set temperature was 280 ° C. using an injection molding machine “J55ELII” (manufactured by Nippon Steel Works). A 100 mm × 10 mm × 4 mm strip test piece was molded at a mold temperature of 40 ° C., and the impact strength of the test piece was determined by Charpy impact test (U notch, R = 1 mm) according to “JIS-K7111”. The impact strength was measured. The results are shown in Table 2. In addition, if the impact strength is 120 kJ / m ² or more, it is regarded as an acceptable level.

<Example 7>
Using the polycarbonate resin [1] obtained in Production Example 1 of the polycarbonate resin, it was processed by an injection molding method to obtain a molded product, and this molded product was pulverized to obtain a recycled polycarbonate resin [1]. A raw material comprising the recycled polycarbonate resin [1] and the components shown in Table 3 was subjected to a premixing treatment, a melting / kneading treatment, a gap passing treatment and a cooling treatment at a predetermined content ratio in the same manner as in Example 1 to obtain a molding material [13 ] Was obtained. The recycled polycarbonate resin [1] had a branched structure, the degree of branching was 0.47 [nm / (g / mol)], and the weight average molecular weight was 10,000.
The obtained molding material [13] was evaluated in the same manner as the above evaluation. The results are shown in Table 3.

  In addition, “PET” in the polyester resin shown in Table 2 and Table 3 is obtained from a PET bottle that has been used and discarded (melting point: 270 ° C., glass transition temperature (Tg): 76 ° C.). Yes, “PBT” is “Novaduran” (manufactured by Mitsubishi Engineering Plastics Co., Ltd.), and the flame retardant in an optional component is a phosphate ester flame retardant “CR733S” (manufactured by Daihachi Chemical Industry Co., Ltd.).

1a, 1b Reservoir 2a, 2b Slit 5 Inlet 6 Discharge 10A Device (die)

Claims (5)

The degree of branching in the molecule is 0.35 to 0.55 [nm / (g / mol)], and the polycarbonate resin having a weight average molecular weight of 10,000 to 80,000 is contained in a proportion of 40 to 90% by mass,
An injection molding material comprising a resin composition containing a thermoplastic polyester resin having a weight average molecular weight of 10,000 to 50,000 in a proportion of 5 to 30% by mass.   The injection molding material according to claim 1, wherein the polycarbonate resin has a weight average molecular weight of 12,000 to 50,000.   The injection molding material according to claim 1 or 2, wherein the polyester resin has a weight average molecular weight of 15,000 to 40,000.   The injection molding material according to any one of claims 1 to 3, wherein the polycarbonate resin has a branching degree of 0.39 to 0.53 [nm / (g / mol)].   (A) a polycarbonate resin having a degree of branching in the molecule of 0.35 to 0.55 [nm / (g / mol)] and a weight average molecular weight of 10,000 to 80,000, and (B) a weight average molecular weight Production of an injection molding material characterized by melting and kneading a raw material containing a thermoplastic polyester resin having a thickness of 10,000 to 50,000, followed by a gap passage treatment for passing through a slit having a gap distance of 5 mm or less Method.