JPH05163393A - Thermoplastic resin composition - Google Patents

Thermoplastic resin composition

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Publication number
JPH05163393A
JPH05163393A JP3332158A JP33215891A JPH05163393A JP H05163393 A JPH05163393 A JP H05163393A JP 3332158 A JP3332158 A JP 3332158A JP 33215891 A JP33215891 A JP 33215891A JP H05163393 A JPH05163393 A JP H05163393A
Authority
JP
Japan
Prior art keywords
polypropylene
weight
resin composition
thermoplastic resin
modified polyolefin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP3332158A
Other languages
Japanese (ja)
Inventor
Sadafumi Furukawa
禎史 古川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Bakelite Co Ltd
Original Assignee
Sumitomo Bakelite Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Bakelite Co Ltd filed Critical Sumitomo Bakelite Co Ltd
Priority to JP3332158A priority Critical patent/JPH05163393A/en
Publication of JPH05163393A publication Critical patent/JPH05163393A/en
Pending legal-status Critical Current

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Abstract

PURPOSE:To prepare the title compsn. which is excellent in moldability and in the balance among various properties such as stiffness and resistances to scratch, heat, impact, oil, and chemicals and gives a film or sheet excellent in appearance and clarity by compounding polypropylene, a methacrylic resin, and a modified polyolefin and homogeneously dispersing the modified polyolefin into microparticles having a particle diameter of 1mum or lower. CONSTITUTION:100 pts.wt. resin compsn. comprising 5-95wt.% polypropylene and 95-5wt.% methacrylic resin obtd. by polymerizing methyl methacrylate alone or together with another copolymerizable vinyl or vinylidene monomer is compounded with 1-20 pts.wt. modified polyolefin.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、射出成形や押出成形等
により、成形品、シートあるいは、フィルム等として利
用できる新規な熱可塑性樹脂組成物に関するものであ
る。更に詳しくは、ポリプロピレンとメタクリル樹脂と
の相溶性が著しく改善され、物性バランス及び外観、透
明性に優れた新規な熱可塑性樹脂組成物に関するもので
ある。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thermoplastic resin composition which can be used as a molded product, sheet or film by injection molding, extrusion molding or the like. More specifically, the present invention relates to a novel thermoplastic resin composition in which the compatibility between polypropylene and a methacrylic resin is remarkably improved and the balance of physical properties, appearance and transparency are excellent.

【0002】[0002]

【従来の技術】ポリプロピレンは成形加工性、強靭性、
耐水性、耐ガソリン性、耐薬品性などに優れ、低比重で
安価であることから各種成形品やフィルム、シート等に
従来から広く利用されている。しかし、ポリプロピレン
は、耐熱性、剛性、耐傷付性、塗装性、接着性、印刷性
等において難点、あるいは改良点を有し、新規な用途開
拓をはかるためには、これらを更に改良することが望ま
れている。一方、メタクリル樹脂は、高分子材料の中で
も透明性や表面光沢などの光学的性質、機械的性質、高
度の引掻き抵抗、耐候性などに卓越した特性を有し、ま
た成形加工せいにおいても優れた特性を有している。こ
れらの特性を生かして照明器具、看板、窓材、光学レン
ズ、車両部品及び各種ディスプレイなど多くの分野で使
用されている。しかし、メタクリル樹脂は、耐衝撃性が
不足しているため、多くの用途分野においてその改良が
強く望まれており、上述のメタクリル樹脂本来の特性を
損なわず、耐衝撃性を付与する方法が古くから検討され
てる。例えば、MBS樹脂あるいは、ABSM樹脂(ア
クリロニトリル−ブタジエン−スチレン−メチルメタク
リレート)を混合するとたしかに透明性を低下させずに
著しく耐衝撃性を改良することができるが、フィッシュ
アイと呼ばれる未溶融物が発生する場合があり、特に押
出成形物ではこのため表面に凹凸が生じやすく、その外
観特性を阻害してしまい、その用途が著しく制限される
場合を生じるとともに、耐水性、耐薬品性においては、
満足なものが得られていない。
2. Description of the Related Art Polypropylene has a good moldability, toughness,
Since it is excellent in water resistance, gasoline resistance, chemical resistance, etc., and has low specific gravity and is inexpensive, it has been widely used for various molded products, films, sheets and the like. However, polypropylene has drawbacks or improvements in heat resistance, rigidity, scratch resistance, paintability, adhesiveness, printability, etc., and in order to develop new applications, it is necessary to further improve these. Is desired. On the other hand, methacrylic resin has excellent properties among polymer materials such as optical properties such as transparency and surface gloss, mechanical properties, high scratch resistance and weather resistance, and is also excellent in molding processing. It has characteristics. Utilizing these characteristics, it is used in many fields such as lighting equipment, signboards, window materials, optical lenses, vehicle parts and various displays. However, since the methacrylic resin lacks impact resistance, there is a strong demand for improvement in many fields of application, and the method of imparting impact resistance without impairing the original characteristics of the methacrylic resin is old. Is being considered by. For example, when MBS resin or ABSM resin (acrylonitrile-butadiene-styrene-methylmethacrylate) is mixed, the impact resistance can be remarkably improved without lowering the transparency, but an unmelted material called fish eye is generated. In particular, in the case of an extruded product, unevenness is likely to occur on the surface, which hinders its appearance properties, resulting in a case where its use is significantly limited, and in water resistance and chemical resistance,
Satisfaction has not been obtained.

【0003】[0003]

【発明が解決しようとする課題】本発明は、ポリプロピ
レンとメタクリル樹脂に変性ポリプロピレンを配合する
ことにより、分散粒子径を0.3μm以下にミクロに均
一分散させ、成形加工性、剛性、耐傷付性、耐熱性、耐
衝撃性、耐油性、耐薬品性、耐水性等の物性のバランス
がきわめて良好で、かつフィルム、シート等成形加工時
の外観及び透明性の優れた新規な熱可塑性樹脂組成物を
提供することを目的とするものである。
DISCLOSURE OF THE INVENTION According to the present invention, a polypropylene and a methacrylic resin are blended with a modified polypropylene to uniformly disperse the dispersed particles to a size of 0.3 μm or less, thereby forming processability, rigidity and scratch resistance. , A new thermoplastic resin composition having a very good balance of physical properties such as heat resistance, impact resistance, oil resistance, chemical resistance, and water resistance, and having excellent appearance and transparency during molding of films, sheets, etc. It is intended to provide.

【0004】[0004]

【課題を解決するための手段】本発明は、ポリプロピレ
ン(A)5〜95重量%及び、メタクリル酸メチル単
独、またはメタクリル酸メチルと他の共重合性のビニル
またはビニリデン系単量体の混合物を重合して得られた
メタクリル樹脂(B)95〜5重量%からなる樹脂組成
物100重量部に対して、変性ポリオレフィン(C)1
〜20重量部を配合してなることを特徴とする熱可塑性
樹脂組成物に関するものである。
The present invention comprises 5 to 95% by weight of polypropylene (A) and methyl methacrylate alone or a mixture of methyl methacrylate and another copolymerizable vinyl or vinylidene monomer. Modified polyolefin (C) 1 to 100 parts by weight of a resin composition consisting of 95 to 5% by weight of a methacrylic resin (B) obtained by polymerization.
The present invention relates to a thermoplastic resin composition characterized by being mixed in an amount of up to 20 parts by weight.

【0005】一般に、二種以上の樹脂を組み合わせた場
合に透明性良好なものを得るためには、各々の樹脂の屈
折率がほとんど同じものを選ぶことと、分散粒子径をミ
クロに分散させることが考えられる。本発明の場合は、
樹脂としては屈折率がほぼ同一のものを選び、なおかつ
分散粒子径を微細にすることで今までにない、物性のバ
ランスが良好でかつ透明性に優れた熱可塑性樹脂を得る
ことができた。
In general, in order to obtain a resin having good transparency when two or more kinds of resins are combined, it is necessary to select resins having almost the same refractive index and to disperse dispersed particles in a microscopic size. Can be considered. In the case of the present invention,
By selecting resins having almost the same refractive index and making the dispersed particle diameter finer, it was possible to obtain a thermoplastic resin having a good balance of physical properties and excellent transparency, which has never existed before.

【0006】本発明に、用いられるポリプロピレン
(A)とは結晶性のポリプロピレンであり、ポリプロピ
レンのホモポリマーのほかに第1工程でポリプロピレ
ン、第2工程でたとえばエチレンとポリプロピレン、ブ
テン−1などのα−オレフィンとを共重合させたランダ
ムコポリマー等を含む。ポリプロピレンのホモポリマ
ー、ブロックあるいはランダムコポリマーは、例えば、
通常チーグラーナッタ型触媒と呼称される三塩化チタン
及びアルキルアルミニウム化合物との組み合わせ触媒の
存在下に反応させて得ることができる。
The polypropylene (A) used in the present invention is crystalline polypropylene, and in addition to polypropylene homopolymer, polypropylene is used in the first step, and α and α, such as ethylene and polypropylene, butene-1 in the second step. -Including random copolymers copolymerized with olefins. Homopolymer, block or random copolymer of polypropylene, for example,
It can be obtained by reacting in the presence of a combination catalyst of titanium trichloride and an alkylaluminum compound, which is usually called Ziegler-Natta type catalyst.

【0007】本発明に、用いられるメタクリル樹脂
(B)は、メタクリル酸メチル単独、またはメタクリル
酸メチルと他の共重合性のビニルまたはビニリデン系単
量体の混合物を重合して得られるものであり、好ましく
は80重量%以上のメタクリル酸メチルを含有するもの
である。他の共重合性のビニルまたはビニリデン系単量
体としては、好ましくはアクリル酸メチル、アクリル酸
エチル、アクリル酸ブチル、アクリル酸2−エチルヘキ
シルなどの炭素数1〜8のアクリル酸アルキルエステ
ル、スチレン、及びアクリロニトリルが挙げられる。
The methacrylic resin (B) used in the present invention is obtained by polymerizing methyl methacrylate alone or a mixture of methyl methacrylate and another copolymerizable vinyl or vinylidene monomer. , Preferably containing 80% by weight or more of methyl methacrylate. Other copolymerizable vinyl or vinylidene-based monomers are preferably methyl acrylate, ethyl acrylate, butyl acrylate, alkyl acrylates having 1 to 8 carbon atoms such as 2-ethylhexyl acrylate, styrene, And acrylonitrile.

【0008】次に、本発明において使用する変性ポリオ
レフィン(C)とは、炭素数2〜20のα−オレフィン
やジエン、例えばエチレン、プロピレン、ブテン−1、
ペンテン−1、4−メチルペンテン−1、イソブチレ
ン、1,4−ヘキサジエン、ジシクロペンタジエン、
2,5−ノルボルナジエン、5−エチル−2,5−ノル
ボルナジエン、5−エチリデンノルボルネン、5−
(1’−プロペニル)−2−ノルボルネン、ブタジエ
ン、イソプレン、クロロプレン等の単独共重合体、ラン
ダムまたはブロック等の共重合体などを主たる構成成分
とし、酸無水物基、カルボン酸基及びカルボン酸金属塩
基、水酸基、グリシジル基から選ばれた少なくとも一種
の官能基を有する単量体成分を導入した重合体を意味す
る。中でも、平均分子量が1000〜12000のポリ
エチレン、及びポリプロピレンの末端を水酸基変性した
ものが特に好ましい。なお、これらは2種類以上の混合
物としても使用できる。
Next, the modified polyolefin (C) used in the present invention means an α-olefin or a diene having 2 to 20 carbon atoms such as ethylene, propylene, butene-1,
Pentene-1,4-methylpentene-1, isobutylene, 1,4-hexadiene, dicyclopentadiene,
2,5-norbornadiene, 5-ethyl-2,5-norbornadiene, 5-ethylidene norbornene, 5-
(1'-propenyl) -2-norbornene, butadiene, isoprene, chloroprene and other homocopolymers, random or block copolymers, etc. as main constituents, and acid anhydride group, carboxylic acid group and carboxylic acid metal It means a polymer into which a monomer component having at least one functional group selected from a base, a hydroxyl group and a glycidyl group is introduced. Among them, polyethylene having an average molecular weight of 1000 to 12000 and polypropylene in which a terminal of polypropylene is modified with a hydroxyl group are particularly preferable. In addition, these can also be used as a mixture of 2 or more types.

【0009】本発明による熱可塑性樹脂組成物におい
て、ポリプロピレン(A)5〜95重量%及び、メタク
リル酸メチル単独、またはメタクリル酸メチルと他の共
重合性のビニルまたはビニリデン系単量体の混合物を重
合して得られたメタクリル樹脂(B)95〜5重量%か
らなる樹脂組成物100重量部に対して、変性ポリオレ
フィン(C)1〜20重量部配合しなければならない。 (A)成分の含量が5重量%より少ない場合は、成形加
工性、耐水性、及び耐薬品性が十分でなく、95重量%
より多い場合は、剛性において好ましい性質が得られな
い。 (B)成分の含量が5重量%より少ない場合は、剛性、
表面光沢が十分でなく、95重量%より多い場合は、耐
衝撃性が不十分である。 また、(C)成分については、含量が1重量部より少な
い場合は、樹脂組成物の相溶分散性に問題があり、分散
粒子径が数十〜数百μmと大きく、外観、及び透明性が
不十分である。また、含量が20重量部より多い場合
は、耐熱性、剛性等の低下が著しく好ましい結果が得ら
れない。
In the thermoplastic resin composition according to the present invention, 5 to 95% by weight of polypropylene (A) and methyl methacrylate alone or a mixture of methyl methacrylate and another copolymerizable vinyl or vinylidene monomer are used. 1 to 20 parts by weight of the modified polyolefin (C) must be added to 100 parts by weight of the resin composition consisting of 95 to 5% by weight of the methacrylic resin (B) obtained by polymerization. When the content of the component (A) is less than 5% by weight, moldability, water resistance, and chemical resistance are insufficient, and 95% by weight.
If the amount is larger than the above range, favorable properties in rigidity cannot be obtained. When the content of the component (B) is less than 5% by weight, the rigidity,
If the surface gloss is insufficient and is more than 95% by weight, the impact resistance is insufficient. Further, regarding the component (C), when the content is less than 1 part by weight, there is a problem in the compatibility dispersibility of the resin composition, the dispersed particle diameter is as large as several tens to several hundreds μm, and the appearance and transparency are high. Is insufficient. When the content is more than 20 parts by weight, heat resistance, rigidity and the like are remarkably deteriorated and a desirable result cannot be obtained.

【0010】更に、必要に応じて基本的性質を損なわな
い範囲で添加剤、例えば染顔料、安定剤、可塑剤、帯電
防止剤、紫外線吸収剤、酸化防止剤、滑剤、充填剤等、
及び柔軟性を付与するエラストマー等も添加することも
できる。本発明による熱可塑性樹脂組成物は、通常の熱
可塑性樹脂組成物に用いられている加工方法、例えば射
出成形、押出成形等により、容易に成形品、フィルム、
シート等に加工されるが、射出成形等で成形品が肉厚の
場合は、冷却過程でポリプロピレンの結晶化により透明
性が損なわれる場合があるので、冷却条件を30〜60
℃の範囲で急冷するよう設定するのが望ましい。
Further, if necessary, additives such as dyes and pigments, stabilizers, plasticizers, antistatic agents, ultraviolet absorbers, antioxidants, lubricants, fillers, etc. are added to the extent that basic properties are not impaired.
Also, an elastomer or the like which imparts flexibility can be added. The thermoplastic resin composition according to the present invention is easily processed into a molded product, a film, by a processing method used for a usual thermoplastic resin composition, such as injection molding or extrusion molding.
Although it is processed into a sheet or the like, if the molded product is thick by injection molding or the like, transparency may be impaired by crystallization of polypropylene in the cooling process.
It is desirable to set the temperature to cool rapidly in the range of ° C.

【0011】[0011]

【実施例】以下実施例により、本発明を説明するが、こ
れは単なる例示であり、本発明はこれに限定されるもの
ではない。なお、0.25mmのT−ダイシートを使用
し、光線透過率、及びHAZEはASTM−D1003
により、また引張試験はASTM−D638、曲げ試験
はASTM−D790、アイゾット衝撃試験はASTM
−D256によって測定した結果である。また、外観に
ついては目視により判定した。配合組成及び各特性値の
結果は表1に示した。
EXAMPLES The present invention will be described with reference to the following examples, but these are merely examples and the present invention is not limited thereto. A T-die sheet of 0.25 mm was used, and light transmittance and Haze were ASTM-D1003.
Also, the tensile test is ASTM-D638, the bending test is ASTM-D790, and the Izod impact test is ASTM.
It is a result measured by -D256. The appearance was visually determined. The results of the blended composition and each characteristic value are shown in Table 1.

【0012】(実施例1〜3)(A)成分としては、ノ
ーブレンS131(PP;住友化学工業製)を使用し、
(B)成分としては、スミペックス−B LO−6(P
MMA;住友化学工業製)を使用し、(C)成分として
は、平均分子量が4000のポリプロピレンオリゴマー
の末端を水酸基変性したもの(PP−OH)を使用し
た。
(Examples 1 to 3) Noblene S131 (PP; manufactured by Sumitomo Chemical Co., Ltd.) was used as the component (A),
As the component (B), Sumipex-B LO-6 (P
(MMA; manufactured by Sumitomo Chemical Co., Ltd.) was used, and as the component (C), a polypropylene oligomer having an average molecular weight of 4000 and a terminal modified with hydroxyl groups (PP-OH) was used.

【0013】(実施例4)(A)成分としては、ノーブ
レンS131(PP;住友化学工業製)を使用し、
(B)成分としては、スミペックス−B LO−6(P
MMA;住友化学工業製)を使用し、(C)成分として
は、平均分子量が4000のポリプロピレンオリゴマー
の末端を無水マレイン酸変性したもの(PP−MAH)
を使用した。
Example 4 As the component (A), Noblene S131 (PP; manufactured by Sumitomo Chemical Co., Ltd.) was used,
As the component (B), Sumipex-B LO-6 (P
MMA; manufactured by Sumitomo Chemical Co., Ltd.), and as the component (C), a polypropylene oligomer having an average molecular weight of 4000 is modified with maleic anhydride at its end (PP-MAH).
It was used.

【0014】(実施例5)(A)成分としては、ノーブ
レンS131(PP;住友化学工業製)を使用し、
(B)成分としては、スミペックス−B LO−6(P
MMA;住友化学工業製)を使用し、(C)成分として
は、エチレン−グリシジルメタクリレート共重合体(E
−GMA)で、GMA含量が12wt%のものを使用し
た。
Example 5 As the component (A), Noblene S131 (PP; manufactured by Sumitomo Chemical Co., Ltd.) was used,
As the component (B), Sumipex-B LO-6 (P
MMA; manufactured by Sumitomo Chemical Co., Ltd., and an ethylene-glycidyl methacrylate copolymer (E) is used as the component (C).
-GMA) having a GMA content of 12 wt% was used.

【0015】(実施例6)(A)成分としては、ノーブ
レンS131(PP;住友化学工業製)を使用し、
(B)成分としては、スミペックス−B LO−6(P
MMA;住友化学工業製)を使用し、(C)成分として
は、平均分子量が4000のポリプロピレンオリゴマー
の末端を水酸基変性したもの及び、エチレン−グリシジ
ルメタクリレート共重合体(E−GMA)で、GMA含
量が12wt%のものを使用した。
Example 6 As the component (A), Nobrene S131 (PP; manufactured by Sumitomo Chemical Co., Ltd.) was used.
As the component (B), Sumipex-B LO-6 (P
MMA; manufactured by Sumitomo Chemical Co., Ltd.), and as the component (C), a polypropylene oligomer having an average molecular weight of 4000 is modified with a hydroxyl group at the terminal and an ethylene-glycidyl methacrylate copolymer (E-GMA) with a GMA content Of 12 wt% was used.

【0016】(比較例1)(A)成分としては、ノーブ
レンS131(PP;住友化学工業製)を使用し、
(B)成分としては、スミペックス−B LO−6(P
MMA;住友化学工業製)を使用した。
Comparative Example 1 Noblene S131 (PP; manufactured by Sumitomo Chemical Co., Ltd.) was used as the component (A),
As the component (B), Sumipex-B LO-6 (P
MMA; manufactured by Sumitomo Chemical Co., Ltd.) was used.

【0017】[0017]

【表1】 [Table 1]

【0018】[0018]

【発明の効果】本発明による熱可塑性樹脂組成物は、通
常の熱可塑性樹脂組成物に用いられている加工方法、例
えば射出成形、押出成形等により、容易に成形品、フィ
ルム、シート等に加工され、成形加工性、剛性、耐傷付
性、耐熱性、耐衝撃性、耐油性、耐薬品性、耐水性等の
物性のバランスがきわめて良好でかつ、フィルム、シー
ト等成形加工時の外観及び透明性の優れた製品を与え
る。
EFFECT OF THE INVENTION The thermoplastic resin composition according to the present invention can be easily processed into molded articles, films, sheets, etc. by the processing methods used for ordinary thermoplastic resin compositions such as injection molding and extrusion molding. It has an excellent balance of physical properties such as moldability, rigidity, scratch resistance, heat resistance, impact resistance, oil resistance, chemical resistance, water resistance, etc., and the appearance and transparency of the film and sheet during molding. Gives excellent product.

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】 ポリプロピレン(A)5〜95重量%及
び、メタクリル酸メチル単独、またはメタクリル酸メチ
ルと他の共重合性のビニルまたはビニリデン系単量体の
混合物を重合して得られたメタクリル樹脂(B)95〜
5重量%からなる樹脂組成物100重量部に対して、変
性ポリオレフィン(C)1〜20重量部を配合してなる
ことを特徴とする熱可塑性樹脂組成物。
1. A methacrylic resin obtained by polymerizing 5 to 95% by weight of polypropylene (A) and methyl methacrylate alone or a mixture of methyl methacrylate and another copolymerizable vinyl or vinylidene monomer. (B) 95-
A thermoplastic resin composition comprising 100 parts by weight of a resin composition of 5% by weight and 1 to 20 parts by weight of a modified polyolefin (C).
【請求項2】 変性ポリオレフィンが酸無水物基、カル
ボン酸基及びカルボン酸金属塩基、水酸基、グリシジル
基から選ばれた少なくとも一種の官能基を有する単量体
で変性されたポリオレフィンである請求項1記載の熱可
塑性樹脂組成物。
2. The modified polyolefin is a polyolefin modified with a monomer having at least one functional group selected from an acid anhydride group, a carboxylic acid group, a metal carboxylate group, a hydroxyl group and a glycidyl group. The thermoplastic resin composition described.
JP3332158A 1991-12-16 1991-12-16 Thermoplastic resin composition Pending JPH05163393A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP3332158A JPH05163393A (en) 1991-12-16 1991-12-16 Thermoplastic resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP3332158A JPH05163393A (en) 1991-12-16 1991-12-16 Thermoplastic resin composition

Publications (1)

Publication Number Publication Date
JPH05163393A true JPH05163393A (en) 1993-06-29

Family

ID=18251803

Family Applications (1)

Application Number Title Priority Date Filing Date
JP3332158A Pending JPH05163393A (en) 1991-12-16 1991-12-16 Thermoplastic resin composition

Country Status (1)

Country Link
JP (1) JPH05163393A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017031319A (en) * 2015-07-31 2017-02-09 三井・デュポンポリケミカル株式会社 Methacrylic resin composition and molded body

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017031319A (en) * 2015-07-31 2017-02-09 三井・デュポンポリケミカル株式会社 Methacrylic resin composition and molded body

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