JPH06184389A - Methacrylic resin composition - Google Patents

Methacrylic resin composition

Info

Publication number
JPH06184389A
JPH06184389A JP33576192A JP33576192A JPH06184389A JP H06184389 A JPH06184389 A JP H06184389A JP 33576192 A JP33576192 A JP 33576192A JP 33576192 A JP33576192 A JP 33576192A JP H06184389 A JPH06184389 A JP H06184389A
Authority
JP
Japan
Prior art keywords
formula
resin composition
methyl methacrylate
acid amide
mold
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
JP33576192A
Other languages
Japanese (ja)
Inventor
Takeshi Hashimoto
剛 橋本
Takashi Sakamoto
坂本  隆
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 Chemical Co Ltd
Original Assignee
Sumitomo Chemical 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 Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Priority to JP33576192A priority Critical patent/JPH06184389A/en
Publication of JPH06184389A publication Critical patent/JPH06184389A/en
Pending legal-status Critical Current

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE:To obtain a resin composition having excellent mold release performance by incorporating both pentaerythritol or an analogue thereof and a higher fatty amide into a methyl methacrylate polymer. CONSTITUTION:This resin composition comprises 100 pts.wt. methyl methacrylate polymer and 0.02-0.5wt.% mixture of at lease one compound selected from pentaerythritol and analogues thereof represented by formula I or V and a 10-22C fatty amide in a weight ratio of 10/90 to 90/10. In formula I, X<1>, X<2>, X<3>, and X<4> each is H or a group represented by formula II (wherein R is a 10-22C hydrocarbon group), formula III (wherein (f) is 1-5), or formula IV (wherein (g) is 1-5). In formula V, X<5>, X<6>, X<7>, X<8>, X<9>, X<10>, X<11>, and X<12> have the same meaning as X<1> to X<4> and (n) is 0-3.

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、加工性に優れたメタク
リル系樹脂組成物に関するものである。特に、金型を用
いた成形加工時の離型性に優れたメタクリル系樹脂組成
物に関する物である。
FIELD OF THE INVENTION The present invention relates to a methacrylic resin composition having excellent processability. In particular, the present invention relates to a methacrylic resin composition having excellent mold releasability at the time of molding using a mold.

【0002】[0002]

【従来の技術】メタクリル系樹脂は、本来の特性の優れ
た透明性、耐候性、良好な機械的性質を生かして、メー
ターカバー等の自動車部品、光ディスク、レンズ等の光
学部品、電灯カバー等の照明部品等に使用されている。
これらの成形品は一般に射出成形、射出圧縮成形等で得
られているが、光学レンズや光ディスクのような精密金
型成形においては、成形品と金型面との密着性が極めて
高くなるために型離れ不良が発生し、生産性を低下させ
る結果となっている。
BACKGROUND OF THE INVENTION Methacrylic resins are used in automobile parts such as meter covers, optical parts such as optical discs and lenses, and electric lamp covers, etc. by taking advantage of their original excellent transparency, weather resistance and good mechanical properties. Used for lighting parts.
These molded products are generally obtained by injection molding, injection compression molding, etc., but in precision mold molding such as optical lenses and optical disks, the adhesion between the molded product and the mold surface becomes extremely high. Mold release failure occurs, resulting in a decrease in productivity.

【0003】そこでメタクリル樹脂に各種離型剤を含有
させることが提案されている。例えば、特開昭61-73754
号公報には、メタクリル系樹脂に、多価アルコール、高
級脂肪酸エステル、高級アルコール、高級脂肪酸、高級
脂肪酸アミド、高級脂肪酸金属塩を添加した樹脂組成物
が提案されている。
Therefore, it has been proposed to add various release agents to the methacrylic resin. For example, Japanese Patent Laid-Open No. 61-73754
The publication discloses a resin composition in which a polyhydric alcohol, a higher fatty acid ester, a higher alcohol, a higher fatty acid, a higher fatty acid amide, and a higher fatty acid metal salt are added to a methacrylic resin.

【0004】[0004]

【発明が解決しようとする課題】しかしながらこれらの
樹脂組成物での射出成形を行った場合、ある程度の離型
性能は認められるものの未だ充分でない。その上添加さ
れている離型剤やその他の添加剤が樹脂表面に移行し
て、金型表面あるいは成形品表面を汚したり、成形品の
着色をもたらすなど成形品の商品価値を著しく低下させ
る。
However, when injection molding is performed using these resin compositions, some degree of mold release performance is recognized, but it is still insufficient. In addition, the release agent and other additives added to the resin migrate to the surface of the resin to stain the surface of the mold or the surface of the molded product and to color the molded product, thereby significantly reducing the commercial value of the molded product.

【0005】本発明は、従来の離型剤のもつ欠点を克服
し、より少ない配合量によって優れた離型効果を発揮す
るメタクリル系樹脂組成物を提供する。
The present invention provides a methacrylic resin composition which overcomes the drawbacks of conventional mold release agents and exhibits an excellent mold release effect with a smaller amount.

【0006】[0006]

【課題を解決するための手段】本発明は、メタクリル酸
メチル系重合体100重量部に対して、下記〔化3〕又
は〔化4〕で表されるペンタエリスリトール類から選ば
れた少なくとも1種と炭素数10〜22の高級脂肪酸ア
ミドを重量比10/90〜90/10で、0.02〜
0.5重量部を含有してなるメタクリル系樹脂組成物に
関するものである。
The present invention provides at least one selected from pentaerythritols represented by the following [Chemical formula 3] or [Chemical formula 4] with respect to 100 parts by weight of a methyl methacrylate polymer. And a higher fatty acid amide having 10 to 22 carbon atoms in a weight ratio of 10/90 to 90/10 and 0.02 to
The present invention relates to a methacrylic resin composition containing 0.5 part by weight.

【0007】[0007]

【化3】 [Chemical 3]

【0008】式中X1 ,X2 ,X3 及びX4 は、下記
〔外2〕で示されるものの1つである。
In the formula, X 1 , X 2 , X 3 and X 4 are ones shown in the following [External 2].

【0009】[0009]

【外2】 [Outside 2]

【0010】[0010]

【化4】 [Chemical 4]

【0011】式中X5 ,X6 ,X7 ,X8 ,X9
10,X11及びX12は、上記X1 ,X2,X3 及びX4
に同じ、nは0〜3である。
Where X 5 , X 6 , X 7 , X 8 , X 9 ,
X 10 , X 11 and X 12 are the above X 1 , X 2 , X 3 and X 4
And n is 0 to 3.

【0012】本発明でいうメタクリル酸メチル系重合体
とは、メタクリル酸メチル単独重合体、またはメタクリ
ル酸メチルと20重量%以下のアクリル酸エステルもし
くはメタクリル酸エステル、アクリル酸、メタクリル
酸、スチレン、アクリロニトリルあるいは、ジエン系ゴ
ムやグルタル酸無水物、グルタルイミドなどとの共重合
体をいう。なお、アクリル酸エステルとしてはアクリル
酸メチル、アクリル酸エチル、アクリル酸ブチルなど、
メタクリル酸エステルとしてはメタクリル酸エチル、メ
タクリル酸ブチル、メタクリル酸シクロヘキシルなどで
ある。
The term "methyl methacrylate polymer" as used in the present invention means a homopolymer of methyl methacrylate, or methyl methacrylate and 20% by weight or less of acrylic acid ester or methacrylic acid ester, acrylic acid, methacrylic acid, styrene, acrylonitrile. Alternatively, it refers to a copolymer with a diene rubber, glutaric anhydride, glutarimide, or the like. As the acrylic ester, methyl acrylate, ethyl acrylate, butyl acrylate, etc.
Examples of the methacrylic acid ester include ethyl methacrylate, butyl methacrylate and cyclohexyl methacrylate.

【0013】本発明の〔化3〕又は〔化4〕で表される
ペンタエリスリトール類としては、例えばモノペンタエ
リスリトール,ジペンタエリスリトール,トリペンタエ
リスリトール,テトラペンタエリスリトール,及びペン
タペンタエリスリトールと、これらのペンタエリスリト
ールとラウリン酸、ミリスチン酸、ステアリン酸、ベヘ
ン酸、オレイン酸、リノール酸、リノレン酸等の如き炭
素数10〜22の炭化水素基Rを有するカルボン酸との
各エステル化合物、更にはこれらペンタエリスリトール
のエチレンオキシド及び/又はプロピレンオキシドの1
〜5個の付加物等が挙げられる。
The pentaerythritols represented by [Chemical Formula 3] or [Chemical Formula 4] of the present invention include, for example, monopentaerythritol, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, and pentapentaerythritol, and these. Each ester compound of pentaerythritol and a carboxylic acid having a hydrocarbon group R having 10 to 22 carbon atoms such as lauric acid, myristic acid, stearic acid, behenic acid, oleic acid, linoleic acid and linolenic acid, and further these penta compounds Erythritol ethylene oxide and / or propylene oxide 1
.About.5 adducts and the like.

【0014】該ペンタエリスリトールのカルボン酸との
各エステル化合物の炭化水素基Rの炭素数が10未満の
ものは、揮発性が高く成形時に揮散して充分な離型効果
が得られない。一方炭素数が22を超えるものは、メタ
クリル酸メチル系重合体との相溶性が小さいため、樹脂
表面に出易く、金型汚れ、成形品汚れの原因となり好ま
しくない。又、前記〔化3〕又は〔化4〕のf,gが5
を超えるもの、及び〔化4〕のnが3を超えるものは、
メタクリル酸メチル系重合体との相溶性が小さいため、
樹脂表面に出易く、金型汚れ、成形品汚れの原因となり
好ましくない。
If the hydrocarbon group R of each ester compound of the pentaerythritol with a carboxylic acid has a hydrocarbon group R of less than 10, it has a high volatility and volatilizes during molding, and a sufficient releasing effect cannot be obtained. On the other hand, those having more than 22 carbon atoms are not preferable because they have low compatibility with the methyl methacrylate-based polymer, so that they easily appear on the resin surface and cause mold stains and molded product stains. In addition, f and g in [Chemical Formula 3] or [Chemical Formula 4] are 5
And those in which n in [Chemical Formula 4] exceeds 3,
Due to its low compatibility with methyl methacrylate polymers,
It is not preferable because it easily appears on the resin surface and causes stains on the mold and molded articles.

【0015】本発明の炭素数10〜22の高級脂肪酸ア
ミドとしては、例えばラウリン酸アミド、パルミチン酸
アミド、ステアリン酸アミド、オレイン酸アミド、エル
カ酸アミド、N−オレイルステアロアミド等が挙げられ
る。
Examples of the higher fatty acid amide having 10 to 22 carbon atoms of the present invention include lauric acid amide, palmitic acid amide, stearic acid amide, oleic acid amide, erucic acid amide and N-oleyl stearoamide.

【0016】該高級脂肪酸アミドの炭素数が10未満の
ものは、揮発性が高く成形時に揮散して充分な離型効果
が得られない。一方炭素数が22をこえるものは、メタ
クリル酸メチル系重合体との相溶性が小さいため、樹脂
表面に出易く、金型汚れ、成形品汚れの原因となり好ま
しくない。
When the higher fatty acid amide has less than 10 carbon atoms, it has a high volatility and is volatilized during molding, and a sufficient releasing effect cannot be obtained. On the other hand, those having more than 22 carbon atoms are not preferable because they have a low compatibility with the methyl methacrylate-based polymer and are likely to appear on the surface of the resin, causing mold stains and molded product stains.

【0017】本発明においては、該ペンタエリスリトー
ル類と、該高級脂肪酸アミドは、10/90〜90/1
0、好ましくは、25/75〜75/25の比率で用い
ることにより、顕著な相乗効果が現われる。この比率の
範囲内で、使用されるメタクリル酸メチル系重合体の組
成、分子量、流動性などに応じて選択する。
In the present invention, the pentaerythritols and the higher fatty acid amide are contained in an amount of 10/90 to 90/1.
When used in a ratio of 0, preferably 25/75 to 75/25, a remarkable synergistic effect is exhibited. Within the range of this ratio, it is selected according to the composition, molecular weight, fluidity, etc. of the methyl methacrylate polymer used.

【0018】該ペンタエリスリトール類と該高級脂肪酸
アミドの合計量は、メタクリル酸メチル系重合体100
重量部当り0.02〜0.5重量部、好ましくは、0.
05〜0.2重量部である。これらの合計量が0.02
重量部未満の場合には、離型性能が不足し、成形品表面
層が剥離したり、割れ易くなる。一方添加量が0.5重
量部を越えた場合には、成形品の着色をもたらし、また
余剰の離型剤が金型面に付着し、金型が汚れ、汚染され
た成形品となり好ましくない。
The total amount of the pentaerythritols and the higher fatty acid amide is 100% of the methyl methacrylate polymer.
0.02 to 0.5 part by weight, preferably 0.
05 to 0.2 parts by weight. The total amount of these is 0.02
When the amount is less than the weight part, the mold release performance is insufficient and the surface layer of the molded product is easily peeled off or cracked. On the other hand, if the addition amount exceeds 0.5 parts by weight, the molded product is colored, and the surplus mold release agent adheres to the surface of the mold, so that the mold becomes dirty and contaminated. .

【0019】本発明で用いられるメタクリル酸メチル系
重合体に、該ペンタエリスリトール類、該高級脂肪酸ア
ミドを含ませて、組成物とするには、周知の方法を用い
ることができる。例えば、各成分を、溶融状態で混練す
る方法があり、該溶融混練は、一般的に使用されている
一軸または二軸の押出機、各種のニーダー等の混練装置
を用いる方法のみならず、射出成形や押出成形のごとく
溶融加工操作中に直接混練する方法がある。
A well-known method can be used to prepare a composition by incorporating the pentaerythritols and the higher fatty acid amide into the methyl methacrylate polymer used in the present invention. For example, there is a method of kneading each component in a molten state, and the melt kneading is not limited to a method using a commonly used kneading device such as a single-screw or twin-screw extruder, various kneaders, and injection. There is a method of directly kneading during a melt processing operation such as molding and extrusion molding.

【0020】又、メタクリル酸メチルを主成分とする単
量体、あるいはシロップに、該ペンタエリスリトール類
と該高級脂肪酸アミドを添加混合し、これを塊状重合
法、懸濁重合法、乳化重合法、溶液重合法など周知の方
法で重合する方法がある。
Further, the pentaerythritols and the higher fatty acid amide are added to and mixed with a monomer or syrup containing methyl methacrylate as a main component, and the mixture is subjected to a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, There is a known method such as a solution polymerization method.

【0021】なお、本発明のメタクリル系樹脂組成物に
は周知のヒンダードフェノール系酸化防止剤、リン系酸
化防止剤及びイオウ系酸化防止剤等の酸化防止剤、紫外
線吸収剤やヒンダードアミン型光安定剤等の耐候剤、難
燃剤、着色剤、顔料等を添加することも出来るし、さら
に目的によってはガラス繊維等の強化繊維、無機充填剤
等も配合することも出来る。
The methacrylic resin composition of the present invention includes antioxidants such as well-known hindered phenolic antioxidants, phosphorus antioxidants and sulfur antioxidants, ultraviolet absorbers and hindered amine type photostabilizers. It is also possible to add weathering agents such as agents, flame retardants, colorants, pigments, etc., and depending on the purpose, reinforcing fibers such as glass fibers, inorganic fillers, etc. may also be added.

【0022】[0022]

【発明の効果】本発明のメタクリル系樹脂組成物は、従
来のメタクリル系樹脂に比べ、金型を用いて成形した際
に、優れた離型性を有し、かつメタクリル系樹脂本来の
優れた透明性、耐候性も有している。 従って、メータ
ーカバー等の自動車部品、ビデオディスク、レンズ等の
光学部品、照明部品、OA機器部品等の複雑な形状の成
形品を金型を用いて成形するのに適している。
EFFECTS OF THE INVENTION The methacrylic resin composition of the present invention has excellent releasability when molded by using a mold and is excellent in original methacrylic resin as compared with the conventional methacrylic resin. It also has transparency and weather resistance. Therefore, it is suitable for molding a molded product having a complicated shape such as an automobile part such as a meter cover, an optical part such as a video disk and a lens, a lighting part, and an OA equipment part using a mold.

【0023】[0023]

【実施例】以下実施例によって本発明をさらに説明す
る。なお、実施例において用いた評価方法は次の通り。 ・離型性:容量13オンスの射出成形機(各機製作所
製、M−140SJ型)に、25mm×76.5mm×3.
2mmのASTM試験片金型を取りつけ、成形温度260
℃、射出圧力80kg/cm2 G 、金型温度60℃の条件
下、60秒サイクルで、連続40回試験片を作成した。
この時の成形品のヒビ、ワレ等の不良品の発生した個数
の比率で表わした。 ・汚染性:前記の成形を終えた直後の金型表面(鏡面
部)の曇りの状態を目視観察して曇りが見られないもの
を○、曇りが有るものを×とした。 ・外観;成形品の汚れ、着色状況を見視で観察した。
The present invention will be further described with reference to the following examples. The evaluation methods used in the examples are as follows. -Releasability: Injection molding machine with capacity of 13 ounces (M-140SJ type, manufactured by each machine) with 25 mm x 76.5 mm x
Attach a 2mm ASTM test piece mold, molding temperature 260
° C., injection pressure 80 kg / cm 2 G, under the conditions of mold temperature 60 ° C., 60 seconds cycle, have created a continuous 40 times the test piece.
It was expressed by the ratio of the number of defective products such as cracks and cracks in the molded product at this time. Contamination: Immediately after completion of the above-mentioned molding, the state of cloudiness on the surface of the mold (mirror surface portion) was visually observed, and the case where no cloudiness was observed was rated as ◯, and the case where there was cloudiness was rated as x. -Appearance: The stains and coloring of the molded product were visually observed.

【0024】実施例1 懸濁重合で得られた粒状メタアクリル樹脂、(スミペッ
クスB LO、住友化学工業(株)製)100部と、ジペン
タエリスリトールトリパルミテート0.025部及びス
テアリン酸アミド0.025部とを、ヘンシェル型ミキ
サーで混合後、スクリュー径40mmのベント型押出機を
用いてペレット化した。該ペレットを評価した。得られ
た結果を表1に示す。
Example 1 100 parts of granular methacrylic resin obtained by suspension polymerization (SUMIPEX B LO, manufactured by Sumitomo Chemical Co., Ltd.), 0.025 part of dipentaerythritol tripalmitate and 0 of stearic acid amide 0.025 parts was mixed with a Henschel mixer and then pelletized using a vent type extruder having a screw diameter of 40 mm. The pellets were evaluated. The results obtained are shown in Table 1.

【0025】実施例2〜5、比較例1〜4 ジペンタエリスリトールトリパルミテート及びステアリ
ン酸アミドの添加量を表1に示すように変更した以外
は、実施例1と同様に行った。得られた結果を表1に示
す。
Examples 2 to 5, Comparative Examples 1 to 4 Example 1 was repeated except that the amounts of dipentaerythritol tripalmitate and stearic acid amide added were changed as shown in Table 1. The results obtained are shown in Table 1.

【0026】実施例6〜8 ペンタエリスリトールを表1に示すように変更した以外
は、実施例2と同様に行った。得られた結果を表1に示
す。
Examples 6 to 8 The procedure of Example 2 was repeated except that pentaerythritol was changed as shown in Table 1. The results obtained are shown in Table 1.

【0027】実施例9 ステアリン酸アミドに代えて、パルミチン酸アミドとし
た以外は、実施例2と同様に行った。得られた結果を表
1に示す。
Example 9 The procedure of Example 2 was repeated, except that palmitic acid amide was used instead of stearic acid amide. The results obtained are shown in Table 1.

【0028】[0028]

【表1】 注 はジペンタエリスリトールトリパルミテート はジペンタエリスリトールヘキサベヘネート はモノペンタエリスリトール はトリペンタエリスリトール はステアリン酸アミド はパルミチン酸アミド[Table 1] Note: dipentaerythritol tripalmitate is dipentaerythritol hexabehenate is monopentaerythritol is tripentaerythritol is stearic acid amide is palmitic acid amide

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】メタクリル酸メチル系重合体100重量部
に対して、下記〔化1〕又は〔化2〕で表されるペンタ
エリスリトール類から選ばれた少なくとも1種と炭素数
10〜22の高級脂肪酸アミドを重量比10/90〜9
0/10で、0.02〜0.5重量部を含有してなるメ
タクリル系樹脂組成物。 【化1】 式中X1 ,X2 ,X3 及びX4 は、下記〔外1〕で示さ
れるものの1つである。 【外1】 【化2】 式中X5 ,X6 ,X7 ,X8 ,X9 ,X10,X11及びX
12は、上記X1 ,X2,X3 及びX4 に同じ、nは0〜
3である。
1. At least one selected from pentaerythritols represented by the following [Chemical formula 1] or [Chemical formula 2] and a higher carbon number of 10 to 22 per 100 parts by weight of a methyl methacrylate polymer. Weight ratio of fatty acid amide 10 / 90-9
A methacrylic resin composition, which is 0/10 and contains 0.02 to 0.5 part by weight. [Chemical 1] In the formula, X 1 , X 2 , X 3 and X 4 are ones shown in the following [External 1]. [Outer 1] [Chemical 2] In the formula, X 5 , X 6 , X 7 , X 8 , X 9 , X 10 , X 11 and X
12 is the same as the above X 1 , X 2 , X 3 and X 4 , and n is 0 to
It is 3.
JP33576192A 1992-12-16 1992-12-16 Methacrylic resin composition Pending JPH06184389A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP33576192A JPH06184389A (en) 1992-12-16 1992-12-16 Methacrylic resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP33576192A JPH06184389A (en) 1992-12-16 1992-12-16 Methacrylic resin composition

Publications (1)

Publication Number Publication Date
JPH06184389A true JPH06184389A (en) 1994-07-05

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Family Applications (1)

Application Number Title Priority Date Filing Date
JP33576192A Pending JPH06184389A (en) 1992-12-16 1992-12-16 Methacrylic resin composition

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JP (1) JPH06184389A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009125766A1 (en) 2008-04-08 2009-10-15 住友化学株式会社 Methacrylic resin composition for hot plate melt-bonding, use of the same for hot plate melt-bonding, and melt-bonding method
WO2009125768A1 (en) 2008-04-08 2009-10-15 住友化学株式会社 Methacrylic resin composition for hot plate melt-bonding, use of the same for hot plate melt-bonding, and melt-bonding method
WO2009125764A1 (en) 2008-04-08 2009-10-15 住友化学株式会社 Methacrylic resin composition for hot plate melt-bonding, use of the same for hot plate melt-bonding, and melt-bonding method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009125766A1 (en) 2008-04-08 2009-10-15 住友化学株式会社 Methacrylic resin composition for hot plate melt-bonding, use of the same for hot plate melt-bonding, and melt-bonding method
WO2009125768A1 (en) 2008-04-08 2009-10-15 住友化学株式会社 Methacrylic resin composition for hot plate melt-bonding, use of the same for hot plate melt-bonding, and melt-bonding method
WO2009125764A1 (en) 2008-04-08 2009-10-15 住友化学株式会社 Methacrylic resin composition for hot plate melt-bonding, use of the same for hot plate melt-bonding, and melt-bonding method
KR20160025036A (en) 2008-04-08 2016-03-07 스미또모 가가꾸 가부시끼가이샤 Methacrylic resin composition for hot plate melt-bonding, use of the same for hot plate melt-bonding, and melt-bonding method

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