JPH06285943A - Co-extrusion molded object - Google Patents
Co-extrusion molded objectInfo
- Publication number
- JPH06285943A JPH06285943A JP4256311A JP25631192A JPH06285943A JP H06285943 A JPH06285943 A JP H06285943A JP 4256311 A JP4256311 A JP 4256311A JP 25631192 A JP25631192 A JP 25631192A JP H06285943 A JPH06285943 A JP H06285943A
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- Japan
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- weight
- monomer
- resin
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- terpolymer
- 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.)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Molding Of Porous Articles (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、耐候性だけでなく、
耐衝撃性や成形性(共押出成形時の円滑性)等の点におい
ても優れた被覆層を有する共押出成形体に関する。BACKGROUND OF THE INVENTION The present invention is not limited to weather resistance,
The present invention relates to a coextrusion molded article having a coating layer excellent in impact resistance and moldability (smoothness during coextrusion molding).
【０００２】[0002]
【従来の技術】従来から、住宅用外装材等として、樹脂
発泡成形体、例えば、ポリ塩化ビニル樹脂発泡成形体が
広く利用されているが、耐候性が悪いため、暴露経時変
化による表面白化が問題となっていた。このような問題
の一般的な解決策としては、耐候性に優れたアクリル系
樹脂を樹脂発泡基材と共押出成形することによって発泡
成形体の表面をアクリル系樹脂で被覆する方法が知られ
ている。2. Description of the Related Art Conventionally, resin foam moldings, such as polyvinyl chloride resin foam moldings, have been widely used as exterior materials for homes, etc. However, due to poor weather resistance, surface whitening due to aging It was a problem. As a general solution to such a problem, there is known a method in which an acrylic resin having excellent weather resistance is coextruded with a resin foaming base material to coat the surface of the foamed molded article with the acrylic resin. There is.
【０００３】しかしながら、従来からこのような目的に
使用されているアクリル系樹脂は耐衝撃性に劣るだけで
なく、成形性が悪いという難点があり、当該分野におい
ては、このような難点の改良が要請されている。However, acrylic resins conventionally used for such purposes have the drawbacks of not only being inferior in impact resistance but also being inferior in moldability, and in the art, improvement of such difficulties is required. Has been requested.
【０００４】[0004]
【発明が解決しようとする課題】この発明は、このよう
な要請に応え、耐候性だけでなく、耐衝撃性や成形性等
の点においても優れた被覆層を有する共押出成形体を提
供するためになされたものである。The present invention meets these requirements and provides a coextrusion molded article having a coating layer excellent not only in weather resistance but also in impact resistance and moldability. It was done for good.
【０００５】[0005]
【課題を解決するための手段】即ちこの発明は、下記の
被覆組成物を発泡樹脂基材と共押出成形することによっ
て製造される共押出成形体に関する： (i)(a)芳香族ビニル単量体とアクリル酸エステルとアク
リル酸アリルおよび／またはメタクリル酸アリルとを反
応させて得られる三元共重合弾性体の存在下に、メタク
リル酸メチルとこれと共重合可能なビニル単量体または
ビニリデン単量体とから成る単量体とを反応させて得ら
れるグラフト共重合体、および(b)メタクリル酸メチル
とこれと共重合可能なビニル単量体またはビニリデン単
量体とから成る単量体を重合させて得られる重合体を、
該三元共重合弾性体の含有量が５〜５０重量％になるよ
うに配合して成るメタクリル系樹脂組成物２０〜７９．
８重量％、 (ii)ブタジエン系ゴム０．１〜４０重量％ (iii)フッ素系樹脂０．１〜１０重量％、および (iv)ビニル芳香族単量体５０〜９０重量％、Ｃ1-13アル
キル基を有するアクリル酸アルキルエステルまたはメタ
クリル酸アルキルエステル１０〜５０重量％およびその
他のモノエチレン性不飽和単量体０〜４０重量％から成
る非架橋性単量体１００重量部と２個以上の二重結合を
有する架橋性単量体０．５〜５重量部から成る混合単量
体を懸濁重合することによって得られる架橋重合体(平
均粒径:３５〜５００μ)２０〜３０重量％を含有する被
覆組成物。That is, the present invention relates to a coextrusion molded article produced by coextrusion molding the following coating composition with a foamed resin substrate: (i) (a) an aromatic vinyl unit Methyl methacrylate and a vinyl monomer or vinylidene copolymerizable therewith in the presence of a terpolymer elastomer obtained by reacting a monomer, an acrylate ester and allyl acrylate and / or allyl methacrylate Graft copolymer obtained by reacting a monomer consisting of a monomer, and (b) a monomer consisting of methyl methacrylate and a vinyl monomer or vinylidene monomer copolymerizable therewith A polymer obtained by polymerizing
Methacrylic resin composition 20-79. Blended so that the content of the terpolymer elastic body is 5 to 50% by weight.
8% by weight, (ii) butadiene rubber 0.1 to 40% by weight (iii) fluorine resin 0.1 to 10% by weight, and (iv) vinyl aromatic monomer 50 to 90% by weight, C 1- 100 parts by weight of non-crosslinkable monomer consisting of 10 to 50% by weight of alkyl or methacrylic acid alkyl ester having 13 alkyl groups and 0 to 40% by weight of other monoethylenically unsaturated monomer, and 2 or more 20-30% by weight of a cross-linked polymer (average particle size: 35-500μ) obtained by suspension-polymerizing a mixed monomer consisting of 0.5-5 parts by weight of a cross-linking monomer having a double bond A coating composition containing:
【０００６】本発明において使用する被覆組成物の配合
成分であるメタクリル系樹脂組成物を得るためには、例
えば、まず、スチレン、モノクロロスチレン、ジクロロ
スチレンおよびビニルトルエンから成る群から選択され
る芳香族ビニル単量体１０〜３０重量％とＣ2-8アルキ
ル基を有するアクリル酸エステル７０〜９０重量％から
成る混合単量体１００重量部とアクリル酸アリルおよび
／またはメタクリル酸アリル０．１〜５．０重量部との
混合物を重合することによって三元共重合弾性体を調製
する。In order to obtain a methacrylic resin composition which is a blending component of the coating composition used in the present invention, for example, first, an aromatic selected from the group consisting of styrene, monochlorostyrene, dichlorostyrene and vinyltoluene. 100 parts by weight of a mixed monomer consisting of 10 to 30% by weight of a vinyl monomer and 70 to 90% by weight of an acrylic ester having a C 2-8 alkyl group, and 0.1 to 5 allyl acrylate and / or allyl methacrylate. A terpolymer elastomer is prepared by polymerizing a mixture with 0.0 part by weight.
【０００７】上記重合反応は、水性媒体中において、所
定量の前記単量体成分を、乳化剤(例えば、長鎖脂肪酸
アルカリ塩、アルキルベンゼンスルホン酸塩または長鎖
アルキル硫酸エステル等)および重合開始剤(例えば、過
硫酸塩、過硼酸塩または有機ヒドロパーオキシド第一鉄
塩等)の存在下、常温〜１２０℃で乳化重合させること
によっておこなう。In the above-mentioned polymerization reaction, a predetermined amount of the above-mentioned monomer component is mixed with an emulsifier (for example, long-chain fatty acid alkali salt, alkylbenzene sulfonate or long-chain alkyl sulfate ester) and a polymerization initiator in an aqueous medium. For example, it is carried out by emulsion polymerization at room temperature to 120 ° C. in the presence of a persulfate, a perborate, a ferrous organic hydroperoxide, etc.).
【０００８】上記の乳化重合反応においては、反応条件
(例えば、単量体の量比、乳化剤や重合開始剤の種類、
単量体や乳化剤の添加方法および反応温度や反応時間
等)を適宜選定することによって、生成する三元共重合
弾性体の膨潤度、ゲル含量および粒径がそれぞれ３〜２
０、８０％以上および０．０５〜０．２５μになるよう
にする。膨潤度およびゲル含量(％)はそれぞれ(Ｗ1−Ｗ
0)／Ｗ0および(Ｗ2／Ｗ0)×１００で定義される。ここ
で、Ｗ0は生成した弾性体の重さを示し、Ｗ1は該弾性体
を約５０倍量のトルエンに３０℃で４８時間浸漬した膨
潤弾性体の重さを示し、また、Ｗ2は該膨潤弾性体の恒
量になるまで真空乾燥した後の重さを示す。In the above emulsion polymerization reaction, the reaction conditions
(For example, the amount ratio of monomers, the type of emulsifier and polymerization initiator,
By appropriately selecting the addition method of the monomer and the emulsifier and the reaction temperature, the reaction time, etc., the swelling degree, gel content and particle size of the terpolymer elastomer to be produced are 3 to 2 respectively.
It should be 0, 80% or more and 0.05 to 0.25 μ. The degree of swelling and the gel content (%) are (W 1 -W
0 ) / W 0 and (W 2 / W 0 ) × 100. Here, W 0 represents the weight of the generated elastic body, W 1 represents the weight of the swollen elastic body in which the elastic body was immersed in about 50 times the amount of toluene at 30 ° C. for 48 hours, and W 2 Indicates the weight of the swelled elastic body after vacuum drying to a constant weight.
【０００９】上記反応によって得られる三元共重合弾性
体は十分な架橋度を有しているが、さらに過酸化物(例
えば、ジイソプロピルパーオキシジカーボネート、ジ−
２−エチルヘキシルパーオキシジカーボネートまたはt
−ブチルパーオキシピバレート等)を用いて架橋度を高
めてもよく、これによって、樹脂組成物の透明性と表面
光沢性を高めることができる。The terpolymer elastomer obtained by the above reaction has a sufficient degree of cross-linking, but further contains a peroxide (for example, diisopropyl peroxydicarbonate, di-
2-ethylhexyl peroxydicarbonate or t
-Butyl peroxypivalate, etc.) may be used to increase the degree of crosslinking, whereby the transparency and surface gloss of the resin composition can be increased.
【００１０】本発明に用いるメタクリル系樹脂組成物の
一方の成分であるグラフト共重合体は、上記のようにし
て得られる三元共重合弾性体１００重量部に対して、例
えば、メタクリル酸メチル８０〜１００重量％およびこ
れと共重合可能な少なくとも１種のビニル単量体または
ビニリデン単量体２０〜０重量％から成る単量体５〜９
００重量部反応させることによって調製される。このグ
ラフト重合反応は、開始剤(例えば、クメンヒドロパー
オキシドやt−ブチルヒドロパーオキシド等の有機ヒド
ロパーオキシドとナトリウムホルムアルデヒドスルフォ
キシレートまたはナトリウムメタバイサルフェートとの
混合物等)、重合度調節剤(例えば、Ｃ2-18のアルキルメ
ルカプタン、チオグリコール酸エステル、チオグリコー
ル酸またはメルカプト酸等)および所望による水の存在
下において、通常５０〜１００℃でおこなう。生成する
グラフト共重合体は、常法に従って、塩析、凝固、濾
過、洗浄および乾燥等の後処理に付すことによって、一
般的には白色粉末として得られる。The graft copolymer which is one of the components of the methacrylic resin composition used in the present invention is, for example, 80 parts by weight of methyl methacrylate based on 100 parts by weight of the terpolymer elastic body obtained as described above. 5 to 9 consisting of 20 to 100% by weight and 20 to 0% by weight of at least one vinyl or vinylidene monomer copolymerizable therewith
It is prepared by reacting 00 parts by weight. This graft polymerization reaction is carried out by using an initiator (for example, a mixture of organic hydroperoxide such as cumene hydroperoxide or t-butyl hydroperoxide and sodium formaldehyde sulfoxylate or sodium metabisulfate), a polymerization degree modifier. (Eg, C 2-18 alkyl mercaptan, thioglycolic acid ester, thioglycolic acid or mercapto acid) and optionally water, usually at 50 to 100 ° C. The resulting graft copolymer is generally obtained as a white powder by subjecting it to post-treatments such as salting out, coagulation, filtration, washing and drying according to a conventional method.
【００１１】メタクリル系樹脂組成物の他方の成分であ
る重合体は、メタクリル酸メチル８０〜１００重量％お
よびこれと共重合可能な少なくとも１種のビニル単量体
またはビニリデン単量体２０〜０重量％から成る単量体
を重合させて得られるメタクリル酸メチル系重合体であ
る。The polymer, which is the other component of the methacrylic resin composition, comprises 80 to 100% by weight of methyl methacrylate and 20 to 0% by weight of at least one vinyl monomer or vinylidene monomer copolymerizable therewith. Is a methyl methacrylate-based polymer obtained by polymerizing a monomer composed of 100% by weight.
【００１２】本発明に用いるメタクリル系樹脂組成物
は、上述のようにして調製されるグラフト共重合体とメ
タクリル酸メチル系重合体を、前記の三元共重合体の含
有量が５〜５０重量％になるように配合することによっ
て得られる。両成分の配合は、両者を予め所望の添加剤
(例えば、染料、顔料、フィラーまたは滑剤等)と共に、
ブレンダー等の混合機を用いて均一に混合した後、バン
バリーミキサーやミキシングロール等を用いて溶融混練
することによっておこなう。The methacrylic resin composition used in the present invention comprises the graft copolymer prepared as described above and the methyl methacrylate polymer, and the content of the terpolymer is 5 to 50% by weight. It is obtained by blending so that it becomes%. Both components should be mixed in advance with the desired additives.
(E.g., dye, pigment, filler or lubricant, etc.),
The mixture is uniformly mixed using a mixer such as a blender, and then melt-kneaded using a Banbury mixer or a mixing roll.
【００１３】本発明において使用する被覆組成物の配合
成分であるブタジエン系ゴムとしてはブタジエン−アク
リロニトリルゴム、ブタジエンゴムおよびスチレン−ブ
タジエンゴム等が例示され、これらの配合量は０．１〜
４０重量％である。ブタジエン系ゴムの配合量が０．１
重量％よりも少ない場合には、耐衝撃性が低下し、ま
た、４０重量％よりも多くなると、耐候性が低下する。Examples of the butadiene-based rubber which is a compounding component of the coating composition used in the present invention include butadiene-acrylonitrile rubber, butadiene rubber and styrene-butadiene rubber.
It is 40% by weight. Compounding amount of butadiene rubber is 0.1
When it is less than 40% by weight, impact resistance is lowered, and when it is more than 40% by weight, weather resistance is lowered.
【００１４】本発明において使用する被覆組成物の配合
成分であるフッ素系樹脂としては、フッ化ビニリデン、
エチレン−テトラフルオロエチレン共重合体およびエチ
レン−クロロトリフルオロエチレン共重合体等が例示さ
れ、これらの配合量は０．１〜１０重量％である。フッ
素系樹脂の配合量が０．１重量％よりも少ない場合に
は、衝撃強度が十分でなくなり、また、１０重量％より
も多くなると、成形性が悪くなる。The fluororesin which is a blending component of the coating composition used in the present invention includes vinylidene fluoride,
Examples thereof include ethylene-tetrafluoroethylene copolymers and ethylene-chlorotrifluoroethylene copolymers, and the blending amount thereof is 0.1 to 10% by weight. When the content of the fluorine-based resin is less than 0.1% by weight, the impact strength is insufficient, and when it is more than 10% by weight, the moldability is deteriorated.
【００１５】本発明において使用する被覆組成物の配合
成分である架橋重合体は、ビニル芳香族単量体５０〜９
０重量％、Ｃ1-13アルキル基を有するアクリル酸アルキ
ルエステルまたはメタクリル酸アルキルエステル１０〜
５０重量％およびその他のモノエチレン性不飽和単量体
０〜４０重量％から成る非架橋性単量体１００重量部と
二重結合を２個以上有する架橋性単量体０．５〜５重量
部から成る混合単量体を懸濁重合することによって得ら
れる。The cross-linked polymer, which is a blending component of the coating composition used in the present invention, is a vinyl aromatic monomer 50-9.
0% by weight, C 1-13 alkyl group-containing acrylic acid alkyl ester or methacrylic acid alkyl ester 10-
100 parts by weight of a non-crosslinkable monomer consisting of 50% by weight and 0 to 40% by weight of another monoethylenically unsaturated monomer and 0.5 to 5 parts by weight of a crosslinkable monomer having two or more double bonds. It is obtained by suspension polymerization of a mixed monomer consisting of parts.
【００１６】非架橋性単量体であるビニル芳香族単量体
としては、スチレン、ビニルトルエン、α−メチルスチ
レンおよびハロゲン化スチレン等が例示され、アクリル
酸アルキルエステルまたはメタクリル酸アルキルエステ
ルとしては、アクリル酸エチル、アクリル酸ブチル、メ
タクリル酸メチルおよびメタクリル酸エチル等が例示さ
れ、また、その他のモノエチレン性不飽和単量体として
は、メタクリル酸、フマール酸、マレイン酸、塩化ビニ
ル、酢酸ビニルおよびアクリロニトリル等が例示され
る。Examples of the vinyl aromatic monomer which is a non-crosslinking monomer include styrene, vinyltoluene, α-methylstyrene and halogenated styrene, and examples of the acrylic acid alkyl ester or methacrylic acid alkyl ester include Examples thereof include ethyl acrylate, butyl acrylate, methyl methacrylate and ethyl methacrylate, and other monoethylenically unsaturated monomers include methacrylic acid, fumaric acid, maleic acid, vinyl chloride, vinyl acetate and Acrylonitrile and the like are exemplified.
【００１７】二重結合を２個以上有する架橋性単量体と
しては、アリルメタクリレート、トリアリルシアヌレー
ト、エチレングリコールジメタクリレート、プロピレン
グリコールジアリルエーテルおよびジビニルベンゼン等
が例示される。架橋性単量体の使用量は、上記の非架橋
性単量体１００重量部に対して０．５〜５重量部、好ま
しくは１．５〜４重量部であり、０．５重量部よりも少
ない場合には、架橋性単量体を添加してもその効果がな
く、また、５重量部よりも多くなると、流動性が下が
る。Examples of the crosslinkable monomer having two or more double bonds include allyl methacrylate, triallyl cyanurate, ethylene glycol dimethacrylate, propylene glycol diallyl ether and divinylbenzene. The amount of the crosslinkable monomer used is 0.5 to 5 parts by weight, preferably 1.5 to 4 parts by weight, based on 100 parts by weight of the above-mentioned non-crosslinkable monomer. If it is too small, the effect will not be obtained even if the crosslinkable monomer is added, and if it exceeds 5 parts by weight, the fluidity will decrease.
【００１８】架橋重合体は、水性媒体中において、上記
の所定量の非架橋性単量体と架橋性単量体を、通常は懸
濁安定剤(例えば、ポリビニルアルコール、ポリアクリ
ル酸塩、カルボキシメチルセルロース、硫酸バリウムま
たは炭酸マグネシウム等)の存在下において、重合開始
剤(例えば、ベンゾイルパーオキシド、ラウロイルパー
オキシドまたはアゾビスイソブチロニトリル等)と共に
懸濁重合することによって調製される。この場合、重合
度調整剤(例えば、n−オクチルメルカプタンまたはt−
ドデシルメルカプタン等)を用いて分子量分布を調整し
てもよい。The crosslinked polymer is a suspension stabilizer (for example, polyvinyl alcohol, polyacrylic acid salt, carboxy, etc.) containing the above-mentioned predetermined amount of non-crosslinkable monomer and crosslinkable monomer in an aqueous medium. It is prepared by suspension polymerization with a polymerization initiator (eg, benzoyl peroxide, lauroyl peroxide or azobisisobutyronitrile) in the presence of methyl cellulose, barium sulfate or magnesium carbonate). In this case, a polymerization degree adjusting agent (for example, n-octyl mercaptan or t-
The molecular weight distribution may be adjusted using dodecyl mercaptan etc.).
【００１９】本発明に用いる架橋重合体の平均粒径は３
５〜５００μであり、該粒径が３５μよりも小さくなる
と、流動性が下がり、また、５００μよりも大きくなる
と、同じく流動性がおちる。The average particle size of the crosslinked polymer used in the present invention is 3
When the particle size is smaller than 35 μ, the fluidity is lowered, and when it is larger than 500 μ, the fluidity is similarly reduced.
【００２０】上述の被覆組成物は、従来から押出成形
体、例えば、住宅用外装材等として汎用されている樹脂
(例えば、ポリ塩化ビニル樹脂、ポリエチレン樹脂、ポ
リプロピレン樹脂、ポリスチレン樹脂、スチレン・アク
リロニトリル・ブタジエン樹脂およびポリカーボネート
樹脂等)に適当な発泡剤(例えば、重炭酸ナトリウム、ア
ゾジカルボンアミドおよびp,p'−オキシ−ビス(ベンゼ
ンスルホニルヒドラジド)等)を配合した基材と共に、常
套の共押出成形機、例えば、図１に示すようなダイスを
備えた共押出成形機を用いて成形することによって、共
押出成形体の表面被覆層を形成する。即ち、図１の矢印
の方向からは、発泡剤を含有するポリ塩化ビニル樹脂等
の基材樹脂を供給すると共に、矢印Ｂに方向からは上述
の被覆組成物を供給し、押出された成形体は、通常は、
サイザーを用いて冷却する。発泡樹脂基材と被覆組成物
の供給速度は特に限定的ではないが、通常は、それぞれ
１５〜１５０kg／Ｈおよび１．５〜１５kg／Ｈである。
この場合、共押出成形は非常に円滑におこなわれ、該被
覆層は優れた耐候性、耐衝撃性、耐水分白化性および耐
薬品性等の特性を示す。該被覆層の厚さは特に限定的で
はないが、通常は１００〜４００μｍである。The above-mentioned coating composition is a resin which has been generally used as an extruded product such as a housing exterior material.
(E.g., polyvinyl chloride resin, polyethylene resin, polypropylene resin, polystyrene resin, styrene-acrylonitrile-butadiene resin, polycarbonate resin, etc.) suitable foaming agents (e.g., sodium bicarbonate, azodicarbonamide and p, p'-oxy) -Bis (benzenesulfonyl hydrazide) etc.) together with a base material blended with a conventional coextrusion machine, for example, a coextrusion machine equipped with a die as shown in FIG. Form the surface coating layer of the body. That is, a base resin such as a polyvinyl chloride resin containing a foaming agent is supplied from the direction of the arrow in FIG. 1, and the above-mentioned coating composition is supplied from the direction of the arrow B, and an extruded molded product is obtained. Is usually
Cool using a sizer. Although the supply rates of the foamed resin substrate and the coating composition are not particularly limited, they are usually 15 to 150 kg / H and 1.5 to 15 kg / H, respectively.
In this case, the co-extrusion molding is carried out very smoothly, and the coating layer exhibits excellent properties such as weather resistance, impact resistance, moisture whitening resistance and chemical resistance. The thickness of the coating layer is not particularly limited, but is usually 100 to 400 μm.
【００２１】[0021]
【実施例】以下、本発明を実施例によって説明する。 実施例１メタクリル系樹脂組成物の調製 本発明において使用する被覆組成物の一組成物であるメ
タクリル系樹脂組成物は以下のように調製される。スチ
レン２２．８重量％とアクリル酸ブチル７７．２重量％
から成る混合単量体１００重量部とメタクリル酸アリル
１．５重量部との混合物を重合することにより、三元共
重合体を得る。つづいて、当該三元共重合体１００重量
部に対し、メタクリル酸メチル９７重量％およびアクリ
ル酸メチル３重量％から成る単量体７．５重量部を反応
させることによりグラフト共重合体が得られる。さら
に、当該グラフト共重合体３２．５重量％、メタクリル
酸メチル６７．５重量％の割合でブレンドさせることに
よりメタクリル系樹脂組成物が調製される。被覆組成物の調製 本発明に使用する被覆組成物の調製原料として、前記の
メタクリル系樹脂組成物１００重量部に対してブタジエ
ン系ゴム１０重量部配合した樹脂組成物(Ａ)、該メタク
リル系樹脂組成物１００重量部に対してフッ化ビニリデ
ン３重量部配合した樹脂組成物(Ｂ)、および次の配合処
方による懸濁重合することによって製造した粒状の架橋
重合体(平均粒径:約１５０μ)(Ｃ)を使用した。 配合成分 重量部 スチレン ７０ アクリル酸エチル ３０ アリルメタクリレート ２．５ n−オクチルメルカプタン ０．１ ラウロイルパーオキシド ０．５ ポリビニルアルコール ０．５ 水 ２００ 樹脂組成物(Ａ)１００重量部、樹脂組成物(Ｂ)１００重
量部、架橋重合体(Ｃ)２２重量部および顔料１．０重量
部配合することによって、被覆組成物を調製した。EXAMPLES The present invention will be described below with reference to examples. Example 1 Preparation of Methacrylic Resin Composition A methacrylic resin composition, which is one composition of the coating composition used in the present invention, is prepared as follows. Styrene 22.8% by weight and butyl acrylate 77.2% by weight
A terpolymer is obtained by polymerizing a mixture of 100 parts by weight of the mixed monomer consisting of 1.5 parts by weight of allyl methacrylate. Subsequently, with respect to 100 parts by weight of the terpolymer, 7.5 parts by weight of a monomer composed of 97% by weight of methyl methacrylate and 3% by weight of methyl acrylate is reacted to obtain a graft copolymer. . Further, the methacrylic resin composition is prepared by blending the graft copolymer in an amount of 32.5% by weight and methyl methacrylate in an amount of 67.5% by weight. Preparation of coating composition As a raw material for preparing the coating composition used in the present invention, a resin composition (A) in which 10 parts by weight of butadiene rubber is mixed with 100 parts by weight of the methacrylic resin composition, and the methacrylic resin Resin composition (B) in which 3 parts by weight of vinylidene fluoride is added to 100 parts by weight of the composition, and a granular crosslinked polymer produced by suspension polymerization according to the following formulation (average particle size: about 150 μ) (C) was used. Ingredients by weight Styrene 70 Ethyl acrylate 30 Allyl methacrylate 2.5 n-Octyl mercaptan 0.1 Lauroyl peroxide 0.5 Polyvinyl alcohol 0.5 Water 200 Resin composition (A) 100 parts by weight, resin composition (B ) 100 parts by weight, 22 parts by weight of the crosslinked polymer (C) and 1.0 part by weight of the pigment were blended to prepare a coating composition.
【００２２】共押出成形体の製造 常法に従い、図１に示すダイスを備えた共押出成形機を
用いて、図２に示す横断図を有する共押出成形体を製造
した。即ち、図１の矢印Ａの方向からは、重炭酸ナトリ
ウムを１．５重量％配合したポリ塩化ビニル樹脂を供給
する(供給速度:６０ｋｇ／Ｈ)と共に、矢印Ｂの方向か
らは上記被覆組成物を供給し(供給速度:６ｋｇ／Ｈ)、
押出された成形体をサイザーを用いて急冷した後、真空
ボックス内に入れてさらに冷却することによって、図２
に示す横断図を有する共押出成形体を得た。図２におい
て、(１)は樹脂被覆層を示し、(２)はポリ塩化ビニル樹
脂発泡体を示す。 Manufacture of Coextrusion Molded Product A coextrusion molded product having a cross section shown in FIG. 2 was manufactured using a coextrusion molding machine equipped with a die shown in FIG. 1 according to a conventional method. That is, from the direction of arrow A in FIG. 1, a polyvinyl chloride resin containing 1.5% by weight of sodium bicarbonate is supplied (supply rate: 60 kg / H), and from the direction of arrow B, the above coating composition. Is supplied (supply rate: 6 kg / H),
The extruded compact is rapidly cooled using a sizer, and then placed in a vacuum box for further cooling.
A co-extruded product having a cross section shown in FIG. In FIG. 2, (1) shows a resin coating layer, and (2) shows a polyvinyl chloride resin foam.
【００２３】得られた共押出成形体の樹脂被覆層(１)の
耐衝撃性等の特性を次の方法によって評価し、結果を以
下の表１に示す。耐衝撃性 …ＪＩＳ Ｋ７１１１に準拠し、ポリ塩化ビニ
ル樹脂の衝撃値の８０％以上の衝撃値の場合を「○」で評
価し、２０％以下の衝撃値の場合を「×」で評価し、これ
らの中間の場合を「△」で評価した。成形性 …３種類の金型を用いた共押出成形ラインの運
転者にとっての成形体製造の難易さによって、容易に成
形できる場合を「○」で評価し、成形が困難な場合を「×」
で評価し、これらの中間の場合を「△」で評価した。耐候性 …アイスーパー試験機(岩崎電気株式会社製Ｓ
ＵＶ−Ｆ１)を用いて試験し、１５０時間経過後に、表
面状態にほとんど変化がない場合を「○」で評価し、表面
に著しい変化や変形がみられる場合を「×」で評価し、こ
れらの中間の場合を「△」で評価した。耐水分白化性 …沸騰水の液面から約３cm上方に成形体を
３分間保持し、表面状態に変化がない場合を「○」で評価
し、表面に明らかな白化が認められる場合を「×」で評価
し、これらの中間の場合を「△」で評価した。耐薬品性 …家庭用洗剤、シンナーおよびメチレンクロリ
ドを用いて成形体表面を拭いたときに、目視により３種
の薬品に対して変化がない場合を「○」で評価し、１種以
上の薬品に対して明らかな変化が認められる場合を「×」
で評価し、１種以上の薬品に対してわずかな変化が認め
られる場合を「△」で評価した。耐熱性 …７０℃のオーブンに２４時間入れた時の変形を
目視で確認する。変形がない場合を「○」で評価し、著し
い変形がある場合を「×」で評価し、これらの中間の場合
を「△」で評価した。The resin coating layer (1) of the obtained coextrusion molded article was evaluated for properties such as impact resistance by the following methods, and the results are shown in Table 1 below. Impact resistance : In accordance with JIS K7111, an impact value of 80% or more of the polyvinyl chloride resin impact value is evaluated as "○", and an impact value of 20% or less is evaluated as "x", The intermediate case between these was evaluated by "△". Moldability: Due to the difficulty of manufacturing a molded product for the driver of a coextrusion molding line that uses three types of dies, the case where it can be easily molded is evaluated as "○", and the case where molding is difficult is evaluated as "x".
Was evaluated, and the intermediate case between these was evaluated by "△". Weather resistance : Eye super testing machine (S manufactured by Iwasaki Electric Co., Ltd.
UV-F1) was used for the test, and after 150 hours, there was almost no change in the surface condition, which was evaluated as "○", and when significant change or deformation was observed on the surface, as "X". The case of the middle of was evaluated by "(triangle | delta)." Moisture resistance to whitening: A molded product is held for about 3 cm above the surface of boiling water for 3 minutes, and when there is no change in the surface condition, it is evaluated as "○", and when obvious whitening is observed on the surface, it is evaluated as "×". ", And the intermediate case between these was evaluated by" △ ". Chemical resistance: When the surface of the molded product is wiped with household detergent, thinner and methylene chloride, the case where there is no change with respect to the three chemicals is evaluated as "○" and one or more chemicals are evaluated. If there is a clear change in
When a slight change was observed for one or more chemicals, it was evaluated as “Δ”. Heat resistance : Visually confirm the deformation when placed in an oven at 70 ° C for 24 hours. The case where there was no deformation was evaluated as “◯”, the case where there was significant deformation was evaluated as “x”, and the case between these was evaluated as “Δ”.
【００２４】比較例１ 実施例１で使用した樹脂組成物(Ａ)および樹脂組成物
(Ｂ)の基材成分であるメタクリル系樹脂粗製物に顔料
１．０重量％配合した試料を被覆組成物として使用する
以外は、実施例１の場合と同様の手順に従って、共押出
成形体を製造し、該成形体の樹脂被覆層の特性を評価
し、結果を以下の表１に示す。 Comparative Example 1 Resin composition (A) and resin composition used in Example 1
A coextrusion molded article was prepared according to the same procedure as in Example 1 except that a sample prepared by adding 1.0% by weight of pigment to the methacrylic resin crude product as the base component of (B) was used as the coating composition. The characteristics of the resin coating layer of the molded product produced were evaluated, and the results are shown in Table 1 below.
【００２５】比較例２および３ 樹脂組成物(Ａ)(比較例２)または樹脂組成物(Ｂ)(比較
例３)に顔料１．０重量％配合した試料を被覆組成物と
して使用する以外は、実施例１の場合と同様の手順に従
って、共押出成形体を製造し、該成形体の樹脂被覆層の
特性を評価し、結果を以下の表１に示す。 Comparative Examples 2 and 3 A resin composition (A) (Comparative Example 2) or a resin composition (B) (Comparative Example 3) containing 1.0% by weight of a pigment was used as a coating composition. According to the same procedure as in Example 1, a coextrusion molded article was produced, the characteristics of the resin coating layer of the molded article were evaluated, and the results are shown in Table 1 below.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【発明の効果】本発明による共押出成形体は、耐候性、
耐衝撃性および成形性の点において優れているだけでな
く、耐水分白化性、耐薬品性、および耐熱性等の点にお
いても実用上問題がなく、特に住宅用外装材、例えば、
見切り、胴差しおよび化粧柱等として有用である。The coextrusion molded article according to the present invention has weather resistance,
Not only in terms of impact resistance and moldability, but also practically no problem in terms of moisture whitening resistance, chemical resistance, and heat resistance.
It is useful as a parting-out, a glove and a makeup pillar.
【図１】 共押出成形用ダイスの模式的縦断面図であ
る。FIG. 1 is a schematic vertical sectional view of a coextrusion molding die.
【図２】 共押出成形体の模式的横断面図である。FIG. 2 is a schematic cross-sectional view of a coextrusion molded article.
Ａ ポリ塩化ビニル発泡樹脂の供給方向 Ｂ 被覆組成物の供給方向 １ 樹脂被覆層 ２ ポリ塩化ビニル樹脂発泡体 A Polyvinyl chloride foam resin supply direction B Coating composition supply direction 1 Resin coating layer 2 Polyvinyl chloride resin foam
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ２９Ｌ 9:00 4Ｆ (72)発明者 向井 俊晴 大阪府大阪市中央区久太郎町２丁目４番31 号 倉敷紡績株式会社大阪本社内 (72)発明者 横田 克彦 大阪府大阪市中央区久太郎町２丁目４番31 号 倉敷紡績株式会社大阪本社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Reference number within the agency FI Technical display location B29L 9:00 4F (72) Inventor Toshiharu Mukai 2-4-3, Kutaro-cho, Chuo-ku, Osaka-shi, Osaka No. Kurashiki Spinning Co., Ltd. Osaka Main Office (72) Inventor Katsuhiko Yokota 2-4-3 Kutarocho, Chuo-ku, Osaka-shi, Osaka Kurashiki Spinning Co., Ltd. Osaka Main Office
Claims (1)
出成形することによって製造される共押出成形体：(i)
(a)芳香族ビニル単量体とアクリル酸エステルとアクリ
ル酸アリルおよび／またはメタクリル酸アリルとを反応
させて得られる三元共重合弾性体の存在下に、メタクリ
ル酸メチルとこれと共重合可能なビニル単量体またはビ
ニリデン単量体とから成る単量体とを反応させて得られ
るグラフト共重合体、および(b)メタクリル酸メチルと
これと共重合可能なビニル単量体またはビニリデン単量
体とから成る単量体を重合させて得られる重合体を、該
三元共重合弾性体の含有量が５〜５０重量％になるよう
に配合して成るメタクリル系樹脂組成物２０〜７９.８
重量％、 (ii)ブタジエン系ゴム０.１〜４０重量％ (iii)フッ素系樹脂０.１〜１０重量％、および (iv)ビニル芳香族単量体５０〜９０重量％、Ｃ1-13アル
キル基を有するアクリル酸アルキルエステルまたはメタ
クリル酸アルキルエステル１０〜５０重量％およびその
他のモノエチレン性不飽和単量体０〜４０重量％から成
る非架橋性単量体１００重量部と２個以上の二重結合を
有する架橋性単量体０．５〜５重量部から成る混合単量
体を懸濁重合することによって得られる架橋重合体(平
均粒径:３５〜５００μ)２０〜３０重量％を含有する被
覆組成物。1. A coextruded product produced by coextruding the following coating composition with a foamed resin substrate: (i)
(a) Methyl methacrylate can be copolymerized with this in the presence of a ternary copolymer elastic body obtained by reacting an aromatic vinyl monomer, an acrylate ester, and allyl acrylate and / or allyl methacrylate. Graft copolymer obtained by reacting a vinyl monomer or a vinylidene monomer-containing monomer, and (b) methyl methacrylate and a vinyl monomer or vinylidene monomer copolymerizable therewith A methacrylic resin composition 20 to 79. which is obtained by polymerizing a polymer obtained by polymerizing a monomer consisting of a terpolymer and a terpolymer copolymer so that the content of the terpolymer elastomer is 5 to 50% by weight. 8
% By weight, (ii) butadiene rubber 0.1 to 40% by weight (iii) fluorine resin 0.1 to 10% by weight, and (iv) vinyl aromatic monomer 50 to 90% by weight, C 1-13 100 parts by weight of a non-crosslinkable monomer consisting of 10 to 50% by weight of an alkyl acrylate or methacrylic acid alkyl ester having an alkyl group and 0 to 40% by weight of another monoethylenically unsaturated monomer, and 2 or more of them. 20-30% by weight of a crosslinked polymer (average particle size: 35-500μ) obtained by suspension-polymerizing a mixed monomer consisting of 0.5-5 parts by weight of a crosslinkable monomer having a double bond A coating composition containing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4256311A JPH0722954B2 (en) | 1992-09-25 | 1992-09-25 | Coextrusion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4256311A JPH0722954B2 (en) | 1992-09-25 | 1992-09-25 | Coextrusion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06285943A true JPH06285943A (en) | 1994-10-11 |
| JPH0722954B2 JPH0722954B2 (en) | 1995-03-15 |
Family
ID=17290906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4256311A Expired - Fee Related JPH0722954B2 (en) | 1992-09-25 | 1992-09-25 | Coextrusion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0722954B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040024106A (en) * | 2002-09-13 | 2004-03-20 | 영보화학 주식회사 | Composition for Thermoplastic Elastomer Foam and Manufacturing Method of the same |
-
1992
- 1992-09-25 JP JP4256311A patent/JPH0722954B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040024106A (en) * | 2002-09-13 | 2004-03-20 | 영보화학 주식회사 | Composition for Thermoplastic Elastomer Foam and Manufacturing Method of the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0722954B2 (en) | 1995-03-15 |
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