NL2007946C2 - Polyphosphonate, method of preparing the same, and flame retardant thermoplastic resin composition including the same. - Google Patents
Polyphosphonate, method of preparing the same, and flame retardant thermoplastic resin composition including the same. Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
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- Engineering & Computer Science (AREA)
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Description
POLYPHOSPHONATE, METHOD OF PREPARING THE SAME, AND FLAME
RETARDANT THERMOPLASTIC RESIN COMPOSITION INCLUDING THE SAME
Field of the Invention 5 The present invention relates to polyphosphonate and a flame retardant thermoplastic resin composition including the same. More specifically, the present invention relates to polyphosphonate which has an improved acid value by postprocessing with an alkylene oxide in manufacture of polyphosphonate, and a thermoplastic resin composition using the same as a flame retardant.
10
Description of the Related Art
To impart flame retardancy without use of halogen flame retardants, phosphorus flame retardants are used. Conventionally, monomolecular phosphorus flame retardants, such as triphenyl phosphate and resorcinol bisphenol phosphate, are 15 used. However, such monomolecular phosphorus flame retardants have a low molecular weight and thus volatilize at a high molding temperature in molding plastic, causing appearance deterioration of the plastic. Further, monomolecular phosphorus flame retardants can escape to the external environment during use of products containing the same, causing environmental contamination. Thus, polyphosphonate 20 receives increasing attention as a polymerizable phosphorus flame retardant. Polyphosphonate in a polymer form exhibits excellent flame retardancy, mechanical properties, heat resistance, and transparency, as compared with monomolecular phosphorus flame retardants, and thus is suited to resins requiring high heat resistance and high transparency, particularly, to polycarbonate resins.
25 Such polyphosphonate may be prepared by deoxidation of a diol and phosphonic dichloride. However, phosphonic dichloride has a strong tendency to hydrolyze into phosphonic acid, thereby causing decomposition of a polycarbonate resin and decomposition of polyphosphonate.
Polyphosphonate may be polymerized through solution polymerization (US 30 Patent Nos. 2534252; 3946093; 3919363), interfacial polymerization (US Patent Publication No. 2002/0058779) and melt polymerization (US Patent Nos. 3719727; 3829405; 3830771; 4229552). Particularly, melt polymerization uses phosphonic dialkyl or aryl instead of phosphonic dichloride and thus does not cause hydrolysis. However, this method requires specialized equipment to remove by-products and requires strict 35 polymerization conditions. Solution polymerization and interfacial polymerization can 2 cause hydrolysis due to the presence of phosphonic chloride at a polymer terminal.
A method of endcapping using an alcohol has been developed to prevent hydrolysis of terminal phosphonic chloride. However, if an excessive amount of an endcapping agent is used, an acid value can increase and a polycarbonate resin can 5 be decomposed due to the remaining endcapping agent. Moreover, it is not easy to remove the hydrolyzed phosphonic acid.
Conventionally, neutralization using a base containing an alkali metal is used to reduce an acid value. In this case, however, alkali metal ions can remain in the polycarbonate thus decomposing the polycarbonate.
10 Thus, there is a need for a flame retardant for polycarbonate which has a low acid value and does not allow an agent used for reducing an acid value to remain.
Summary of the Invention
Aspects of the present invention provide polyphosphonate which has a 15 remarkably low acid value without using an endcapping agent, and a method of preparing the same. Using the polyphosphonate as a flame retardant, a flame retardant thermoplastic resin composition exhibiting excellent flame retardancy and heat resistance without causing deterioration in other physical properties may be provided.
An aspect of the invention provides polyphosphonate. The polyphosphonate 20 has an acid value of about 5.5 mg KOH/g or less and is represented by Formula 1: [Formula 1] 0 — 25 ;^RiW ;<R2)b ^ " where A represents a single bond, C1 to C5 alkylene, C1 to C5 alkylidene, C5 to C6 cycloalkylidene, -S- or -S02-, R represents a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C6 to C20 aryloxy group, and R2 30 each independently represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group or a halogen atom, a and b each independently represent an integer from about 0 to about 4, and n represents an integer from about 1 to about 500.
In one embodiment, the polyphosphonate may be post-treated with alkylene 35 oxide.
3
In one embodiment, the polyphosphonate may have an acid value of 4.5 mg KOH /g or less and have a structure represented by Formula 1-1: [Formula 1-1] 0 5 — (R2>b where R represents a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C6 to C20 aryloxy group, R^ and R2 each independently 10 represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group or a halogen atom, a and b each independently represent an integer from about 0 to about 4, and n represents an integer from about 1 to about 500.
Another aspect of the present invention provides a method of preparing the 15 polyphosphonate. The method includes reacting a diol represented by Formula 2 with phosphonic dichloride represented by Formula 3, and treating the reaction product with alkylene oxide: [Formula 2] <Rl>a (R2)b where A represents a single bond, C1 to C5 alkylene, C1 to C5 alkylidene, C5 25 to C6 cycloalkylidene, -S- or -S02-, R^ and R2 each independently represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group or a halogen atom, and a and b each independently represent an integer from about 0 to about 4; and 30 [Formula 3] 0
Cl —P-Ci
D
35 H
4 where R represents a C6 to C20 aryl group or C6 to C20 aryloxy group.
The alkylene oxide may be represented by Formula 4: [Formula 4] 5 \ /XR:
O
where R2 represents hydrogen, a C1 to C6 alkyl group, a C6 to C20 aryl group, a C6 to C20 alkyl substituted aryl group, or a C6 to C20 aralkyl group.
In one embodiment, the alkylene oxide may be added in an equivalent of 10 about 2 to 7 of the acid value of the reaction product.
In another embodiment, the reaction product may be treated with the alkylene oxide after reaction with 4-cumylphenol to adjust a terminal group.
A further aspect of the present invention provides polyphosphonate prepared by the method and having an acid value of about 5.5 mg KOH/g or less.
15 Yet another aspect of the present invention provides a flame retardant thermoplastic resin composition including the polyphosphonate. The composition may include about 0.1 to about 30 parts by weight of the polyphosphonate based on 100 parts by weight of polycarbonate resin.
Further, the flame retardant thermoplastic resin composition may have a 20 number average molecular weight of about 12,000 to 20,000 g/mol, a weight average molecular weight of about 23,000 to 40,000 g/mol, and a heat distortion temperature of about 90 to 180°C according to ASTM D648 (1/4, 18.6 kg).
Detailed description of the Invention 25 Polyphosphonate in accordance with an aspect of the invention has an acid value of about 5.5 mg KOH /g and is represented by Formula 1: [Formula 1] 30 —
L <Rl'a (R2>b J
where A represents a single bond, C1 to C5 alkylene, C1 to C5 alkylidene, C5 35 to C6 cycloalkylidene, -S- or -S02-, R represents a substituted or unsubstituted C6 to 5 C20 aryl group or a substituted or unsubstituted C6 to C20 aryloxy group, and R2 each independently represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group or a halogen atom, a and b each independently represent an 5 integer from about 0 to about 4, and n represents an integer from about 1 to about 500.
In one embodiment, the polyphosphonate may have an acid value of 4.5 mg KOH/g or less and have a structure represented by Formula 1-1: [Formula 1-1] o
10 II
--0^_^O-P
(R2>b where R represents a substituted or unsubstituted C6 to C20 aryl group or a 15 substituted or unsubstituted C6 to C20 aryloxy group, R^ and R2 each independently represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group or a halogen atom, a and b each independently represent an integer from about 0 to about 4, and n represents an integer from about 1 to about 500.
20 The polyphosphonate may be prepared by reaction of a diol with phosphonic dichloride.
In one embodiment, the polyphosphonate may be prepared by reacting a diol represented by Formula 2 with phosphonic dichloride represented by Formula 3 and by treating the reaction product with alkylene oxide: 25 [Formula 2]
HQ , x /=yOH
<Rl>a (R2)b 30 where A represents a single bond, C1 to C5 alkylene, C1 to C5 alkylidene, C5 to C6 cycloalkylidene, -S- or -S02-, R^ and R2 each independently represent a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C3 to C6 cycloalkyl group, a substituted or unsubstituted C6 to C12 aryl group or a halogen 35 atom, and a and b each independently represent an integer from about 0 to about 4.
6
Examples of the diol may include 4,4'-dihydroxybiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1 -bis-(4-hydroxyphenyl)-cyclohexane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, and 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane.
5 [Formula 3] 0
Cl —P-CI
p
10 H
where R represents a C6 to C20 aryl group or C6 to C20 aryloxy group.
Specifically, the phosphonic dichloride may be reacted with the diol in an equivalent ratio of 1 to 1.
In one embodiment, the reaction of the diol and the phosphonic dichloride may 15 be conducted by a general method in the presence of a Lewis acid as a catalyst. For example, aluminum chloride and magnesium chloride may be used as a catalyst, without being limited thereto. The catalyst may be reacted with the diol in an equivalent ratio of about 0.01 or more to 1, preferably about 0.01 ~ about 0.1 to 1.
In one embodiment, after the reaction terminates, the product may be washed 20 with an acid solution. The acid solution may be phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, and the like, preferably phosphoric acid or hydrochloric acid. Here, the acid solution may have a concentration of about 0.1 to about 10 %, preferably about 1 to about 5 %.
The reaction product washed with the acid solution is reacted with the alkylene 25 oxide represented by Formula 4. In one embodiment, dehydration for removal of water is conducted before reaction with the alkylene oxide, thereby stably conducting the reaction.
[Formula 4] 30 \ R, 0 where R2 represents hydrogen, a C1 to C6 alkyl group, a C6 to C20 aryl group, a C6 to C20 alkyl substituted aryl group or a C6 to C20 aralkyl group.
In one embodiment, R2 may be a C1 to C6 alkyl group.
35 In one embodiment, the alkylene oxide may be added in an equivalent of 7 about 2 to 7, preferably about 3 to 5, of the acid value of the reaction product. Within this range, excellent balance between physical properties can be obtained.
The reaction of the reaction product with the alkylene oxide may be conducted for about 1 minute to about 24 hours, preferably about 1 to about 20 hours. Reaction 5 temperature may be about 30 to about 150°C.
In the present invention, due to use of the alkylene oxide, an acid value may decrease and the alkylene oxide is entirely washed out in washing. Thus, when the polyphosphonate is applied to a polycarbonate resin, metal ions do not remain in the resin.
10 Alternatively, before the reaction with the alkylene oxide, the reaction product may further be subjected to endcapping by a general method. In one embodiment, the reaction product may be reacted with 4-cumylphenol to adjust a terminal group and then be treated with the alkylene oxide.
After reaction of the reaction product with the alkylene oxide, washing and 15 filtering may further be carried out.
The polyphosphonate prepared as above may have an acid value of about 5.5 mg KOH/g or less, preferably about 4.5 mg KOH/g or less, and more preferably about 0.01 to about 3 mgKOH/g.
In particular, if polyphosphonate contains a biphenyl group, the 20 polyphosphonate may have an acid value of about 1 mg KOH/g or less, preferably about 0.5 mg KOH/g or less, and more preferably about 0.001 to about 0.3 mgKOH/g.
As such, the polyphosphonate has a considerably low acid value, which does not cause decomposition of a thermoplastic resin to be mixed and is suited to use as a flame retardant.
25 Another aspect of the present invention relates to a flame retardant thermoplastic resin composition including the polyphosphonate.
There is no particular restriction as to the kind of the thermoplastic resin. Examples of the thermoplastic resin may include styrene resins, polyamide, polycarbonate, polyester, polyvinyl chloride, styrene copolymer resins, (meth)acrylic 30 resins, and polyphenylene ether resins, without being limited thereto.
The polyphosphonate prepared by the method according to the present invention has a low acid value and exhibits flame retardancy, heat resistance and transparency and thus may be properly applied to resins requiring high heat resistance and high transparency.
35 In one embodiment, the flame retardant thermoplastic resin composition may 8 include about 0.1 to about 30 parts by weight, preferably about 1 to about 15 parts by weight of the polyphosphonate based on 100 parts by weight of a polycarbonate resin.
The flame retardant thermoplastic resin composition does not cause decomposition of polycarbonate and may have a number average molecular weight of 5 about 12,000 to 20,000 g/mol, a weight average molecular weight of about 23,000 to 40,000 g/mol, and a heat distortion temperature of about 90 to 180°C according to ASTM D648 (1/4, 18.6 kg).
Next, the present invention will be explained in more detail with reference to the following examples. These examples are provided for illustrative purposes only and 10 are not to be in any way construed as limiting the present invention.
Examples
Preparation of polyphosphonate
Examples 1 to 5: Preparation of polyphosphonate 15 1 equivalent of bisphenol A (Kumho Co., Ltd.) and 0.01 equivalents of aluminum chloride were added to dichlorobenzene (Samchun Chemical Co., Ltd.) and thoroughly mixed through stirring while heating to 140°C. When the temperature reached 140°C, a mixture of 1 equivalent of phenyldichloride phosphonate (Acros Co., Ltd.) with dichlorobenzene (Samchun Chemical Co., Ltd.) was dropped thereinto, 20 thereby initiating reaction. After completion of dropping, the product was further stirred for 8 hours, and then the reaction terminated. Then, the product was washed with a 30 % or less hydrochloric acid solution, followed by elimination of a water layer, elimination of dichlorobenzene through vacuum distillation, and then measurement of an acid value. Toluene and 5 equivalents of propylene oxide (Aldrich Co., Ltd.) of the acid value 25 were added to the product, which was heated to 130°C, followed by stirring for a period of time listed in Table 1. Temperature was lowered to room temperature, and the product was washed with water twice and deposited in normal hexane, thereby obtaining a final product.
30 Examples 6 to 8: Preparation of polyphosphonate containing biphenyl group 1 equivalent of biphenol (Songwon Industrial Co., Ltd.) and 0.01 equivalents of aluminum chloride were added to dichlorobenzene (Samchun Chemical Co., Ltd.) and thoroughly stirred while heating to 140°C. When the temperature reached 140°C, a 35 mixture of 1 equivalent of phenyldichloride phosphonate (Acros Co., Ltd.) with 9 dichlorobenzene (Samchun Chemical Co., Ltd.) was dropped thereinto, thereby initiating reaction. After completion of dropping, the product was further stirred for 8 hours, and then the reaction terminated. Then, the product was washed with a 30 % or less hydrochloric acid solution, followed by elimination of a water layer, elimination of 5 dichlorobenzene through vacuum distillation, and then measurement of an acid value. Toluene and 6 equivalents of propylene oxide (Aldrich Co., Ltd.) of the acid value were added to the product, which was heated to 130°C, followed by stirring for a period of time listed in Table 2. Temperature was lowered to room temperature, and the product was washed with water twice and deposited in normal hexane, thereby obtaining a final 10 product.
Comparative Example 1
The same process as in Example 1 was carried out except that treatment with propylene oxide was not conducted.
15
Comparative Example 2
The same process as in Example 6 was carried out except that treatment with propylene oxide was not conducted.
20 The polyphosphonates prepared in Examples 1 to 8 and Comparative
Examples 1 and 2 were evaluated as to acid value and yield by the following method, and results are listed in Tables 1 and 2.
Acid value (mg KOH/g): 1 to 20 g of a sample was dissolved in dimethyl 25 sulfoxide (50ml) and 0.03 to 0.2 ml of a BTB solution was added thereto, after which the Consumed amount of 0.1N-NaOH solution was measured by titration with a 0.1 N NaOH solution. The acid value of the mixture was calculated by the following equation 1: [Equation 1]
30 Acid value = ((Consumed amount of 0.1N-NaOH solution (ml)) * (0.1N-NaOH
solution Factor) * 5.61) / amount of sample (g) 35 10
Table 1
Process time (h) Add value
Example l 1_5J_ 5 Example 2 2 3..9
Example 3 4_ZO_
Example 4 8 1.2
Example 5 20 0.8 10 Comparative ^
Example 1___
In Table 1, it can be seen that Examples 1 to 5 employing the method of the present invention exhibit a remarkably low acid value as compare with Comparative Example 1.
15
Table 2 _Process time (h) Acid value_
Example 6 1 0.1 20 Example 7 2 0.01
Example 8 4 0.01
Comparative 0 >6
Example 2___ 25 Preparation of thermoplastic resin composition
Polyphosphonate prepared in each of Examples 1 to 8 and Comparative Examples 1 and 2 was added to 100 parts by weight of polycarbonate and extruded into pellets using a general biaxial extruder at 200 to 280°C. 0.01 to 0.015 g of these pellets was dissolved in a 2 ml MC, and the solution was diluted with about 10 ml of 30 THF and then filtered through a 0.45 pm syringe filter. Molecular weight was measured by gel permeation chromatography (GPC) and flame retardancy at a thickness of 1/8" was measured according to UL94 VB standards. Heat resistance (unit: °C) was measured according to ASTM D648 (1/4, 18.6 kg).
35 Comparative Example 3 11
The same process as above was carried out except that phosphate ester (PX-200, Daihachi Co., Ltd.) was used as a flame retardant in 100 parts by weight of polycarbonate having a number average molecular weight of 12,700 g/mol and weight number average molecular weight of 24,300 g/mol.
5
Table 3
Molecular weight
Composition (Phr.) __of PC _Flame He at a r. No. Polv- retar- resis- 1U Mn Mw phos- PX-200 PC dancy tance (g/mol) (g/mol) _phonate__'m______
Example 1 5_-_100 12900 25000 V-2_140
Example 2 5_-_100 14100 26200 V-0_141 15 Example 3 5_-_100 14100 26800 V-0 141
Example 4 5_-_100 14100 26900 V-0 142
Example 5 5 - 100 14300 27000 V-0 143
Comparative 5 - 100 11500 22900 V-2 139
Example 1 20----------
Comparative' 5 100 12700 24300 V-0 133.3
Example 3________
Table 4 25 _____
Molecular weight
Composition (Phr.) Flame Heat ' _of PC _
Mo. retar- resis-
Polyptios- Mn 17 w PX-200 PC , . dancy tance _phonate___fq/mol) (q/rrol)___ 30 Example 6 5_2_100 122CQ 244CQ V-0 140,5
Example 7 5_-_100 138CQ 2S4C0 V-0 140.7
Examples 5 - 100 14500 26000 V-0 141.0
Comparative 5 - 100' 11600 2270Q' V-2 139
Example 2_________ 35 Comparative 5 100 12700 24300 V-0 133.3
Example 3 _______ 12
As shown in Tables 3 and 4, the polyphosphonate prepared by the method according to the present invention did not cause decomposition of polycarbonates, and thus the polycarbonate had a high molecular weight. Further, the resin compositions have remarkably excellent heat resistance as compared with those in Comparative 5 Examples 3 and 4, which used a monomolecular phosphorus flame retardant.
Although some embodiments have been disclosed herein, it should be understood that these embodiments are provided by way of illustration only, and that various modifications, changes, and alterations can be made without departing from the 10 spirit and scope of the invention. Therefore, the scope of the invention should be limited only by the accompanying claims and equivalents thereof.
15
Claims (12)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20100139697 | 2010-12-30 | ||
| KR20100139697 | 2010-12-30 | ||
| KR1020110114177A KR20120078582A (en) | 2010-12-30 | 2011-11-03 | Polyphosphonate, method for preparing thereof and flame retardant thermoplastic resin composition comprising the same |
| KR20110114177 | 2011-11-03 | ||
| KR1020110127937A KR101459123B1 (en) | 2010-12-30 | 2011-12-01 | Polyphosphonate, method for preparing thereof and flame retardant thermoplastic resin composition comprising the same |
| KR20110127937 | 2011-12-01 |
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| NL2007946C2 true NL2007946C2 (en) | 2012-09-24 |
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| KR20140090290A (en) * | 2012-12-17 | 2014-07-17 | 제일모직주식회사 | Flame retardant thermoplastic resin composition and article produced therefrom |
| KR102318469B1 (en) * | 2019-08-30 | 2021-10-27 | 롯데케미칼 주식회사 | Thermoplastic resin composition and article produced therefrom |
| WO2023206073A1 (en) * | 2022-04-26 | 2023-11-02 | Eastman Chemical (China) Co., Ltd. | Flame retardant copolyester compositions |
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| JP3305165B2 (en) * | 1994-06-23 | 2002-07-22 | 大八化学工業株式会社 | Method for purifying phosphates |
| KR100463960B1 (en) * | 2002-07-11 | 2004-12-30 | 제일모직주식회사 | Flame Retardant Thermoplastic Resin Composition |
| KR20050062756A (en) * | 2004-11-12 | 2005-06-27 | 리플우드 포스포러스 엘엘씨 | Epoxy-stabilized polyphosphate compositions |
| US20110263767A1 (en) * | 2009-01-19 | 2011-10-27 | Daihachi Chemical Industry Co., Ltd. | Phosphorus flame retardant, flame-retardant resin composition containing same, and molded body |
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| NL2007946A (en) | 2012-07-03 |
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