JP6370242B2 - Polycarbonate resin foam molding - Google Patents

Description

  The present invention relates to a polycarbonate resin foam molded article. More specifically, the present invention relates to a polycarbonate resin foamed molded article having good fusion properties.

In addition to being light, foamed molded products have good workability and shape retention, and are relatively strong, so they are used in various fields such as food trays and automotive parts, building materials, civil engineering materials, and lighting equipment. ing. In particular, when heat resistance is not required, a foamed molded product made of polystyrene resin is used. When buffer characteristics, recoverability, flexibility, etc. are required, a foamed molded product made of olefinic resin such as polypropylene or polyethylene is used. Tend to be used.
Polycarbonate resins are generally resins having higher heat resistance than polystyrene resins and olefin resins. This is a resin material that can be used in countries other than Japan as well as in harsh climates such as dry and tropical areas. This polycarbonate resin is not only excellent in heat resistance but also excellent in water resistance, electrical characteristics, mechanical strength, aging resistance and chemical resistance. For this reason, polycarbonate resins have been used as interior materials for buildings so far, but in recent years, application development to automobile members, packaging materials, various containers and the like utilizing their excellent characteristics is also expected.

By the way, as a method for producing a polycarbonate resin foam, for example, an extrusion foaming method as disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 9-076332) is well known. However, since the foam obtained by this method has a board shape, it was only possible to obtain a simple building material. Therefore, it is difficult to obtain a foam having a complicated shape such as an automobile member by the extrusion foaming method.
As a method for enabling complicated molding, an in-mold foam molding method in which foamed particles are foamed and fused in a mold is known. This method prepares a mold having a space corresponding to a desired shape, fills the space with foamed particles, and foams and fuses the foamed particles by heating, thereby forming a foamed molded product having a complicated shape. Can be obtained. For example, Patent Document 2 (Japanese Patent Laid-Open No. 6-100724) and Patent Document 3 (Japanese Patent Laid-Open No. 11-287277) disclose methods for obtaining a foam-molded product from foamed particles made of a polycarbonate resin by an in-mold foam molding method. Proposed.

JP 9-076332 A JP-A-6-100724 Japanese Patent Laid-Open No. 11-287277

  However, in Patent Documents 2 and 3, when obtaining a foamed molded product, the foamed particles are fused to each other by steam heating. Therefore, it is difficult to obtain a foamed molded product in which the foamed particles are sufficiently fused. It was. There is a method of using an adhesive for bonding the foamed particles, but it is easily expected that it becomes a factor of reducing the weight and reducing the thermal characteristics of the original polycarbonate resin.

In view of the above problems, the inventors of the present invention can provide a foamed molded article having good fusion properties by using a plasticizer having a specific structure (number of ester bonds and molecular weight) and boiling point. As a result, the present invention was found.
Thus, according to the present invention, it is a foamed molded article composed of a plurality of foamed particles having a polycarbonate resin as a base resin, and the foamed molded article has two or more ester bonds and a molecular weight of 200 to 600. , it looks containing a plasticizer having a boiling point of 250 to 500 ° C.,
There is provided a polycarbonate resin foam molded article , wherein the plasticizer is selected from diisobutyl adipate and glycerin diacetomonolaurate and is contained in the foam molded article in an amount of 14,000 to 37,000 ppm .

By including a plasticizer having a specific structure and boiling point, it is possible to provide a polycarbonate resin foamed molded article having good fusion properties.
In any of the following cases, it is possible to provide a polycarbonate resin foamed molded article having better fusion properties.
(1) A plasticizer is contained at 5 to 50000 ppm.
(2) The plasticizer is selected from an ester of an aliphatic polycarboxylic acid and an aliphatic monoalcohol and an ester of an aliphatic polyhydric alcohol and an aliphatic monocarboxylic acid, and has 2 to 4 ester bonds.
(3) The plasticizer is selected from diisobutyl adipate and glycerin diacetomonolaurate.
(4) The polycarbonate resin has an aromatic skeleton.

  A polycarbonate resin foam molded body (hereinafter also simply referred to as a foam molded body) is composed of a plurality of foamed particles having a polycarbonate resin as a base resin, and contains a plasticizer having a specific structure and boiling point.

[Polycarbonate resin]
The polycarbonate resin preferably has a polyester structure of carbonic acid and glycol or divalent phenol. From the viewpoint of further improving the heat resistance, the polycarbonate resin preferably has an aromatic skeleton. Specific examples of the polycarbonate-based resin include 2,2-bis (4-oxyphenyl) propane, 2,2-bis (4-oxyphenyl) butane, 1,1-bis (4-oxyphenyl) cyclohexane, 1, Examples thereof include polycarbonate resins derived from bisphenols such as 1-bis (4-oxyphenyl) butane, 1,1-bis (4-oxyphenyl) isobutane, and 1,1-bis (4-oxyphenyl) ethane.
Examples of the polycarbonate resin include a linear polycarbonate resin and a branched polycarbonate resin, and both of them may be blended.

The polycarbonate-based resin may contain a resin other than the polycarbonate resin. Examples of other resins include acrylic resins, saturated polyester resins, ABS resins, polystyrene resins, and polyphenylene oxide resins. The polycarbonate resin preferably contains 50% by weight or more of polycarbonate resin.
The polycarbonate-based resin preferably has an MFR of 1 to 20 g / 10 min. Resins in this range are suitable for foaming and are more easily foamed. A more preferable MFR range is 2 to 15 g / 10 min.

[Plasticizer]
The plasticizer functions to plasticize the polycarbonate-based resin and has two or more ester bonds, a molecular weight of 200 to 600, and a boiling point of 250 to 500 ° C.
When there is one ester bond, the affinity with the polycarbonate-based resin is small, and the effect of improving the fusibility may not be sufficient. The upper limit of the number of ester bonds is a value at which the molecular weight is 200 to 600 and the boiling point is 250 to 500 ° C. The number of ester bonds is preferably 2-4.
When the molecular weight is smaller than 200, the resin is easily impregnated inside the resin and the plastic effect becomes too strong, and the resin may easily shrink during foaming and molding. When it is larger than 600, the viscosity of the plasticizer becomes high, and it may be difficult to handle or a desired plasticizing effect may not be obtained. A more preferred molecular weight is 220 to 500, and a more preferred molecular weight is 230 to 450.

When the boiling point is lower than 250 ° C., it tends to dissipate during the molding process, and the desired effect may not be obtained. When the temperature is higher than 500 ° C., some of them have a high viscosity, which may make handling difficult and difficult to obtain a desired plastic effect. A more preferable boiling point is 270 to 500 ° C, and a further preferable melting point is 280 to 450 ° C.
The plasticizer is not particularly limited as long as it has the above structure and boiling point. For example, an ester of an aliphatic polyhydric carboxylic acid and an aliphatic monoalcohol, or an aliphatic polyhydric alcohol and an aliphatic monocarboxylic acid. Compounds selected from esters and having 2 to 4 ester bonds are preferred. These plasticizers may be used alone or in combination of two or more.

Aliphatic polycarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and other aliphatic divalent carboxylic acids, propanetricarboxylic acid, butanetricarboxylic acid Examples thereof include aliphatic trivalent carboxylic acids such as acid and pentanetricarboxylic acid, and aliphatic tetravalent carboxylic acids such as butanetetracarboxylic acid, pentanetetracarboxylic acid, and hexanetetracarboxylic acid. Examples of the aliphatic monoalcohol include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol and the like.
Examples of the aliphatic polyhydric alcohol include aliphatic dihydric alcohols such as ethylene glycol, propylene glycol, butanediol, pentanediol and hexanediol, aliphatic trihydric alcohols such as glycerin and butanetriol, and aliphatics such as erythritol and pentaerythritol. A tetrahydric alcohol etc. are mentioned.
Examples of the aliphatic monocarboxylic acid include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, and coconut fatty acid.
The compounds exemplified as the above aliphatic polycarboxylic acid, aliphatic monoalcohol, aliphatic polyhydric alcohol and aliphatic monocarboxylic acid include all variations of substitutable positions for the carboxyl group and the hydroxyl group. In addition, hydrocarbon groups (alkyl groups, alkanediyl groups, etc.) contain possible structural isomers.
Particularly preferred plasticizers include diisobutyl adipate and glycerin diacetomonolaurate.

Other plasticizers include polyhydric alcohol solvents such as methanol, ethanol, isopropyl alcohol, and glycerin, and hydrocarbon solvents such as toluene and xylene. These other plasticizers are expected to be sufficiently plasticized. It is hard to do. When these other plasticizers are used, they are preferably mixed with a plasticizer having two or more ester bonds, a molecular weight of 200 to 600, and a boiling point of 250 to 500 ° C. The other plasticizer is preferably contained in an amount of 50% by weight or less based on the total plasticizer.
The plasticizer may be present in the expanded particles constituting the expanded molded article, may be present on the surface of the expanded particles, or may be present both in the expanded particles and on the surface. The plasticizer is preferably present at least on the surface of the expanded particles from the viewpoint of improving the fusion property.

[Configuration of foamed molded product]
The foam molded article is composed of a plurality of foam particles. The expanded particles are fused to each other on their surfaces. ADVANTAGE OF THE INVENTION According to this invention, the foaming molding which the meltability improved by presence of a plasticizer can be provided.
The foamed molded product can have various densities. The density can be 0.020 g / cm ³ or more. The lower limit of the preferred density is 0.037 g / cm ³ . Further, the upper limit of the density is preferably 0.4 g / cm ³ .
The foamed molded product is not particularly limited, and can take various shapes depending on applications. For example, the foamed molded product can take various shapes depending on applications such as civil engineering-related building materials, structural members such as automobile structural members and windmills, and FRP core materials as composite members.

[Method for producing foam molded article]
The foamed molded product can be obtained by impregnating resin particles with a foaming agent to obtain foamable particles, foaming the foamable particles to obtain foamed particles, and foaming the foamed particles. Usually, the plasticizer can be included in the foamed molded article by adhering to the foamed particles.
(1) Production of expandable particles Expandable particles can be obtained by impregnating resin particles made of polycarbonate resin with a foaming agent.
The resin particles can be obtained by a known method. For example, a polycarbonate resin is melt-kneaded in an extruder together with other additives as necessary and extruded to obtain a strand. The resulting strand is cut in air, cut in water and heated. The method of granulating is mentioned by cutting while. Commercially available resin particles may be used for the resin particles. The resin particles may contain other additives in addition to the resin, if necessary. Examples of other additives include flame retardants, flame retardant aids, antistatic agents, spreading agents, bubble regulators, fillers, colorants, weathering agents, anti-aging agents, lubricants, antifogging agents, and fragrances. It is done.

Next, as the foaming agent impregnated into the resin particles, known volatile foaming agents and inorganic foaming agents can be used. Examples of the volatile blowing agent include aliphatic hydrocarbons such as propane, butane, and pentane, aromatic hydrocarbons, alicyclic hydrocarbons, aliphatic alcohols, and the like. Examples of the inorganic foaming agent include carbon dioxide gas, nitrogen gas, and air (air). Two or more of these foaming agents may be used in combination. Of these foaming agents, inorganic foaming agents are preferred, and carbon dioxide gas is more preferred.
The content (impregnation amount) of the foaming agent is preferably 3 to 12 parts by weight with respect to 100 parts by weight of the polycarbonate resin. When the content of the foaming agent is less than 3 parts by weight, the foaming power is low, and it may be difficult to foam well. When the content exceeds 12 parts by weight, the plasticizing effect is increased, shrinkage occurs easily during foaming, the productivity is deteriorated, and it is difficult to stably obtain a desired expansion ratio. A more preferable foaming agent content is 4 to 12 parts by weight.

Examples of the impregnation method include a wet impregnation method in which resin particles are dispersed in an aqueous system and agitated by press-fitting a foaming agent while stirring, or a resin particle is introduced into a sealable container and is substantially impregnated by injecting the foaming agent. For example, a dry impregnation method (vapor phase impregnation method) that does not use water is used. In particular, a dry impregnation method that can be impregnated without using water is preferable. The impregnation pressure, impregnation time and impregnation temperature when impregnating the resin particles with the foaming agent are not particularly limited.
The impregnation pressure is preferably 2 to 4.5 MPa from the viewpoint of efficiently performing the impregnation and obtaining better foamed particles and a foamed molded article.

The impregnation time is preferably 0.5 to 200 hours or less. When the time is less than 0.5 hours, the amount of the foaming agent impregnated into the resin particles is reduced, so that sufficient foaming power may not be obtained. When it is longer than 200 hours, productivity may be reduced. A more preferable impregnation time is 1 to 100 hours.
The impregnation temperature is preferably 0 to 60 ° C. When the temperature is lower than 0 ° C., a sufficient amount of impregnation cannot be ensured within a desired time, and thus sufficient foaming power (primary foaming power) may be difficult to obtain. When it is higher than 60 ° C., productivity may be deteriorated. A more preferable impregnation temperature is 5 to 50 ° C.

(2) Production of foamed particles As a method for obtaining foamed particles by foaming the foamable particles, a method of foaming the foamable particles by heating with steam (water vapor) or the like is preferably used.
It is preferable to use a sealed pressure-resistant foaming container for the foaming machine at the time of foaming. The steam pressure is preferably 0.2 to 0.5 MPa, and more preferably 0.25 to 0.45 MPa. The foaming time may be a time required to obtain a desired expansion ratio. The preferred foaming time is 5 to 180 seconds. If it exceeds 180 seconds, shrinkage of the expanded particles may start.
The shape of the expanded particles is not particularly limited. For example, spherical shape, cylindrical shape, etc. are mentioned. Of these, it is preferable that the shape be as spherical as possible. That is, it is preferable that the ratio of the minor axis to the major axis of the expanded particles is as close to 1 as possible.
The expanded particles can have various bulk densities. The bulk density is preferably 0.04 g / cm ³ or more. More preferably, it is 0.06-0.3 g / cm < ³ >.
The expanded particles preferably have an average particle diameter of 1 to 20 mm.

  Any known method may be used as a method of attaching a plasticizer to the expanded particles. For example, a method of spraying a plasticizer on the foamed particles by spraying, a method of immersing the foamed particles in the plasticizer, a method of dropping the plasticizer while stirring the foamed particles, and the like can be mentioned. In the method of immersing the expanded particles in the plasticizer, it is also possible to pre-fill the expanded particles in a porous mold such as a mesh or punching plate and immerse the mold in a container filled with the plasticizer. These methods may be appropriately changed according to the type and amount of plasticizer used and the amount of expanded particles.

  The plasticizer may be adhered as it is in the stock solution. Moreover, after diluting a plasticizer with solvents, such as water and alcohol, you may adhere. Dilution increases the amount of liquid and lowers the viscosity, so that even when the amount of plasticizer is small, it can adhere uniformly. However, if diluted too much, the concentration of the plasticizer becomes too thin and the effect may not be obtained, or the foamed particles may shrink due to penetration of the plasticizer into the inside of the foamed particles. Accordingly, the degree of dilution may be appropriately changed according to the type and amount of plasticizer used.

(3) Manufacture of a foaming molding A foaming molding can be obtained by giving an internal pressure to the said foaming particle, and attaching | subjecting a foaming particle to a formation process then, for example.
Before producing the foamed molded article, it is preferable to impregnate the foamed particles with a foaming agent to impart foaming power (secondary foaming power). As the foaming agent used here, the foaming agent used in the production of foamed particles can be used. Among these, it is preferable to use an inorganic foaming agent. In particular, it is preferable to use one from nitrogen gas, air, and carbon dioxide, or to use two or more in combination.
The pressure for applying the internal pressure is desirably a pressure that does not cause the foamed particles to be crushed and within a range in which the foaming force can be applied. Such pressure is preferably 0.1 to 4 MPa, and more preferably 0.3 to 3 MPa.

After supplying the foamed particles to which the internal pressure is applied to the molding space formed in the molding die of the foam molding machine, the desired foamed molded product can be molded in-mold by introducing a heating medium. As the foam molding machine, an EPS molding machine used when producing a foam molded body from polystyrene resin foam particles or a high-pressure molding used when producing a foam molded body from polypropylene resin foam particles. A machine or the like can be used. Since the heating medium may cause shrinkage or poor fusion of the foamed particles when the heating time becomes long, a heating medium that can give high energy in a short time is desired. Therefore, steam is suitable as such a heating medium. is there.
The steam pressure is preferably 0.2 to 0.5 MPa. The heating time is preferably 10 to 90 seconds, more preferably 20 to 80 seconds.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. First, methods for measuring various physical properties in the examples are described below.
The compound structure of a plasticizer can be identified by a known method, for example, by applying a plasticizer extracted from a foamed molded article to IR or NMR to obtain a graph and comparing it with a known graph.
[Measurement of boiling point]
Examples of the measurement of the boiling point include a method described in JIS K 2233: 2006. Moreover, if it is a known compound, you may refer to the boiling point described in SDS etc.

[Measurement of MFR]
Melt flow rate (MFR) was measured using “Semi-auto melt indexer 2A” manufactured by Toyo Seiki Seisakusho Co., Ltd., JIS K7210: 1999 “Plastic-thermoplastic melt flow rate (MFR) and melt volume flow rate (MVR)”. B) Measured in accordance with b) a method for measuring the time required for the piston to move a predetermined distance as described in “Method B”. Specifically, the measurement conditions are as follows: sample 3 to 8 g, preheating 270 seconds, load hold 30 seconds, test temperature 300 ° C., test load 11.77 N, and piston moving distance (interval) 25 mm. The number of test of the sample is 3, and the average is the value of melt flow rate (g / 10 minutes). In addition, as a measurement sample, a sample dried at 120 ° C. under a reduced pressure of 100 kPa for 5 hours is used in the measurement.

[Measurement of average particle size]
The average particle diameter is a value expressed by D50.
Specifically, using a low tap type sieve shaker (manufactured by Iida Seisakusho), sieve openings 26.5 mm, 22.4 mm, 19.0 mm, 16.0 mm, 13.2 mm, 11.20 mm, 9.50 mm 8.80 mm, 6.70 mm, 5.66 mm, 4.76 mm, 4.00 mm, 3.35 mm, 2.80 mm, 2.36 mm, 2.00 mm, 1.70 mm, 1.40 mm, 1.18 mm, 1 .00mm, 0.85mm, 0.71mm, 0.60mm, 0.50mm, 0.425mm, 0.355mm, 0.300mm, 0.250mm, 0.212mm and 0.180mm JIS standard sieves (JIS Z8801) Classify about 25 g of the sample for 10 minutes and measure the sample weight on the sieve mesh. A cumulative weight distribution curve is created from the obtained results, and the particle diameter (median diameter) at which the cumulative weight is 50% is defined as the average particle diameter.

[Measurement of bulk density of expanded particles]
About 1000 cm ³ of expanded particles are filled into a graduated cylinder to a scale of 1000 cm ³ . The graduated cylinder is visually observed from the horizontal direction, and if at least one expanded particle reaches the scale of 1000 cm ³ , the filling of the expanded particle into the graduated cylinder is terminated at that point. Next, the weight of the expanded particles filled in the graduated cylinder is weighed with two significant figures after the decimal point, and the mass is defined as Wg. And the bulk density of foamed particle is calculated | required by a following formula.
Bulk density (g / cm ³ ) = W / 1000
The bulk multiple is a value obtained by adding the density (g / cm ³ ) of the polycarbonate resin to the reciprocal of the bulk density.
The density of the polycarbonate resin is measured by the method specified in ISO1183.

[Measurement of density of foamed molded product]
The mass (a) and volume (b) of a test piece (example 75 × 300 × 30 mm) cut out from a foamed molded product (after being molded and dried at 40 ° C. for 20 hours or more) each have three or more significant figures. Then, the density (g / cm ³ ) of the foamed molded product is obtained by the formula (a) / (b).
The multiple is a value obtained by adding the density (g / cm ³ ) of the polycarbonate resin to the reciprocal of the density.
[Measurement of fusion rate]
A cut line having a depth of about 1 mm is put into the foamed molded article with a cutter knife. Thereafter, the foamed molded product is divided into two parts by a hand or a hammer along the cut line. For any 20 expanded particles exposed on the fracture surface, the number (a) of particles broken in the particles is counted. A value obtained by substituting the result into the formula (a) × 100/20 is defined as a fusion rate (%). A fusion rate of 50% or more is evaluated as ◯, and less than 50% is evaluated as ×.

[Measurement of plasticizer amount]
(A) Riquemar PL-012 and Vinicizer 40
Measurement as glycerin diacetomonolaurate and diisobutyl monolaurate amount (1) Extraction method Approximately 1.0 g of the frozen and ground sample is weighed and collected in a cell container as it is, and ASE-350 (manufactured by Dionex) high-speed solvent extraction. Extraction is performed under the following conditions using an apparatus.
・ Extraction pressure: 10.5 MPa
・ Temperature raising time: 5 minutes ・ Standing time: 10 minutes ・ Extraction temperature: 110 ° C.
・ Purge time: 90 seconds ・ Number of cycles: 3 times ・ Rinse amount: 10%
-Extraction solvent: methanol-Time required: 45 minutes

(2) Measurement method of Riquemar PL-012 The high-speed solvent extract was transferred to a 50 mL volumetric flask, fixed with methanol, filtered through a non-aqueous 0.20 μm chromatodisc, and the filtrate was subjected to HPLC measurement. The measurement conditions are as shown below, and using the standard peak area value obtained from the chromatogram, the concentration of Riquemar PL-012 in the sample solution was determined from the calibration curve, and the content was calculated. The standard for the calibration curve used was Riken Maru PL-012 manufactured by Riken Vitamin.
(HPLC measurement conditions)
Apparatus: Liquid chromatograph apparatus LC-10Avp (manufactured by Shimadzu Corporation)
Column: TSKgel ODS-80TS QA (4.6 * 150 mm) manufactured by TOSOH
Column temperature: 40 ° C
Mobile phase: Methanol Mobile phase Flow rate: 0.7 mL / min Pump temperature: Room temperature Measurement time: 10 minutes Injection volume: 50 μL
Detector: Evaporative light scattering detector ELSD-2000 (Altech)
(Detector setting conditions)
Drift Tube temp .: 60 ° C
GAS Flow: 1.6 mL / min GAIN: 1 (impactor = off)

(3) Measuring method of Vinicizer 40 Into a 2 mL volumetric flask, 20 μL (1000 ppm) of internal standard solution pyrene is added, and the volume is adjusted with an extract of high-speed solvent extraction, and GC / MS analysis is performed under the following conditions.
Calibration of diisobutyl adipate (6.15 ppm, 24.6 ppm, 61.5 ppm) prepared in advance with the diisobutyl adipate concentration as the relative sensitivity to the peak area of pyrene, which is an internal standard substance, as the peak area of diisobutyl adipate in the obtained chromatogram Calculated from the line. Furthermore, the content (% by weight) was calculated from the sample weight and the amount of the extract by the following formula.
Diisobutyl adipate amount (% by weight) = Concentration in test solution (μg / mL) × Extract solution amount 50 (mL) ÷ Sample weight (g) ÷ 10000
(GC / MS measurement conditions)
Measuring device: Shimadzu gas chromatograph mass spectrometer QP2010SE
Column: ZB-5MS (0.25 μm × 0.25 mmφ × 30 m, manufactured by Phenomenex)
GC oven temperature rising condition: initial temperature 70 ° C. (1 minute hold)
First stage heating rate 15 ° C / min (0 min hold up to 260 ° C)
Second stage heating rate 10 ° C / min (up to 300 ° C)
Final temperature 300 ° C (3 minutes hold)
Carrier gas: helium total flow rate, column flow rate: 52 mL / min, 1.02 mL / min column inlet pressure: 74.9 kPa
Detector: 1.00 kV
Inlet temperature: 300 ° C
Interface temperature: 260 ° C
Ion source temperature: 260 ° C
Split ratio: 1/50 (internal standard method)
Test solution injection: 2 μL (using an autosampler)
Measurement mode: SIM method (M / Z = 129, 185, 200, 202)
Internal standard solution: Pyrene

(B) Measurement of the amount of other plasticizers The plasticizer extraction conditions from the sample and the measurement method need to be appropriately changed depending on the type of plasticizer and the remaining amount must be confirmed. For example, a method using a high-speed solvent extraction apparatus is suitable for the quantification of unknown substances having a high boiling point as in the case of Riquemar PL-012. Furthermore, HPLC, GC / MS method, etc. can be suitably selected also as a measuring method. Identification of an unknown compound can be performed using IR, NMR, or the like. For confirmation of the remaining amount, it is desirable to determine the concentration by preparing a calibration curve from identification of the unknown substance.
The measurement method will be described below with respect to a known substance and an analysis method using the GC / MS method.
Measurement sample measurement method: Cut a sample to about 2 mm square, accurately weigh about 0.5 g in an HS vial, immediately put a septum and an aluminum cap, and fix with an aluminum cap clamp. Heat in a thermostatic chamber at 110 ° C. for about 30 minutes, and 0.5 mL of the gas phase in the test vial is directly injected into the GC inlet and the amount of plasticizer is measured.
Standard preparation method: 5 μL of each standard solution 1000 ppm methanol solution is poured into an HS vial, immediately put a septum and an aluminum cap, and fixed with an aluminum cap clamp. Heat for about 30 minutes in a 110 ° C. thermostat, and 0.5 mL of the gas phase in the test vial is directly injected into the GC inlet and measured.

The measurement conditions are as follows, and the concentration is determined from a calibration curve.
(GC / MS measurement conditions)
Measuring device: Shimadzu gas chromatograph mass spectrometer QP2010SE
Column: ZB-5MS (0.25 μm × 0.25 mmφ × 30 m, manufactured by Phenomenex)
GC oven temperature rising condition: initial temperature 70 ° C. (1 minute hold)
First stage heating rate 15 ° C / min (0 min hold up to 260 ° C)
Second stage heating rate 10 ° C / min (up to 300 ° C)
Final temperature 300 ° C (3 minutes hold)
Carrier gas: helium total flow rate, column flow rate: 52 mL / min, 1.02 mL / min column inlet pressure: 74.9 kPa
Detector: 1.00 kV
Inlet temperature: 300 ° C
Interface temperature: 260 ° C
Ion source temperature: 260 ° C
Split ratio: 1/50 (internal standard method)
Test solution injection: 2 μL (using an autosampler)
Measurement mode: SIM method (M / Z = 129, 185, 200, 202)
Internal standard solution: Pyrene

<Example 1> (Reference example)
(Impregnation process)
100 parts by weight (1000 g) of polycarbonate-based resin (SABIC Lexan 153 (density 1.2 g / cm ³ , MFR 4/10 min, average particle size 3 mm)) was charged into a 10 L pressure vessel capable of being sealed, and carbon dioxide gas was introduced. The inside of the pressure vessel was increased to a gauge pressure of 4 MPa, and kept in a room temperature (about 25 ° C.) environment for 24 hours to obtain expandable particles.
(Foaming process)
After the impregnation, the carbon dioxide gas in the pressure vessel was slowly released to take out the expandable particles inside. Immediately, 0.3 part by weight (3 g) of calcium carbonate as a binding inhibitor and 100 parts by weight (1000 g) of expandable particles were mixed. Thereafter, the foamable particles were put into a high-pressure foaming machine equipped with a stirrer, and foamed using 0.34 MPa water vapor with stirring to obtain a bulk density of 0.08 g / cm ³ .

(Second impregnation step: internal pressure application step)
The surface of the obtained expanded particles was washed with 0.01N hydrochloric acid and dried, and then 100 parts by weight (500 g) was put into a 10 L pressure vessel and sealed. The inside of the pressure vessel sealed with nitrogen gas was increased to a gauge pressure of 1 MPa and left for 24 hours to give an internal pressure.

(Molding process)
The nitrogen gas in the pressure vessel to which the internal pressure was applied was slowly removed, and the foamed particles were taken out. 100 parts by weight (500 g) of the foamed particles and 1 part by weight (5 g) of Rikenmar PL-012 (glycerol diacetomonolaurate) manufactured by Riken Vitamin Co., Ltd. ) Was shaken up and down 20 times, mixed well, and then foam-molded using a high-pressure molding machine. A foamed molded article is prepared by filling foamed particles in a molding die having an inner dimension of 400 mm in length × 300 mm in width × 30 mm in thickness, introducing water of 0.30 to 0.35 MPa for 50 seconds, heating and cooling. Got. The obtained foamed molded product was dried in a drying chamber at 30 ° C. for about 8 hours, and showed a density of 0.08 g / cm ³ .

<Example 2> (Reference example)
A foam molded article was obtained in the same manner as in Example 1 except that the plasticizer was changed to Vinicizer 40 (Kao Corporation: diisobutyl adipate) and the amount of plasticizer added was 2.5 parts by weight (12.5 g). It was.
The bulk density of the obtained foamed particles was 0.08 g / cm ³ , and the density of the foamed molded product was 0.08 g / cm ³ .
<Example 3>
A foam molded article was obtained in the same manner as in Example 1 except that the amount of the plasticizer added was 2.5 parts by weight (12.5 g).
The bulk density of the obtained foamed particles was 0.08 g / cm ³ , and the density of the foamed molded product was 0.08 g / cm ³ .
<Example 4>
A foamed molded article was obtained in the same manner as in Example 1 except that the amount of the plasticizer added was 5 parts by weight (25 g) of the impregnation temperature.
The bulk density of the obtained foamed particles was 0.08 g / cm ³ , and the density of the foamed molded product was 0.08 g / cm ³ .

<Comparative Example 1>
A foamed molded article was obtained in the same manner as in Example 1 except that no plasticizer was used.
The bulk density of the resulting expanded beads is 0.085 g / cm ^3, the density of the foamed molded product was 0.087 g / cm ^3.
<Comparative example 2>
A foam molded article was obtained in the same manner as in Example 1 except that the plasticizer was changed to ethyl acetate and the addition amount of the plasticizer was 2.5 parts by weight (12.5 g).
The bulk density of the obtained foamed particles was 0.08 g / cm ³ , and the density of the foamed molded product was 0.08 g / cm ³ .
<Comparative Example 3>
A foam molded article was obtained in the same manner as in Example 1 except that the plasticizer was changed to butyl acetate and the amount of the plasticizer added was 2.5 parts by weight (12.5 g).
The bulk density of the obtained foamed particles was 0.08 g / cm ³ , and the density of the foamed molded product was 0.08 g / cm ³ .

<Comparative example 4>
A foam molded article was obtained in the same manner as in Example 1 except that the plasticizer was changed to ethanol and the amount of the plasticizer added was 10 parts by weight (50 g).
The bulk density of the obtained foamed particles was 0.08 g / cm ³ , and the density of the foamed molded product was 0.08 g / cm ³ .
<Comparative Example 5>
A foamed molded article was obtained in the same manner as in Example 1 except that the plasticizer was changed to toluene and the amount of the plasticizer added was 2.5 parts by weight (12.5 g).
The bulk density of the obtained foamed particles was 0.08 g / cm ³ , and the density of the foamed molded product was 0.08 g / cm ³ .
<Comparative Example 6>
A foamed molded article was obtained in the same manner as in Example 1 except that the plasticizer was changed to xylene and the amount of plasticizer added was 2.5 parts by weight (12.5 g).
The bulk density of the obtained foamed particles was 0.08 g / cm ³ , and the density of the foamed molded product was 0.08 g / cm ³ .

<Comparative Example 7>
A foamed molded article was obtained in the same manner as in Example 1 except that the plasticizer was changed to hexane and the amount of the plasticizer added was 10 parts by weight (50 g).
The bulk density of the obtained foamed particles was 0.08 g / cm ³ , and the density of the foamed molded product was 0.08 g / cm ³ .
<Comparative Example 8>
A foam molded article was obtained in the same manner as in Example 1 except that the plasticizer was changed to cyclohexane and the amount of the plasticizer added was 10 parts by weight (50 g).
The bulk density of the obtained foamed particles was 0.08 g / cm ³ , and the density of the foamed molded product was 0.08 g / cm ³ .

  From the said table | surface, it turns out that the foaming molding containing the plasticizer which has a 2 or more ester bond, the molecular weight of 200-600, and the boiling point of 250-500 degreeC has favorable melt | fusion property.

Claims (2)

A foam-molded article composed of a plurality of foam particles having a polycarbonate resin as a base resin, wherein the foam-molded article has two or more ester bonds, a molecular weight of 200 to 600, and a boiling point of 250 to 500 ° C. A plasticizer having
A polycarbonate resin foam molded article, wherein the plasticizer is selected from diisobutyl adipate and glycerin diacetomonolaurate and contained in the foam molded article in a range of 14,000 to 37,000 ppm. The polycarbonate-based resin, polycarbonate-based resin foamed molded article according to claim 1 having an aromatic skeleton.