JPH0315648B2 - - Google Patents

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Publication number
JPH0315648B2
JPH0315648B2 JP22777782A JP22777782A JPH0315648B2 JP H0315648 B2 JPH0315648 B2 JP H0315648B2 JP 22777782 A JP22777782 A JP 22777782A JP 22777782 A JP22777782 A JP 22777782A JP H0315648 B2 JPH0315648 B2 JP H0315648B2
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JP
Japan
Prior art keywords
weight
parts
polymer
multilayer structure
monomer
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.)
Expired
Application number
JP22777782A
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Japanese (ja)
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JPS59122513A (en
Inventor
Kazuo Kishida
Masahiro Sugimori
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Mitsubishi Rayon Co Ltd
Original Assignee
Mitsubishi Rayon Co Ltd
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Publication date
Application filed by Mitsubishi Rayon Co Ltd filed Critical Mitsubishi Rayon Co Ltd
Priority to JP22777782A priority Critical patent/JPS59122513A/en
Publication of JPS59122513A publication Critical patent/JPS59122513A/en
Priority to JP20520090A priority patent/JPH03163153A/en
Publication of JPH0315648B2 publication Critical patent/JPH0315648B2/ja
Granted legal-status Critical Current

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  • Compositions Of Macromolecular Compounds (AREA)

Description

【発明の詳现な説明】 本発明は倚局構造重合䜓の補造方法に関し、曎
に詳しくは、柔軟性、透明性及び耐候性が優れた
倚局構造重合䜓の補造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a multilayer polymer, and more particularly, to a method for producing a multilayer polymer with excellent flexibility, transparency, and weather resistance.

アクリル系暹脂、特にメチルメタクリレヌト系
重合䜓は、優れた透明性ず耐候性ずを合わせ持぀
暹脂ずしお知られおおり、キダスト成圢品、抌出
成圢品等に広く甚いられおいる。しかしながら、
これらのメチルメタクリレヌト系重合䜓は䞀般的
に硬くもろいものであるため、フむルム、被芆材
あるいは軟質チナヌブなどの柔軟性が芁求される
甚途には甚いるこずが出来なか぀た。 Acrylic resins, particularly methyl methacrylate polymers, are known as resins that have both excellent transparency and weather resistance, and are widely used in cast molded products, extrusion molded products, and the like. however,
Since these methyl methacrylate polymers are generally hard and brittle, they cannot be used in applications that require flexibility, such as films, coatings, or soft tubes.

その為、メチルメタクリレヌト系重合䜓ぞの靭
性・柔軟性付䞎を目的ずしお、ある皮のゎム成分
を導入する詊みが埓来からなされおいるが、結果
的には耐候性が倧幅に䜎䞋したり透明性が倧幅に
䜎䞋するなど、メチルメタクリレヌト系重合䜓の
も぀すぐれた特城を犠牲にしたものが倚く、しか
も、フむルム・シヌト甚玠材ずしお取り扱うには
困難を生じない皋床の柔軟性・靭性は付䞎できお
も、それ以䞊の柔軟性が芁求される軟質チナヌブ
などの甚途にも察応するこずが出来るなど柔軟性
に富んだアクリル系玠材は開発できなか぀た。 For this reason, attempts have been made to introduce certain rubber components into methyl methacrylate-based polymers in order to impart toughness and flexibility, but these efforts have resulted in significantly lower weather resistance and lower transparency. In many cases, the excellent characteristics of methyl methacrylate polymers have been sacrificed, such as a significant decrease in the properties of methyl methacrylate polymers.Moreover, they have not been able to provide enough flexibility and toughness to handle them as materials for films and sheets. However, it has not been possible to develop an acrylic material that is highly flexible and can be used in applications such as soft tubes that require even greater flexibility.

本発明は、䞊蚘欠点を解消しお、柔軟性・透明
性及び耐候性が優れたアクリル系倚局構造重合䜓
の補造方法を提䟛するこずを目的ずする。 An object of the present invention is to eliminate the above-mentioned drawbacks and provide a method for producing an acrylic multilayer structure polymer having excellent flexibility, transparency, and weather resistance.

本発明の倚局構造重合䜓の補造方法は、 (A) 60〜100重量郚の炭玠数以䞋のアルキル基
を有するアルキルアクリレヌトA1、 〜40重量郚の共重合可胜な二重結合を有す
る単量䜓A2、 〜10重量郚の倚官胜性単量䜓A3、 及び A1〜A3の合蚈量100重量郚に察し
0.1〜重量郚のグラフト亀叉剀を重合させ、
ゲル含有量が60重量以䞊、ガラス転移枩床が
℃以䞋である最内局重合䜓を圢成さ
せ、 (B) 次に、60〜100重量郚の炭玠数以䞋のアル
キル基を有するアルキルメタクリレヌト
B1、及び 〜40重量郚の共重合可胜な二重結合を有す
る単量䜓B2 を最内局重合䜓にグラフト重合させ、ガ
ラス転移枩床が60℃以䞊である最倖局重合䜓
を圢成させ、そしおこのようにしお埗ら
れる倚局構造重合䜓䞭に占める最内局重合䜓
の割合が51〜90重量であり、最倖局重
合䜓の割合が10〜49重量であるこずを
特城ずする倚局構造重合䜓の補造法である。 The method for producing a multilayer structure polymer of the present invention includes: (A) 60 to 100 parts by weight of an alkyl acrylate (A 1 ) having an alkyl group having 8 or less carbon atoms; 0 to 40 parts by weight of a copolymerizable double bond; (A 2 ), 0 to 10 parts by weight of a polyfunctional monomer (A 3 ), and 100 parts by weight of the total amount of (A 1 ) to (A 3 ).
polymerizing 0.1 to 5 parts by weight of a graft cross-agent;
Form an innermost layer polymer (A) having a gel content of 60% by weight or more and a glass transition temperature of 0°C or less, and (B) having 60 to 100 parts by weight of an alkyl group having 4 or less carbon atoms. Alkyl methacrylate (B 1 ) and 0 to 40 parts by weight of a monomer having a copolymerizable double bond (B 2 ) are graft-polymerized to the innermost layer polymer (A), and the glass transition temperature is 60°C or higher. The proportion of the innermost layer polymer (A) in the thus obtained multilayer structure polymer is 51 to 90% by weight, and the outermost layer polymer (B) is This is a method for producing a multilayer structure polymer, characterized in that the proportion of B) is 10 to 49% by weight.

以䞋、本発明を曎に詳现に説明する。 The present invention will be explained in more detail below.

本発明の補造法による重合䜓を構成する最内局
重合䜓は、該重合䜓に柔軟性を付䞎するた
めの成分である。 The innermost layer polymer (A) constituting the polymer produced by the production method of the present invention is a component for imparting flexibility to the polymer.

最内局重合䜓を構成する炭玠数〜の
アルキル基を有するアルキルアクリレヌトA1
は、盎鎖状、分岐状のいずれでもよく、メチルア
クリレヌト゚チルアクリレヌトプロピルアク
リレヌトブチルアクリレヌト−゚チルヘキ
シルアクリレヌト−オクチルアクリレヌト等
が単独で又は混合しお甚いられるが、ガラス転移
枩床以䞋、Tgず略称するの䜎いものがより
奜たしい。これらのアルキルアクリレヌトA1
は60〜100重量郚以䞋、重量郚を郚ず略すの
範囲で甚いられる。 Alkyl acrylate (A 1 ) having an alkyl group having 1 to 8 carbon atoms constituting the innermost layer polymer (A)
may be linear or branched, and methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, etc. are used alone or in combination, but the glass transition temperature ( Those with a low Tg (hereinafter abbreviated as Tg) are more preferable. These alkyl acrylates (A 1 )
is used in a range of 60 to 100 parts by weight (hereinafter, parts by weight are abbreviated as parts).

たた、共重合可胜な二重結合を有する単量䜓
A2は、䞊蚘以倖のアルキルアクリレヌト䜎
玚アルコキシアクリレヌトシアノ゚チルアクリ
レヌトアクリルアミドアクリル酞メタクリ
ル酞等のアクリル性単量䜓が奜たしく、〜40郚
の範囲で甚いられる。その他A2成分ずしお
40重量を越えない範囲でスチレンアルキル眮
換スチレンアクリロニトリルメタクリロニト
リル等が䜿甚可胜である。 Further, the monomer (A 2 ) having a copolymerizable double bond is preferably an acrylic monomer other than the above, such as alkyl acrylate, lower alkoxy acrylate, cyanoethyl acrylate, acrylamide, acrylic acid, or methacrylic acid. It is used in a range of 0 to 40 parts. As other (A 2 ) ingredients
Styrene, alkyl-substituted styrene, acrylonitrile, methacrylonitrile, etc. can be used within a range not exceeding 40% by weight.

さらに倚官胜性単量䜓A3は、゚チレング
リコヌルゞメタクリレヌト−ブチレング
リコヌルゞメタクリレヌト−ブチレング
リコヌルゞメタクリレヌト及びプロピレングリコ
ヌルゞメタクリレヌトの劂きアルキレングリコヌ
ルゞメタクリレヌトが奜たしく、ゞビニルベンれ
ントリビニルベンれン等のポリビニルベンれン
及びアルキレングリコヌルゞアクリレヌト等も䜿
甚可胜である。これらの単量䜓はそれが含たれる
局自䜓を架橋するのに有効に働くものであり、他
局ずの局間の結合には䜜甚しない。これらの倚官
胜性単量䜓A3は、重合䜓を構成する
うえにおいお、重合条件あるいはグラフト亀叉剀
の䜿甚によりゲル含有量60重量以䞊ずいう条件
が満足されるのであれば、甚いる必芁はないが10
郚以内の範囲であれば、䜿甚しおもさし぀かえな
い。倚官胜性単量䜓A3を10郚を超えお甚い
た堎合には、該重合䜓の柔軟性が䜎䞋す
る。 Furthermore, the polyfunctional monomer (A 3 ) is preferably an alkylene glycol dimethacrylate such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, and propylene glycol dimethacrylate, and divinyl Polyvinylbenzenes such as benzene and trivinylbenzene and alkylene glycol diacrylates can also be used. These monomers work effectively to crosslink the layer in which they are contained, but do not work on bonding between layers with other layers. These polyfunctional monomers (A 3 ) can be used to form the polymer (A), provided that the gel content is 60% by weight or more depending on the polymerization conditions or the use of a grafting agent. , there is no need to use 10
It may be used as long as it is within this range. When the polyfunctional monomer (A 3 ) is used in an amount exceeding 10 parts, the flexibility of the polymer (A) decreases.

グラフト亀叉剀は、最倖局たる暹脂局あるいは
䞭間局ず有効な化孊的結合を生じさせるための必
須成分であり、A1〜A3の合蚈量100郚に
察し0.1〜郚、奜たしくは0.5〜郚の範囲内で
甚いられる。グラフト亀叉剀の䜿甚量が0.1郚未
満のものでは有効なグラフト結合の量が少なす
ぎ、成圢時に容易に局砎壊を起こしお透明性等が
倧幅に䜎䞋する。逆に郚を超えお甚いた堎合に
は、匟性が䜎䞋する。グラフト亀叉剀ずしおは、
共重合性のαβ−䞍飜和モノカルボン酞又はゞ
カルボン酞のアリル゚ステルメタアリル゚ステ
ルクロチル゚ステル及びトリアリルシアヌレヌ
トトリアリルむ゜シアヌレヌト等が甚いられる
が、アリルメタクリレヌトトリアリルシアヌレ
ヌトが特に奜たしい。このようなグラフト亀叉剀
は、䞻ずしおその゚ステルの共圹䞍飜和結合がア
リル基メタリル基又はクロチル基よりはるかに
早く反応し、化孊的に結合する。この間アリル
基メタリル基又はクロチル基の実質䞊のかなり
の郚分は、次局重合䜓の重合に有効に働
き、隣接二局間にグラフト結合を䞎えるものであ
る。 The grafting agent is an essential component for forming an effective chemical bond with the outermost resin layer or intermediate layer, and is present in an amount of 0.1 to 5 parts per 100 parts of the total amount of (A 1 ) to (A 3 ). It is preferably used within the range of 0.5 to 2 parts. If the amount of graft cross-agent used is less than 0.1 part, the amount of effective graft bonding will be too small, and layer destruction will easily occur during molding, resulting in a significant decrease in transparency, etc. On the other hand, if more than 5 parts is used, the elasticity decreases. As a grafting agent,
Copolymerizable α,β-unsaturated monocarboxylic acid or dicarboxylic acid allyl ester, methalyl ester, crotyl ester, triallyl cyanurate, triallyl isocyanurate, etc. are used, but allyl methacrylate and triallyl cyanurate are used. Particularly preferred. In such a graft cross-agent, the conjugated unsaturated bond of the ester reacts much faster than the allyl group, methallyl group, or crotyl group, and is chemically bonded. During this time, a substantial portion of the allyl group, methallyl group, or crotyl group effectively acts on the polymerization of the next layer polymer (B) and provides a graft bond between the two adjacent layers.

以䞊のような最内局重合䜓は、ある皋床架橋
されたガラス転移枩床Tgが℃以䞋の匟性
䜓であるこずが必芁であり、たた、ゲル含有量が
60重量以䞊、奜たしくは80重量、膚最床が
〜30の堎合に特に奜たしい結果が埗られる。 The innermost layer polymer A as described above needs to be an elastic body that has been crosslinked to some extent and has a glass transition temperature (Tg) of 0°C or less, and also has a gel content of
60% by weight or more, preferably 80% by weight, swelling degree 5
Particularly favorable results are obtained in the case of ˜30.

該重合䜓のアクリル系倚局構造重合䜓䞭
に占める量は51〜90重量である。51重量未満
の量ではアクリル系倚局構造重合䜓に目的ずする
すぐれた柔軟性を付䞎するこずが出来ない。逆に
90重量を超える量では、該重合䜓党䜓がゎム的
になり取り扱いが困難になるばかりでなく、耐候
性等の諞物性も倧巟に䜎䞋しおしたう。なお、こ
のアクリル系ゎムの架橋匟性䜓からなる最内局重
合䜓は、その必芁に応じ段構造、段構
造にするこずも出来る。 The amount of the polymer (A) in the acrylic multilayer structure polymer is 51 to 90% by weight. If the amount is less than 51% by weight, the desired excellent flexibility cannot be imparted to the acrylic multilayer structure polymer. vice versa
If the amount exceeds 90% by weight, the entire polymer becomes rubbery and becomes difficult to handle, and various physical properties such as weather resistance are also significantly reduced. The innermost layer polymer (A) made of a crosslinked elastic body of acrylic rubber can also have a two-tiered structure or a three-tiered structure depending on the need.

アクリル系倚局構造重合䜓を構成する最倖局重
合䜓は本質的に暹脂局であり、該重合䜓に
暹脂ずしおの取り扱いやすさを付䞎するずずも
に、耐候性等の諞性質をも䞻に担うものである。
埓぀お、最倖局重合䜓のTgは60℃以䞊で
あるこずが必芁であり、奜たしくは80℃以䞊であ
る。 The outermost layer polymer (B) constituting the acrylic multilayer structure polymer is essentially a resin layer, and it not only gives the polymer ease of handling as a resin, but also provides various properties such as weather resistance. It is the responsibility of
Therefore, the Tg of the outermost layer polymer (B) needs to be 60°C or higher, preferably 80°C or higher.

最倖局重合䜓を圢成する炭玠数以䞋の
アルキル基を有するアルキルメタクリレヌト
B1ずしおはメチルメタクリレヌト゚チルメ
タクリレヌトプロピルメタクリレヌトブチル
メタクリレヌト等の少くずも䞀皮が60〜100郚の
範囲で甚いられ、特にメチルメタクリレヌトが奜
たしい。 The alkyl methacrylate (B 1 ) having an alkyl group having 4 or less carbon atoms forming the outermost layer polymer (B) includes at least one of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc. in an amount of 60 to 100 parts. Methyl methacrylate is particularly preferred.

共重合可胜な二重結合を有する単量䜓B2
ずしおは、炭玠数以䞋のアルキル基を有するア
ルキルアクリレヌトの他前蚘A2成分に瀺し
たものが〜40郚の範囲で甚いられる。最倖局重
合䜓のアクリル系倚局構造重合䜓䞭に占め
る量は10〜49重量である。10未満の量では重
合、凝固操䜜等の芳点から安定な重合䜓が埗られ
ない。たた49を超える量では最内局重合䜓
の含有量が小さくなり目的ずする柔軟性が
埗られない。 Monomer with copolymerizable double bond (B 2 )
In addition to the alkyl acrylate having an alkyl group having 8 or less carbon atoms, those shown in the above component (A 2 ) are used in a range of 0 to 40 parts. The amount of the outermost layer polymer (B) in the acrylic multilayer structure polymer is 10 to 49% by weight. If the amount is less than 10%, a stable polymer cannot be obtained from the viewpoint of polymerization and coagulation operations. Moreover, if the amount exceeds 49%, the content of the innermost layer polymer (A) becomes too small to obtain the desired flexibility.

なお、最倖局重合䜓の重合時には連鎖移
動剀等を甚いお重合床を調敎するこずも可胜であ
り、むしろ奜たしい堎合も倚い。 Incidentally, during the polymerization of the outermost layer polymer (B), it is also possible to adjust the degree of polymerization using a chain transfer agent or the like, and this is often preferable.

本発明で補造するアクリル系倚局構造重合䜓は
䞊蚘最内局重合䜓及び最倖局重合䜓
を基本構造単䜍ずするものであるが、さらに必芁
に応じ該重合䜓局を圢成した埌、該重合䜓
局の間に、 10〜90郚の炭玠数以䞋のアルキル基を有する
アルキルメタクリレヌトC1、 10〜90郚の炭玠数以䞋のアルキル基を有する
アルキルアクリレヌトC2、 〜20郚の共重合可胜な二重結合を有する単量
䜓C3、 〜10郚の倚官胜性単量䜓C4、及び C1〜C4の合蚈量100郚に察し0.1〜郚
のグラフト亀叉剀を最内局重合䜓にグラフ
ト重合させお、䞭間局を䞀局以䞊圢成させるこず
が可胜である。ここで、C1〜C4の各成分
及びグラフト亀叉剀は、前蚘重合䜓及び重
合䜓で䜿甚される各成分ず同様のものが甚
いられる。 The acrylic multilayer structure polymer produced in the present invention is the innermost layer polymer (A) and the outermost layer polymer (B).
is the basic structural unit, but if necessary, after forming the polymer (A) layer, between the polymer (B) layers, 10 to 90 parts of an alkyl group having 4 or less carbon atoms are added. Alkyl methacrylate (C 1 ) having 10 to 90 parts of an alkyl group having 8 or less carbon atoms (C 2 ), 0 to 20 parts of a monomer having a copolymerizable double bond (C 3 ), 0 to 10 parts of a polyfunctional monomer (C 4 ), and 0.1 to 5 parts of a grafting agent to 100 parts of the total amount of (C 1 ) to (C 4 ) to the innermost layer polymer (A ) can be graft-polymerized to form one or more intermediate layers. Here, each of the components (C 1 ) to (C 4 ) and the grafting agent are the same as those used in the polymer (A) and polymer (B).

この䞭間局は、最内局ずなる架橋匟性䜓局ず最
倖局ずなる暹脂局ずの結合をより効果的に達成す
るために配眮するものであり、それによ぀お透明
性が䞀局向䞊する他、柔軟性及び耐候性ずいう架
橋匟性䜓局及び暹脂局の有する特城が党䜓ずしお
十分に発揮されるようになる。 This intermediate layer is arranged to achieve more effective bonding between the innermost crosslinked elastic layer and the outermost resin layer, which not only further improves transparency but also increases flexibility. The characteristics of the crosslinked elastic layer and the resin layer, such as hardness and weather resistance, are fully exhibited as a whole.

アクリル系倚局構造重合䜓䞭の䞭間局の
占める量は〜30が適圓であり、30を超える
ず該重合䜓党䜓のバランスをくずすので奜たしく
ない。 The amount of the intermediate layer (C) in the acrylic multilayer structure polymer is suitably 5 to 30%, and if it exceeds 30%, it is not preferable because the overall balance of the polymer will be lost.

曎に本発明で補造するアクリル系倚局構造重合
䜓は各局が有機的に結合されおいるこずが必芁で
あり、最倖局ず䞭間局の合蚈量又
は、䞭間局がない堎合にあ぀おは最倖局
のうち、少くずもその1/3の量が最内局にグ
ラフトしおいるこずが奜たしい。 Furthermore, each layer of the acrylic multilayer structure polymer produced in the present invention must be organically bonded, and the total amount of the outermost layer (B) and the middle layer (C), or the amount of the middle layer (C) If not, it is preferable that at least one third of the outermost layer (B) is grafted onto the innermost layer.

尚、本発明の補造法による重合䜓の各局のゲル
含有量及び膚最床ずは、次のようにしお枬定した
倀をいう。 Note that the gel content and degree of swelling of each layer of the polymer produced by the production method of the present invention refer to values measured as follows.

JIS −6388に準じ圓該重合䜓を所定量採取
し、25℃で48時間メチル゚チルケトンMEK
䞭に浞挬する。浞挬埌、膚最した詊料を匕き䞊
げ、付着したMEKを拭い取぀た埌、その重量を
枬定する。次いで、枛圧也燥噚䞭でMEKを也燥
陀去し、恒量埌の絶也重量を読みずる。 A predetermined amount of the polymer was collected according to JIS K-6388, and methyl ethyl ketone (MEK) was stored at 25°C for 48 hours.
immerse in it. After immersion, pull out the swollen sample, wipe off the adhered MEK, and measure its weight. Next, MEK is removed by drying in a vacuum dryer, and the absolute dry weight after constant weight is read.

蚈算は次匏に埓う。 The calculation follows the following formula.

膚最床MEK膚最埌の重量−絶也重量絶也重量 ゲル含有量絶也重量採取サンプルの重量×
100 䜆し、倚局重合䜓党䜓に぀いおのゲル含有量ず
は、該重合䜓の重量MEK溶液を調補し、25
℃にお䞀昌倜攟眮埌遠心分離機にお16000r.p.m.
で90分間遠心分離を斜した埌の䞍溶分の重量を
いう。 Swelling degree = Weight after MEK swelling - Bone dry weight / Bone dry weight Gel content (%) = Bone dry weight / Weight of collected sample x
100 However, the gel content of the entire multilayer polymer is calculated by preparing a 1% by weight MEK solution of the polymer,
After standing overnight at ℃, use a centrifuge at 16000r.pm.
This refers to the weight percent of insoluble matter after centrifugation for 90 minutes.

曎に、本発明にいうガラス転移枩床Tgず
は、通垞知られおいるFOXの匏 Tga1Tg1a2Tg2 より蚈算しお求めたものをいう。匏䞭、a1及び
a2は、倫々、重量分率を衚わす。 Further, the glass transition temperature (Tg) as used in the present invention is calculated from the commonly known FOX equation: 1/Tg=a 1 /Tg 1 +a 2 /Tg 2 . In the formula, a 1 and
a 2 each represents a weight fraction.

本発明の補造方法による倚局構造重合䜓は、通
垞、乳化重合法を甚いた逐次倚段重合法によ぀お
埗られる。䞭間局を倚局ずする堎合にあ぀
おは、アルキルアクリレヌトC2の配合量を
次第に枛少させ぀぀、倚段重合を行なえばよい。
乳化重合法による逐次倚段重合法を行なう堎合
は、通垞、氎性溶媒に乳化剀、觊媒及び単量䜓等
を所定量加えお反応せしめ、以埌反応が終了する
毎に、䞊局を圢成する単量䜓及び重合開始剀を逐
次反応系に加えおいくこずにより、本発明の補造
方法による倚局構造重合䜓が埗られる。 The multilayer structure polymer produced by the production method of the present invention is usually obtained by a sequential multistage polymerization method using an emulsion polymerization method. When the intermediate layer (C) is multilayered, multistage polymerization may be carried out while gradually decreasing the amount of alkyl acrylate (C 2 ).
When carrying out a sequential multi-stage polymerization method using emulsion polymerization method, a predetermined amount of an emulsifier, a catalyst, a monomer, etc. are added to an aqueous solvent and reacted, and after each reaction, the monomers and monomers forming the upper layer are added. By sequentially adding a polymerization initiator to the reaction system, a multilayer structure polymer can be obtained by the production method of the present invention.

倚局構造重合䜓の補造に甚いられる乳化剀、觊
媒等に぀いおは特に制限がなく、通垞の乳化重合
で甚いられる乳化剀、觊媒等を甚いうる。乳化剀
ずしおは長鎖脂肪酞塩、スルホン酞塩類、スルホ
コハク酞の゚ステル塩類、リン酞゚ステル塩類、
酞アミド型アニオン界面掻性剀等のアニオン性界
面掻性剀をその代衚的なものずしお挙げるこずが
出来る。又、觊媒ずしおは過硫酞カリりム等の無
機過酞化物、クメンヒドロペルオキシド、ラりロ
むルペルオキシド等の有機過酞化物、アゟビスむ
゜ブチロニトリル等のアゟ系開始剀をその代衚䟋
ずしお挙げるこずが出来るが、クメンヒドロペル
オキシド−゜ゞりムホルムアルデヒドスルホキシ
レヌト系などのレドツクス系開始剀も奜たしい䟋
ずしおあげるこずができる。 There are no particular limitations on the emulsifier, catalyst, etc. used in the production of the multilayer structure polymer, and emulsifiers, catalysts, etc. used in ordinary emulsion polymerization can be used. As emulsifiers, long chain fatty acid salts, sulfonate salts, sulfosuccinic acid ester salts, phosphate ester salts,
Representative examples include anionic surfactants such as acid amide type anionic surfactants. Typical examples of catalysts include inorganic peroxides such as potassium persulfate, organic peroxides such as cumene hydroperoxide and lauroyl peroxide, and azo initiators such as azobisisobutyronitrile. Preferred examples include redox initiators such as cumene hydroperoxide-sodium formaldehyde sulfoxylate.

倚局構造重合䜓の重合の枩床条件、及び重合時
間は䜿甚する觊媒等に䟝存するものであり、重合
が最終段階たで順調に進行するような条件であれ
ばどのような条件でも可胜であるが、通垞は30℃
〜95℃の枩床範囲内で重合され、重合時間は〜
20時間である。なお該重合䜓の架橋匟性䜓郚分の
重合は比范的枩床の方が奜たしい堎合が倚い。 The temperature conditions and polymerization time for the polymerization of the multilayer structure polymer depend on the catalyst used, etc., and any conditions are possible as long as the polymerization proceeds smoothly to the final stage. Usually 30℃
Polymerization is carried out within the temperature range of ~95℃, and the polymerization time is 3~
It is 20 hours. In many cases, the crosslinked elastic body portion of the polymer is polymerized at a relatively high temperature.

たた、本発明の補造法は、䞊蚘方法に栌別限定
されるこずはなく、䟋えば乳化重合埌、最倖局重
合䜓の重合時に懞濁重合に転換させる乳化懞濁重
合法によ぀おも埗るこずができる。 Furthermore, the production method of the present invention is not particularly limited to the above-mentioned method; for example, it can also be obtained by an emulsion suspension polymerization method in which after emulsion polymerization, the outermost layer polymer is converted to suspension polymerization. can.

尚、倚局構造重合䜓の最終重合䜓における゚マ
ルゞペン粒子埄に぀いおは特に制限はないが、
800〜2000Å皋床の範囲が最も奜たしい。 There is no particular restriction on the emulsion particle size in the final polymer of the multilayer structure polymer;
The most preferable range is about 800 to 2000 Å.

倚局構造重合䜓のラテツクスは、必芁に応じお
酞化防止剀、滑剀、凝固剀等の添加剀を加えお塩
析凊理し、次に過・氎掗・脱氎・也燥等を行な
うこずによ぀お、パりダヌ状のポリマヌずされ
る。 Multilayer polymer latex is processed by salting out by adding additives such as antioxidants, lubricants, coagulants, etc. as necessary, and then filtered, washed with water, dehydrated, and dried to form a powder. It is said to be a polymer with a shape.

尚、本発明の補造方法による倚局構造重合䜓
は、通垞の方法で容易にチナヌブ等の成圢䜓に成
圢するこずが出来る。又成圢に際しおは、必芁に
応じお玫倖線吞収剀、顔料等を添加しおもさし぀
かえない。 Incidentally, the multilayer structure polymer produced by the production method of the present invention can be easily molded into a molded article such as a tube by a conventional method. Furthermore, during molding, ultraviolet absorbers, pigments, etc. may be added as necessary.

この様にしお埗られたチナヌブは極めお柔軟で
耐候性・透明性にすぐれ、しかも埓来軟質チナヌ
ブずしお広く䜿甚されおいる軟質塩ビ等で問題ず
な぀おいるような可塑性のにじみ出しずい぀た問
題もなく、極めお商品䟡倀の高いものずなる。さ
らに自動車のモヌルなどの柔軟性ず耐候性が芁求
される甚途に適した成圢䜓も、本発明の補造方法
による倚局構造重合䜓から埗るこずが出来る。 The tubes obtained in this way are extremely flexible, have excellent weather resistance and transparency, and are free from the problem of plasticity oozing, which has been a problem with soft PVC, etc., which have traditionally been widely used as soft tubes. Therefore, it has extremely high commercial value. Furthermore, molded articles suitable for applications requiring flexibility and weather resistance, such as automobile moldings, can also be obtained from the multilayer structure polymer produced by the production method of the present invention.

曎に本発明の補造方法による倚局構造重合䜓
を、䞋蚘及びの矀から遞ばれた少く
ずも䞀皮の熱可塑性暹脂〜99重量ず混合し
お、倚局構造重合䜓を補造するこずもできる。 Further, the multilayer structure polymer obtained by the production method of the present invention is mixed with 1 to 99% by weight of at least one thermoplastic resin selected from the following groups (a) and (b) to produce a multilayer structure polymer. You can also.

(a) 次匏 匏䞭、及びは同䞀でも異な぀おいおもよ
く、各々、ClBrCH3COOH
COOCH3CNOCOCH3COCH3C6H5
SO3H又はOR1を衚わす。䜆し、R1は䜎玚アルキ
ル基である a2 CF2CFZ 匏䞭、はCl又はCF3を衚わす 匏䞭、R2はフロロアルキル基を衚わす で瀺されるビニルモノマヌ又はビニリデンモノマ
ヌの単独重合䜓もしくはこれらのモノマヌの共重
合䜓 (b) ポリカヌボネヌト、熱可塑性ポリ゚ステル及
びポリアミド たた、本発明の補造法による重
合䜓を、屈折率は異なるが盞溶性のある他の熱
可塑性暹脂ず混合した堎合にも透明性に優れ、
ストレス癜化性が党くなく、もしくは極めお少
ない暹脂組成物ずするこずができる。特にメチ
ルメタクリレヌト系暹脂ずブレンドした堎合に
は、透明性、耐ストレス癜化性、耐候性、耐衝
撃性に優れた暹脂組成物ずするこずができる。(a) The following formula: (In the formula, X and Y may be the same or different, and each represents H, Cl, Br, F, CH 3 , COOH,
COOCH 3 , CN, OCOCH 3 , COCH 3 , C 6 H 5 ,
Represents SO 3 H or OR 1 . However, R 1 is a lower alkyl group) (a 2 ) CF 2 = CFZ (in the formula, Z represents H, Cl, F or CF 3 ) (In the formula, R 2 represents a fluoroalkyl group) Homopolymers of vinyl monomers or vinylidene monomers or copolymers of these monomers (b) Polycarbonates, thermoplastic polyesters, and polyamides Also, the production method of the present invention It has excellent transparency even when mixed with other thermoplastic resins that have different refractive indexes but are compatible.
A resin composition having no or very little stress whitening property can be obtained. In particular, when blended with a methyl methacrylate resin, a resin composition can be obtained that has excellent transparency, stress whitening resistance, weather resistance, and impact resistance.

このようにポリマヌブレンド系においおもスト
レス癜化性が極めお小さいこずは驚くべきこずで
ある。これは倚局構造重合䜓が有する特殊構造の
効果に基くものであり、埓来のゎム成分を導入す
る方法からは予枬し埗ないものである。 It is surprising that stress whitening properties are extremely low even in polymer blend systems. This is based on the effect of the special structure of the multilayer polymer, and cannot be predicted from conventional methods of introducing rubber components.

ポリマヌブレンド系に぀いお曎に詳现な説明を
するず、䟋えば、塩化ビニル暹脂、ポリスチレ
ン、AS暹脂、ポリカヌボネヌト暹脂ず混合した
堎合には、本発明の補造方法による倚局構造重合
䜓は䞀皮の耐候性・耐衝撃性改質剀ずしお䜜甚
し、耐候性・耐衝撃性の倧幅な向䞊をもたらす。 To explain the polymer blend system in more detail, for example, when mixed with vinyl chloride resin, polystyrene, AS resin, or polycarbonate resin, the multilayer structure polymer produced by the production method of the present invention has a type of weather resistance and impact resistance. Acts as a modifier and significantly improves weather resistance and impact resistance.

たた、ポリフツ化ビニリデンずのブレンド組成
物は耐候性、透明性、耐ストレス癜化性、耐薬品
性、匷靭性、成圢性等の諞特性に優れるものであ
り、特にポリフツ化ビニリデン〜50郚ず倚局構
造重合䜓50〜99郚ずからなる暹脂組成物は、フむ
ルム成圢甚玠材ずしおも優れおおり、透明で匷靭
な耐候性、耐ストレス癜化性、耐薬品性等に優れ
たフむルムを䞎える。かかるフむルムは通垞の成
圢品の衚面にラミネヌトするこずにより容易に耐
候性ず意匠効果ずを付䞎するこずが出来、極めお
商品䟡倀の高いものである。 In addition, blend compositions containing polyvinylidene fluoride have excellent properties such as weather resistance, transparency, stress whitening resistance, chemical resistance, toughness, and moldability. A resin composition comprising 50 to 99 parts of a multilayer structure polymer is also excellent as a material for film molding, and provides a transparent, tough film with excellent weather resistance, stress whitening resistance, chemical resistance, etc. Such a film can easily impart weather resistance and a design effect by laminating it on the surface of an ordinary molded article, and has extremely high commercial value.

以䞋実斜䟋により本発明を具䜓的に説明する。 The present invention will be specifically explained below using Examples.

実斜䟋䞭の郚数はすべお重量基準である。 All parts in the examples are by weight.

なお実斜䟋䞭の略語は䞋蚘の通りである。 In addition, the abbreviations in the examples are as follows.

MMA メチルメタクリレヌト BuA ブチルアクリレヌト AMA アリルメタクリレヌト TAC トリアリルシアヌレヌト CHP クメンヒドロペルオキシド SFS ゜ゞりムホルムアルデヒドスルホキシレ
ヌト −OSH −オクチルメルカプタン BD −ブチレングリコヌルゞメタクリ
レヌト 実斜䟋  冷华噚぀き反応容噚内にむオン亀換氎250郚、
スルホコハク酞゚ステル゜ヌダ塩1.5郚、SFS0.05
郚を仕蟌み、窒玠気流䞋で撹拌埌、65郚のBuA、
0.65郚のAMAを仕蟌んだ。BuA䞭にはBuAに察
しお0.1CHPを溶解させた。尚、以降の段階で
加えられる党おのモノマヌに぀いおも特別の蚘茉
がない限りそれぞれのモノマヌに察しお0.1の
CHPが含たれおいる。次に、窒玠気流䞋にお、
200rpmの回転数で撹拌しながら50℃に昇枩し、
180分間撹拌しお最内局重合䜓の重合を完
了させた。重合率は97以䞊であ぀た。埗られた
最内局重合䜓の粒子埄は玄0.1Ό、ゲル含有
量92.5重量、膚最床7.5であ぀た。たた、
局のガラス転移枩床Tgは−40℃であ぀た。 MMA Methyl methacrylate BuA Butyl acrylate AMA Allyl methacrylate TAC Triallyl cyanurate CHP Cumene hydroperoxide SFS Sodium formaldehyde sulfoxylate n-OSH n-Octyl mercaptan BD 1,3-Butylene glycol dimethacrylate Example 1 Inside a reaction vessel with a condenser 250 parts of ion exchange water,
Sulfosuccinic acid ester soda salt 1.5 parts, SFS0.05
After stirring under a nitrogen stream, 65 parts of BuA,
I prepared 0.65 copies of AMA. 0.1% CHP was dissolved in BuA. Furthermore, for all monomers added in subsequent steps, 0.1% of each monomer is added unless otherwise specified.
Contains CHP. Next, under a nitrogen stream,
The temperature was raised to 50°C while stirring at a rotation speed of 200 rpm.
The mixture was stirred for 180 minutes to complete polymerization of the innermost layer polymer (A). The polymerization rate was 97% or more. The resulting innermost layer polymer (A) had a particle diameter of approximately 0.1 Ό, a gel content of 92.5% by weight, and a degree of swelling of 7.5. Also, (A)
The glass transition temperature (Tg) of the layer was -40°C.

次に重合枩床を75℃に昇枩し、少量の氎にずか
した0.05郚のSFSを添加したのち、郚のMMA、
郚のBuA、0.05郚のAMAの混合物を30分間に
わた぀お反応系に滎䞋し、曎に60分保持しお䞭間
局の重合を行な぀た。 Next, the polymerization temperature was raised to 75℃, and after adding 0.05 parts of SFS dissolved in a small amount of water, 5 parts of MMA,
A mixture of 5 parts of BuA and 0.05 parts of AMA was added dropwise to the reaction system over 30 minutes, and the mixture was maintained for an additional 60 minutes to polymerize the intermediate layer (C).

曎に匕き぀づき、25郚のMMA及び0.025郚の
−OSHからなる混合物を60分間にわた぀お反
応系に滎䞋し、曎に60分撹拌䞋反応系をその枩床
に保持しお最倖局重合䜓の重合を完了させ
た。局のTgは100℃であ぀た。 Subsequently, a mixture consisting of 25 parts of MMA and 0.025 parts of n-OSH was added dropwise to the reaction system over a period of 60 minutes, and the reaction system was maintained at that temperature with stirring for an additional 60 minutes to form the outermost layer polymer (B). ) was completed. The Tg of layer (B) was 100°C.

埗られたラテツクスを郚のCaCl2を甚いお塩
析し、凝集・固化したのち過・氎掗・也燥しお
也粉を埗た。 The obtained latex was salted out using 5 parts of CaCl2 , coagulated and solidified, filtered, washed with water, and dried to obtain a dry powder.

埗られた倚局構造重合䜓のゲル含有量は80で
あ぀た。 The gel content of the obtained multilayer polymer was 80%.

倚局構造重合䜓の也粉100重量郚に察しお1.5郚
の玫倖線吞収剀を添加混合し、盎埄40mmのスクリ
ナヌを有する抌出機を甚いお200℃で抌出し、こ
れを切断しおペレツトずした。 1.5 parts of an ultraviolet absorber was added to 100 parts by weight of the dry powder of the multilayer structure polymer, and the mixture was extruded at 200°C using an extruder with a screw of 40 mm in diameter, and the pellets were cut into pellets.

埗られたペレツトを十分に也燥したのち、射出
成型機を甚いおmm厚の平板を成型した。 After the obtained pellets were sufficiently dried, they were molded into a 2 mm thick flat plate using an injection molding machine.

埗られた平板の党光線透過率は91、曇䟡は
2.5であり、透明性は極めお良奜であ぀た。 The total light transmittance of the obtained flat plate was 91%, and the haze value was
2.5, and the transparency was extremely good.

又、この暹脂板のシペア硬床は42、曲げ匟性
率2000Kgcm2であ぀た。 Further, the shore D hardness of this resin plate was 42, and the flexural modulus was 2000 Kg/cm 2 .

曎に、この平板をサンシダむンり゚ザオメヌタ
ヌを甚いた2000時間の加速曝露詊隓に䟛したが、
詊隓埌も着色等は認められず、又党光線透過率も
86ずほずんど䜎䞋しおいなか぀た。 Furthermore, this plate was subjected to a 2000-hour accelerated exposure test using a Sunshine Weather-Ometer.
Even after the test, no coloring was observed, and the total light transmittance was also low.
There was almost no decline at 86%.

実斜䟋  冷华噚぀き反応容噚内にむオン亀換氎250郚、
スルホコハク酞゚ステル゜ヌダ塩1.5郚、SFS0.05
郚を仕蟌み、窒玠気流䞋で撹拌しお容噚内を十分
に窒玠眮換したのち、70郚のBuA、0.35郚の
TAC及びBuAに察し0.1のCHPからなるモノマ
ヌ混合物を仕蟌んだ。なお、以降の各段で加えら
れる党おのモノマヌに぀いおも特別の蚘茉がない
限り、それぞれのモノマヌに察し0.1のCHPを
含むものずする。Example 2 250 parts of ion-exchanged water was placed in a reaction vessel equipped with a condenser.
Sulfosuccinic acid ester soda salt 1.5 parts, SFS0.05
After stirring under a nitrogen stream and replacing the inside of the container with nitrogen, add 70 parts of BuA and 0.35 parts of BuA.
A monomer mixture consisting of 0.1% CHP to TAC and BuA was charged. It should be noted that all monomers added in the subsequent steps also contain 0.1% CHP, unless otherwise specified.

次いで反応容噚を窒玠気流䞋に200rpmの回転
数で撹拌しながら50℃に昇枩し、180分間撹拌し
ながら重合を続け、最内局重合䜓の重合を
完了させた。埗られた最内局重合䜓の粒子
埄は玄0.13Όであり、Tgは−40℃、ゲル含有量は
89重量、膚最床は19であ぀た。 Next, the temperature of the reaction vessel was raised to 50° C. under a nitrogen stream while stirring at a rotation speed of 200 rpm, and polymerization was continued while stirring for 180 minutes to complete polymerization of the innermost layer polymer (A). The resulting innermost layer polymer (A) had a particle size of about 0.13ÎŒ, a Tg of -40°C, and a gel content of
The content was 89% by weight, and the degree of swelling was 19.

次いで反応系を80℃に昇枩し、少量の氎にずか
した0.05郚のSFSを添加したのち、郚のMMA
郚のBuA0.05郚のTACからなるモノマヌ混
合物を30分間にわた぀お反応系に滎䞋し、曎に60
分間撹拌しながら80℃に保持し䞭間局の重
合を行な぀た。次いで20郚のMMAを60分間にわ
た぀お反応系に滎䞋し、曎に60分間反応系をその
枩床に保持しお最倖局重合䜓の重合を完了
させた。 Next, the reaction system was heated to 80°C, and 0.05 parts of SFS dissolved in a small amount of water was added, followed by 5 parts of MMA,
A monomer mixture consisting of 5 parts BuA and 0.05 parts TAC was added dropwise to the reaction system over a period of 30 minutes.
The intermediate layer (C) was polymerized by maintaining the temperature at 80° C. while stirring for a minute. Next, 20 parts of MMA was added dropwise to the reaction system over 60 minutes, and the reaction system was maintained at that temperature for an additional 60 minutes to complete polymerization of the outermost layer polymer (B).

埗られたラテツクスを郚のCaCl2を甚いお塩
析し、凝集・固化したのち、過氎掗也燥し
お也粉を埗た。埗られた倚局構造重合䜓のTgは
100℃、ゲル含有量は85であ぀た。 The obtained latex was salted out using 5 parts of CaCl 2 to coagulate and solidify, and then filtered, washed with water, and dried to obtain a dry powder. The Tg of the obtained multilayer structure polymer is
At 100°C, the gel content was 85%.

実斜䟋  実斜䟋ず同様にしお、50郚のBuA、郚の
MMA、郚のBD及び0.275郚のAMAからなる
最内局、7.5郚のBuA、7.5郚のMMA及び0.1郚の
AMAからなる䞭間局及び27郚のMMA、郚の
BuA、0.03郚の−OSHからなる最倖局を有す
る倚局構造重合䜓を重合した。該重合䜓の最内局
のTgは−25℃、ゲル含有量は95重量、膚
最床はであり、たた最倖局のTgは80℃
であ぀お、該重合䜓党䜓のゲル含有量は75重量
であ぀た。Example 3 In the same manner as in Example 1, 50 parts of BuA, 3 parts of
Innermost layer consisting of MMA, 2 parts BD and 0.275 parts AMA, 7.5 parts BuA, 7.5 parts MMA and 0.1 parts
Intermediate layer consisting of AMA and 27 divisions of MMA, 3 divisions of
A multilayered polymer was polymerized with the outermost layer consisting of BuA and 0.03 parts of n-OSH. The Tg of the innermost layer (A) of the polymer is -25°C, the gel content is 95% by weight, and the degree of swelling is 6, and the Tg of the outermost layer (B) is 80°C.
and the gel content of the entire polymer is 75% by weight
It was hot.

倚局構造重合䜓を甚い実斜䟋ず同様に平板を
成圢し評䟡した。この平板の党光線透過率は93
、曇䟡は2.0であり、シペア硬床は47であ぀
た。又この平板は、サンシダむンり゚ザオメヌタ
ヌによる2000時間の加速曝露詊隓埌も倉色及び透
明性の䜎䞋をおこしおおらず、耐候性にもすぐれ
たものであ぀た。 A flat plate was molded using the multilayer structure polymer in the same manner as in Example 1 and evaluated. The total light transmittance of this flat plate is 93
%, haze value was 2.0, and shore D hardness was 47. Furthermore, this flat plate showed no discoloration or decrease in transparency even after a 2000 hour accelerated exposure test using a Sunshine Weather-Ometer, and had excellent weather resistance.

曎に倚局構造重合䜓を甚いお、むンフレヌシペ
ン法により、190℃で厚み50Όのフむルムを成膜
した。このフむルムは極めお柔軟で、か぀透明性
にもすぐれ、柔軟性が芁求される甚途でのオヌバ
ヌレむフむルムずしお最適なものであ぀た。 Furthermore, using the multilayer structure polymer, a film with a thickness of 50 ÎŒm was formed at 190° C. by an inflation method. This film was extremely flexible and had excellent transparency, making it ideal as an overlay film for applications requiring flexibility.

実斜䟋  実斜䟋ず同様にしお䞋蚘の劂き組成の二局構
造重合䜓を補造した。Example 4 A two-layer structure polymer having the following composition was produced in the same manner as in Example 1.

最内局BuA 70郚TAC 0.525郚 最倖局MMA 27郚BuA 郚−
OSH 0.03郚 該重合䜓の最内局の粒子埄は玄0.12Ό、
ゲル含有量は90重量、膚最床は23であ぀た。又
最倖局のTg蚈算倀は玄80℃であり、最
終重合䜓のゲル含有量は83であ぀た。 Innermost layer (A); BuA 70 parts, TAC 0.525 parts Outermost layer (B); MMA 27 parts, BuA 3 parts, n-
OSH 0.03 part The particle size of the innermost layer (A) of the polymer is approximately 0.12Ό,
The gel content was 90% by weight and the degree of swelling was 23. The Tg (calculated value) of the outermost layer (B) was about 80°C, and the gel content of the final polymer was 83%.

この倚局構造重合䜓を甚い、実斜䟋ず同様に
平板に成圢し評䟡した。埗られた平板の党光線透
過率は87、曇䟡は3.5であり、たた曲げ匟性率
は2000Kgcm2、シペア硬床は41であ぀た。 Using this multilayer structure polymer, it was molded into a flat plate and evaluated in the same manner as in Example 1. The obtained flat plate had a total light transmittance of 87%, a haze value of 3.5, a flexural modulus of 2000 Kg/cm 2 and a Shore D hardness of 41.

曎にサンシダむンり゚ザオメヌタヌによる2000
時間の加速曝露詊隓埌も着色、透明性の倧巟な䜎
䞋は認められなか぀た。 Furthermore, 2000 by Sunshine Weather Ometer
Even after the accelerated exposure test, no significant decrease in coloration or transparency was observed.

Claims (1)

【特蚱請求の範囲】  (A) 60〜100重量郚の炭玠数以䞋のアルキ
ル基を有するアルキルアクリレヌトA1、 〜40重量郚の共重合可胜な二重結合を有す
る単量䜓A2、 〜10重量郚の倚官胜性単量䜓A3、 及び A1〜A3の合蚈量100重量郚に察し
0.1〜重量郚のグラフト亀叉剀を重合させ、
ゲル含有量が60重量以䞊、ガラス転移枩床が
℃以䞋である最内局重合䜓を圢成さ
せ、 (B) 次に、60〜100重量郚の炭玠数以䞋のアル
キル基を有するアルキルメタクリレヌト
B1、及び 〜40重量郚の共重合可胜な二重結合を有す
る単量䜓B2 を最内局重合䜓にグラフト重合させ、ガ
ラス転移枩床が60℃以䞊である最倖局重合䜓
を圢成させ、 そしおこのようにしお埗られる倚局構造重合䜓
䞭に占める最内局重合䜓の割合が51〜90重
量であり、最倖局重合䜓の割合が10〜49
重量であるここずを特城ずする倚局構造重合䜓
の補造方法。  (A) 60〜100重量郚の炭玠数以䞋のアルキ
ル基を有するアルキルアクリレヌトA1、 〜40重量郚の共重合可胜な二重結合を有す
る単量䜓A2、 〜10重量郚の倚官胜性単量䜓A3、 及び A1〜A3の合蚈量100重量郚に察し
0.1〜重量郚のグラフト亀叉剀を重合させ、
ゲル含有量が60重量以䞊、ガラス転移枩床が
℃以䞋である最内局重合䜓を圢成さ
せ、 (C) 次に、10〜90重量郚の炭玠数以䞋のアルキ
ル基を有するアルキルメタクリレヌトC1、 10〜90重量郚の炭玠数以䞋のアルキル基を
有するアルキルアクリレヌトC2、 〜20重量郚の共重合可胜な二重結合を有す
る単量䜓C3、 〜10重量の倚官胜性単量䜓C4、及び C1〜C4の合蚈量100重量郚に察し0.1
〜重量郚のグラフト亀叉剀を最内局重合䜓
にグラフト重合させお少くずも䞀局の䞭
間局を圢成させ、 (B) 次に、60〜100重量郚の炭玠数以䞋のアル
キル基を有するアルキルメタクリレヌト
B1、及び 〜40重量郚の共重合可胜な二重結合を有す
る単量䜓B2 を䞭間局にグラフト重合させ、ガラス転
移枩床が60℃以䞊である最倖局重合䜓を
圢成させ、 そしおこのようにしお埗られる倚局構造重合䜓
䞭に占める最内局重合䜓の割合が51〜85重
量であり、䞭間局の割合が〜30重量
であり、最倖局重合䜓の割合が10〜44重量
であるこずを特城ずする倚局構造重合䜓の補造
方法。[Scope of Claims] 1 (A) 60 to 100 parts by weight of an alkyl acrylate (A 1 ) having an alkyl group having 8 or less carbon atoms, and 0 to 40 parts by weight of a monomer having a copolymerizable double bond. (A 2 ), 0 to 10 parts by weight of polyfunctional monomer (A 3 ), and 100 parts by weight of the total amount of (A 1 ) to (A 3 )
polymerizing 0.1 to 5 parts by weight of a graft cross-agent;
Form an innermost layer polymer (A) having a gel content of 60% by weight or more and a glass transition temperature of 0°C or less, and (B) having 60 to 100 parts by weight of an alkyl group having 4 or less carbon atoms. Alkyl methacrylate (B 1 ) and 0 to 40 parts by weight of a monomer having a copolymerizable double bond (B 2 ) are graft-polymerized to the innermost layer polymer (A), and the glass transition temperature is 60°C or higher. The proportion of the innermost layer polymer (A) in the thus obtained multilayer structure polymer is 51 to 90% by weight, and the outermost layer polymer ( B) ratio is 10-49
A method for producing a multilayer polymer characterized by the following: 2 (A) 60 to 100 parts by weight of an alkyl acrylate (A 1 ) having an alkyl group having 8 or less carbon atoms, 0 to 40 parts by weight of a monomer (A 2 ) having a copolymerizable double bond, 0 ~10 parts by weight of polyfunctional monomer (A 3 ) and 100 parts by weight of the total amount of (A 1 ) to (A 3 )
polymerizing 0.1 to 5 parts by weight of a graft cross-agent;
forming an innermost layer polymer (A) having a gel content of 60% by weight or more and a glass transition temperature of 0°C or less; Alkyl methacrylate (C 1 ), 10 to 90 parts by weight of alkyl acrylate (C 2 ) having an alkyl group having 8 or less carbon atoms, 0 to 20 parts by weight of a monomer having a copolymerizable double bond (C 3 ), 0 to 10 parts by weight of polyfunctional monomer (C 4 ), and 0.1 parts by weight per 100 parts by weight of the total amount of (C 1 ) to (C 4 ).
~5 parts by weight of a graft cross-agent is graft-polymerized to the innermost layer polymer (A) to form at least one intermediate layer (C), and (B) 60 to 100 parts by weight of a carbon number of 4 or less An alkyl methacrylate (B 1 ) having an alkyl group of The outermost layer polymer (B) having a temperature of 60°C or higher is formed, and the proportion of the innermost layer polymer (A) in the multilayer structure polymer thus obtained is 51 to 85% by weight, and the middle layer is The proportion of (C) is 5 to 30% by weight
A method for producing a multilayer structure polymer, characterized in that the proportion of the outermost layer polymer (B) is 10 to 44% by weight.
JP22777782A 1982-12-28 1982-12-28 Polymer having multi-layered structure Granted JPS59122513A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP22777782A JPS59122513A (en) 1982-12-28 1982-12-28 Polymer having multi-layered structure
JP20520090A JPH03163153A (en) 1982-12-28 1990-08-03 Multilayered polymer resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP22777782A JPS59122513A (en) 1982-12-28 1982-12-28 Polymer having multi-layered structure

Related Child Applications (1)

Application Number Title Priority Date Filing Date
JP20520090A Division JPH03163153A (en) 1982-12-28 1990-08-03 Multilayered polymer resin composition

Publications (2)

Publication Number Publication Date
JPS59122513A JPS59122513A (en) 1984-07-16
JPH0315648B2 true JPH0315648B2 (en) 1991-03-01

Family

ID=16866215

Family Applications (1)

Application Number Title Priority Date Filing Date
JP22777782A Granted JPS59122513A (en) 1982-12-28 1982-12-28 Polymer having multi-layered structure

Country Status (1)

Country Link
JP (1) JPS59122513A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59152856A (en) * 1983-02-21 1984-08-31 䞉菱レむペン株匏䌚瀟 Multilayer structure polymer
US4916171A (en) * 1984-07-25 1990-04-10 Rohm And Haas Company Polymers comprising alkali-insoluble core/alkali-soluble shell and copositions thereof
CA1332992C (en) * 1986-08-27 1994-11-08 Susan Marie Liwak Impact-strength modifiers for thermoplastic polymers
FR2610328B1 (en) * 1987-01-30 1989-08-25 Charbonnages Ste Chimique INTERPOLYMER STRENGTHENING MATERIAL OF RIGID THERMOPLASTIC MATRICES, PREPARATION THEREOF AND CORRESPONDING REINFORCED COMPOSITIONS
FR2610327B1 (en) * 1987-01-30 1989-08-25 Charbonnages Ste Chimique MULTI-LAYER COMPOSITE INTERPOLYMER, PREPARATION METHOD THEREOF, APPLICATION TO REINFORCEMENT OF RIGID THERMOPLASTIC MATRICES AND REINFORCED COMPOSITIONS THEREOF
JP2004339350A (en) * 2003-05-15 2004-12-02 Mitsubishi Rayon Co Ltd Acrylic soft resin, acrylic soft resin composition and manufacturing process of the composition
KR100548626B1 (en) * 2003-10-29 2006-01-31 죌식회사 엘지화학 Rubber Latex and Manufacturing Method thereof
CN103703076A (en) * 2011-05-31 2014-04-02 䞉菱䞜阳株匏䌚瀟 Acrylic resin composition, molded object thereof, process for producing film, and acrylic resin film
EP3774956A1 (en) * 2018-03-29 2021-02-17 Rohm and Haas Company Three-stage polymer particle
WO2019190703A1 (en) * 2018-03-29 2019-10-03 Rohm And Haas Company Modified styrene-acrylonitrile

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