JP2011057795A5

JP2011057795A5 -

Info

Publication number: JP2011057795A5
Application number: JP2009207349A
Authority: JP
Filing date: 2009-09-08
Publication date: 2012-07-19
Anticipated expiration: 2029-09-08

Description

本発明者は鋭意検討を行った結果、特定の構成を有するアクリル系樹脂の重合時に、ゴ
ム質含有共重合体粒子を分散させた状態で塊状重合することにより、上記従来技術の課題
を解決できることを見出し、本発明を完成するに至った。
１．メタクリル酸エステル単量体単独又はアクリル酸エステル単量体との共重合体（Ａ
）、芳香族ビニル化合物単量体（Ｂ）、及び、六員環構造化合物単量体、不飽和ジカルボ
ン酸無水物単量体、五員環構造化合物単量体の少なくとも一つから選ばれる単量体（Ｃ）
の合計１００質量部に対して、ゴム質含有共重合体粒子１質量部以上５０質量部以下が分
散され、かつ、上記ゴム質含有共重合体粒子が、以下の（ｉ）〜（ｉｉｉ）の少なくとも３層を有し、平均粒子径が０．０４〜０．３μｍである多層構造粒子である組成物を成形型内で重合して得られるメタクリル系樹脂成形体。
（ｉ）メタクリル酸メチル５５〜８４質量％、アクリル酸エステル１〜２０質量％、芳香
族ビニル化合物１５〜２５質量％を含有する内層１０〜３０質量％、
（ｉｉ）アクリル酸エステル６０〜７５質量％、芳香族ビニル化合物２５〜４０質量％を
含有する中間層４０〜６０質量％、
（ｉｉｉ）メタクリル酸メチル８０〜９９質量％と前記メタクリル酸メチルと共重合可能
な他の共重合性単量体１〜２０質量％を含有する外層３０〜５０質量％。
２．単量体（Ｃ）が不飽和ジカルボン酸無水物単量体であることを特徴とする上記１の
メタクリル系樹脂成形体。
３．単量体（Ｃ）が下記式（１）で表される構造を有する化合物であることを特徴とす
る上記1又は２に記載のメタクリル系樹脂成形体。 As a result of intensive studies, the present inventor can solve the above-described problems of the prior art by performing bulk polymerization in a state where rubber-containing copolymer particles are dispersed during polymerization of an acrylic resin having a specific configuration. As a result, the present invention has been completed.
1. Methacrylic acid ester monomer alone or copolymer with acrylic acid ester monomer (A
), An aromatic vinyl compound monomer (B), and a single member selected from at least one of a six-membered ring structure compound monomer, an unsaturated dicarboxylic acid anhydride monomer, and a five-membered ring structure compound monomer. Mass (C)
1 to 50 parts by mass of the rubber-containing copolymer particles are dispersed with respect to 100 parts by mass in total , and the rubber-containing copolymer particles are the following (i) to (iii): A methacrylic resin molded article obtained by polymerizing a composition which is a multilayer structure particle having at least three layers and having an average particle diameter of 0.04 to 0.3 μm in a mold.
(I) 55-84% by weight of methyl methacrylate, 1-20% by weight of acrylic ester, aroma
10-30% by mass of an inner layer containing 15-25% by mass of an aromatic vinyl compound,
(Ii) Acrylic acid ester 60-75 mass%, aromatic vinyl compound 25-40 mass%
Containing 40-60 mass% of intermediate layer,
(Iii) 80 to 99% by mass of methyl methacrylate and copolymerizable with the methyl methacrylate
30-50 mass% of outer layers containing 1-20 mass% of other copolymerizable monomers.
2. The methacrylic resin molded article according to 1 above, wherein the monomer (C) is an unsaturated dicarboxylic acid anhydride monomer.
3. 3. The methacrylic resin molded article according to 1 or 2 above, wherein the monomer (C) is a compound having a structure represented by the following formula (1).

４．成形体中の単量体（Ａ）、（Ｂ）、（Ｃ）の質量比が、（Ａ）３０質量％以上９０
質量％以下、（Ｂ）５質量％以上４０質量％以下、および（Ｃ）５質量％以上３０質量％
以下であることを特徴とする上記１乃至３に記載のいずれか１項に樹脂成形体。
５．上記１〜４を粉砕して得られる樹脂組成物。
６．メタクリル酸エステル単量体単独又はアクリル酸エステル単量体との共重合体（Ａ
）、芳香族ビニル化合物単量体（Ｂ）、及び、六員環構造化合物単量体、不飽和ジカルボ
ン酸無水物単量体、五員環構造化合物単量体の少なくとも一つから選ばれる単量体（Ｃ）
の合計１００質量部に対して、ゴム質含有共重合体粒子１質量部以上５０質量部以下を分
散させ、かつ、上記ゴム質含有共重合体粒子が、以下の（ｉ）〜（ｉｉｉ）の少なくとも３層を有し、平均粒子径が０．０４〜０．３μｍである多層構造粒子である組成物を成形型内で重合する、メタクリル系樹脂組成物の成形体の製造方法。
（ｉ）メタクリル酸メチル５５〜８４質量％、アクリル酸エステル１〜２０質量％、芳香
族ビニル化合物１５〜２５質量％を含有する内層１０〜３０質量％、
（ｉｉ）アクリル酸エステル６０〜７５質量％、芳香族ビニル化合物２５〜４０質量％を
含有する中間層４０〜６０質量％、
（ｉｉｉ）メタクリル酸メチル８０〜９９質量％と前記メタクリル酸メチルと共重合可能
な他の共重合性単量体１〜２０質量％を含有する外層３０〜５０質量％。
７．単量体（Ｃ）が不飽和ジカルボン酸無水物単量体であることを特徴とする上記６に記載のメタクリル系樹脂組成物の成形体の製造方法。
８.単量体（Ｃ）が下記式（１）で表される構造を有する化合物であることを特徴とする上記６又は７に記載のメタクリル系樹脂組成物の成形体の製造方法。 4). The mass ratio of the monomers (A), (B), (C) in the molded body is (A) 30% by mass or more 90
% By mass or less, (B) 5% by mass or more and 40% by mass or less, and (C) 5% by mass or more and 30% by mass or less.
4. The resin molded product according to any one of items 1 to 3, which is as follows.
5 . The resin composition obtained by grind | pulverizing said 1-4 .
6 . Methacrylic acid ester monomer alone or copolymer with acrylic acid ester monomer (A
), An aromatic vinyl compound monomer (B), and a single member selected from at least one of a six-membered ring structure compound monomer, an unsaturated dicarboxylic acid anhydride monomer, and a five-membered ring structure compound monomer. Mass (C)
1 to 50 parts by mass of the rubber-containing copolymer particles are dispersed with respect to 100 parts by mass in total , and the rubber-containing copolymer particles are the following (i) to (iii): at least three layers, you polymerizing an average particle size of the composition is a multi-layered structure particle is 0.04~0.3μm in the mold, the process for producing a molded article of main methacrylic resin composition.
(I) 55-84% by weight of methyl methacrylate, 1-20% by weight of acrylic ester, aroma
10-30% by mass of an inner layer containing 15-25% by mass of an aromatic vinyl compound,
(Ii) Acrylic acid ester 60-75 mass%, aromatic vinyl compound 25-40 mass%
Containing 40-60 mass% of intermediate layer,
(Iii) 80 to 99% by mass of methyl methacrylate and copolymerizable with the methyl methacrylate
30-50 mass% of outer layers containing 1-20 mass% of other copolymerizable monomers.
7). The method for producing a molded body of a methacrylic resin composition as described in 6 above, wherein the monomer (C) is an unsaturated dicarboxylic acid anhydride monomer.
8. The method for producing a molded body of a methacrylic resin composition as described in 6 or 7 above, wherein the monomer (C) is a compound having a structure represented by the following formula (1).

(Wherein X represents O or N—R, O represents an oxygen atom, N represents a nitrogen atom, R represents a hydrogen atom,
And any one selected from the group consisting of a ru group, an aryl group, and a cycloalkyl group. )
9. The mass ratio of the monomers (A), (B), and (C) in the molded body is (A) 30% by mass to 90% by mass, (B) 5% by mass to 40% by mass, and (C) It is 5 mass% or more and 30 mass% or less, The manufacturing method of the molded object of the methacrylic resin composition in any one of said 6-8 characterized by the above-mentioned.

内層（ａ−ｉ）を形成する共重合体中の芳香族ビニル化合物単量体は、アクリル酸エステル単量体に対して、芳香族環の粒子内分子間がπ―πスタッキング作用を与えることに
より粒子自体を安定化させる役目を果たす。結果として、粒径制御や粒子間の凝集低減に
繋がり、このことによりゴム質含有共重合体粒子の分散性がより高まり、凝集由来による
異物発生原因の低減に繋がる。芳香族ビニル化合物単量体としては、上述の第二の単量体
成分として挙げたものと同様のものを用いることができるが、好ましくは、スチレン又は
その誘導体が用いられる。ゴム質含有共重合体粒子の分散性がよくなることから１５質量
％含有している必要があり、耐候性が向上することから２５質量％以下が必要である。 The aromatic vinyl compound monomer in the copolymer forming the inner layer (ai) has a π-π stacking action between the intramolecular particles of the aromatic ring for the acrylate monomer. To stabilize the particles themselves. As a result, it leads to particle size control and agglomeration reduction between particles, and this further increases the dispersibility of the rubber-containing copolymer particles, leading to a reduction in the cause of foreign matter generation due to agglomeration. As the aromatic vinyl compound monomer, those similar to those exemplified as the second monomer component described above can be used, but styrene or a derivative thereof is preferably used. It is necessary to contain 15% by mass because the dispersibility of the rubber-containing copolymer particles is improved, and 25% by mass or less is necessary because the weather resistance is improved.

〔中間層の説明〕
ゴム質含有共重合体粒子の中間層（ａ−ｉｉ）を形成する共重合体は、優れた靭性を付
与する観点から、軟質なゴム弾性を示す共重合体であることが好ましい。アクリル酸エス
テル系の共重合体が挙げられ、より好ましくは、アクリル酸エステル、芳香族ビニル化合
物、多官能性グラフト剤、多官能性架橋剤を共重合させてなる樹脂である。
中間層（ａ−ｉｉ）を構成するアクリル酸エステルとしては、特に限定されないが、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ｎ−ブチル、アクリル酸２
−エチルへキシル等から１種又は２種以上を併用して用いる。中でも、アクリル酸ｎ−ブ
チル、アクリル酸２−へキシルがより好ましい。アクリル酸エステルの中間層中の含有量
は６０〜７５質量％である。アクリル酸エステルの含有量が６０質量％以上であると、ゴム強度が良好であり、７５質量％以下であるとゴム強度と光学特性バランスが良好である。より好ましくは６０〜７０質量％である。
中間層（ａ−ｉｉ）を構成する芳香族ビニル化合物単量体は、内層（ａ−ｉ）と同様の
理由から内層（ａ−ｉ）と同様のものを用いることができ、好ましくはスチレン又はその
誘導体である。ゴム質含有共重合体粒子の分散性が向上することから２５質量％以上が必要であり、耐候性及び機械強度が良好なことから４０質量％以下が必要である。より好ましくは３０〜４０質量％である。 [Explanation of intermediate layer]
The copolymer forming the intermediate layer (a-ii) of the rubber-containing copolymer particles is preferably a copolymer exhibiting soft rubber elasticity from the viewpoint of imparting excellent toughness. Acrylic ester-based copolymers may be mentioned, and a resin obtained by copolymerizing an acrylic ester, an aromatic vinyl compound, a polyfunctional grafting agent, and a polyfunctional crosslinking agent is more preferable.
Although it does not specifically limit as acrylic acid ester which comprises an intermediate | middle layer (a-ii), Preferably, methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid 2
-Use together 1 type (s) or 2 or more types from ethylhexyl etc. Of these, n-butyl acrylate and 2-hexyl acrylate are more preferable. Content of acrylic ester in the intermediate layer
Is 60-75 mass%. When the content of the acrylic acid ester is 60 mass% or more, rubber strength is good, Ru rubber strength and optical properties balance good der If it is 75 mass% or less. More preferably, it is 60-70 mass%.
The aromatic vinyl compound monomer constituting the intermediate layer (a-ii) can be the same as the inner layer (ai) for the same reason as the inner layer (ai), preferably styrene or Its derivatives. 25% by mass or more is necessary because the dispersibility of the rubber-containing copolymer particles is improved , and 40% by mass or less is necessary because the weather resistance and mechanical strength are good. More preferably, it is 30-40 mass%.

〔外層の説明〕
ゴム質含有共重合体粒子の外層（ａ−ｉｉｉ）を形成する共重合体は、ゴム凝集抑制と
ベース樹脂との相溶性の観点より、メタクリル系共重合体であることが好ましい。より好
ましくは、メタクリル酸メチル、これと共重合可能な他の共重合性単量体を含有する共重
合体である。
外層（ａ−ｉｉｉ）の共重合体中を構成するメタクリル酸メチルの含有量は、８０〜９
９質量％である。８０質量％以上であると光学特性が良好であり、９９質量％以下であることにより、強度が維持されるという効果を有する。より好ましくは９０〜９９質量％である。
上記のメタクリル酸メチルと共重合可能な他の共重合性単量体としては、特に限定され
ないが、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ｎ−ブチル、ア
クリル酸２−エチルへキシル等から１種又は２種以上を併用して用いる。中でも、アクリ
ル酸ｎ−ブチル、アクリル酸２−へキシルがより好ましい。好ましくは、アクリル酸エス
テルであり、特にアクリル酸ｎ−ブチル、アクリル酸２−へキシルである。 [Description of outer layer]
The copolymer forming the outer layer (a-iii) of the rubber-containing copolymer particles is preferably a methacrylic copolymer from the viewpoint of rubber aggregation suppression and compatibility with the base resin. More preferred is a copolymer containing methyl methacrylate and another copolymerizable monomer copolymerizable therewith.
The content of methyl methacrylate constituting the outer layer (a-iii) copolymer is 80 to 9
Ru 9% by mass. When it is 80% by mass or more, the optical characteristics are good, and when it is 99% by mass or less, the strength is maintained. More preferably, it is 90-99 mass%.
Although it does not specifically limit as said other copolymerizable monomer copolymerizable with said methyl methacrylate, Preferably, methyl acrylate, ethyl acrylate, acrylate n-butyl, 2-ethylhexyl acrylate 1 type or 2 types or more are used together. Of these, n-butyl acrylate and 2-hexyl acrylate are more preferable. Acrylic acid esters are preferable, and n-butyl acrylate and 2-hexyl acrylate are particularly preferable.

外層（ａ−ｉｉｉ）におけるアクリル酸エステル単量体の割合は、１〜２０質量％である。該割合が１質重量％以上であると、重合体の熱分解がより起こりにくくなり、一方、該割合が２０質量％以下であると、ゴム質含有共重合体粒子の粘着性も上昇しにくく取り扱いやすい。また、他のアクリル系樹脂との相溶性も好ましい範囲であり、耐衝撃性や耐候性に優れるものを得ることができる。
外層（ａ−ｉｉｉ）中には、耐候性の観点から芳香族ビニル化合物単量体を用いない方
が好ましい。
さらに、外層（ａ−ｉｉｉ）の重合時に、ベース樹脂の単量体に対する分散性の向上を
目的として、分子量を調節するためアルキルメルカプタン等を連鎖移動剤として用いるこ
ともできる。 The ratio of the acrylate monomer in the outer layer (a-iii) is 1 to 20% by mass. When the proportion is 1% by weight or more, thermal decomposition of the polymer is less likely to occur. On the other hand, when the proportion is 20% by weight or less, the adhesiveness of the rubber-containing copolymer particles is hardly increased. Easy to handle. In addition, the compatibility with other acrylic resins is also in a preferable range, and a material excellent in impact resistance and weather resistance can be obtained.
In the outer layer (a-iii), it is preferable not to use an aromatic vinyl compound monomer from the viewpoint of weather resistance.
Furthermore, during the polymerization of the outer layer (a-iii), an alkyl mercaptan or the like can be used as a chain transfer agent in order to adjust the molecular weight for the purpose of improving the dispersibility of the base resin with respect to the monomer.

Claims

Methacrylic acid ester monomer alone or copolymer with acrylic acid ester monomer (A),
Monomer selected from aromatic vinyl compound monomer (B) and at least one of six-membered ring structure compound monomer, unsaturated dicarboxylic acid anhydride monomer, and five-membered ring structure compound monomer 1 part by mass or more and 50 parts by mass or less of the rubber-containing copolymer particles are dispersed with respect to a total of 100 parts by mass of (C) , and the rubber-containing copolymer particles are the following (i) to ( A methacrylic resin molded article obtained by polymerizing a composition having multilayer structure particles having at least three layers of iii) and having an average particle diameter of 0.04 to 0.3 μm in a mold.
(I) 55-84% by weight of methyl methacrylate, 1-20% by weight of acrylic ester, aroma
10-30% by mass of an inner layer containing 15-25% by mass of an aromatic vinyl compound,
(Ii) Acrylic acid ester 60-75 mass%, aromatic vinyl compound 25-40 mass%
Containing 40-60 mass% of intermediate layer,
(Iii) 80 to 99% by mass of methyl methacrylate and copolymerizable with the methyl methacrylate
30-50 mass% of outer layers containing 1-20 mass% of other copolymerizable monomers.

The methacrylic resin molded article according to claim 1, wherein the monomer (C) is an unsaturated dicarboxylic acid anhydride monomer.

The methacrylic resin molded article according to claim 1 or 2, wherein the monomer (C) is a compound having a structure represented by the following formula (1).

(In the formula, X represents O or N—R, O represents an oxygen atom, N represents a nitrogen atom, R represents one selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a cycloalkyl group.)

The mass ratio of the monomers (A), (B), and (C) in the molded product is (A) 30% by mass to 90% by mass, (B) 5% by mass to 40% by mass, and (C The resin molded product according to any one of claims 1 to 3, wherein the content is 5% by mass or more and 30% by mass or less.

The resin composition obtained by grind | pulverizing the resin molding of any one of the said Claims 1-4 .

Methacrylic acid ester monomer alone or copolymer with acrylic acid ester monomer (A),
Monomer selected from aromatic vinyl compound monomer (B) and at least one of six-membered ring structure compound monomer, unsaturated dicarboxylic acid anhydride monomer, and five-membered ring structure compound monomer 1 part by mass or more and 50 parts by mass or less of rubber-containing copolymer particles are dispersed with respect to a total of 100 parts by mass of (C) , and the rubber-containing copolymer particles are the following (i) to ( has at least three layers of iii), polymerized in a mold a composition which is a multi-layer structure particles having an average particle diameter of 0.04～0.3Myuemu, production of moldings of main methacrylic resin composition Method.
(I) 55-84% by weight of methyl methacrylate, 1-20% by weight of acrylic ester, aroma
10-30% by mass of an inner layer containing 15-25% by mass of an aromatic vinyl compound,
(Ii) Acrylic acid ester 60-75 mass%, aromatic vinyl compound 25-40 mass%
Containing 40-60 mass% of intermediate layer,
(Iii) 80 to 99% by mass of methyl methacrylate and copolymerizable with the methyl methacrylate
30-50 mass% of outer layers containing 1-20 mass% of other copolymerizable monomers.

The method for producing a molded body of a methacrylic resin composition according to claim 6, wherein the monomer (C) is an unsaturated dicarboxylic acid anhydride monomer.

The monomer (C) is a compound having a structure represented by the following formula (1):
The manufacturing method of the molded object of the methacrylic resin composition of Claim 6 or 7.

(Wherein X represents O or N—R, O represents an oxygen atom, N represents a nitrogen atom, R represents a hydrogen atom,
And any one selected from the group consisting of a ru group, an aryl group, and a cycloalkyl group. )

The mass ratio of the monomers (A), (B), (C) in the molded product is (A) 30% by mass or more and 90% by mass.
% Or less, (B) 5% by mass or more and 40% by mass or less, and (C) 5% by mass or more and 30% by mass or less.
The method for producing a molded body of a methacrylic resin composition according to any one of claims 6 to 8.