JPH0711031A - Polypropylene resin molded product - Google Patents
Polypropylene resin molded productInfo
- Publication number
- JPH0711031A JPH0711031A JP4359789A JP35978992A JPH0711031A JP H0711031 A JPH0711031 A JP H0711031A JP 4359789 A JP4359789 A JP 4359789A JP 35978992 A JP35978992 A JP 35978992A JP H0711031 A JPH0711031 A JP H0711031A
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene resin
- reactive
- molded product
- ultraviolet absorber
- resin molded
- 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
Links
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、外装用建材などの用途
に好適に使用されるポリプロピレン樹脂成形品に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin molded product that is preferably used for applications such as exterior building materials.
【０００２】[0002]
【従来の技術】従来より、テラスや車庫の屋根材その他
の外装用建材として、ガラス繊維を埋入したポリ塩化ビ
ニル樹脂板やポリカーボネート樹脂板などの樹脂成形品
が使用されている。これらの樹脂板は強度や耐熱性が良
好であるが、廃棄物として安全に焼却しにくく、また、
屋根材などの外装用建材として使用すると、耐紫外線性
に劣るため短期間で劣化しやすいという欠点がある。そ
のため、樹脂板中に紫外線吸収剤を含有させたり、樹脂
板の表面に耐紫外線性の良好なアクリル樹脂フィルムを
ラミネートしたりして、耐紫外線性の向上を図ってい
る。2. Description of the Related Art Conventionally, resin moldings such as polyvinyl chloride resin plates and polycarbonate resin plates in which glass fibers are embedded are used as roofing materials for terraces and garages and other exterior building materials. These resin plates have good strength and heat resistance, but are difficult to safely incinerate as waste, and
When it is used as an exterior building material such as a roofing material, it has a drawback that it is easily deteriorated in a short period of time due to poor ultraviolet resistance. Therefore, the ultraviolet resistance is improved by including an ultraviolet absorber in the resin plate or laminating an acrylic resin film having good ultraviolet resistance on the surface of the resin plate.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、紫外線
吸収剤を含有させた前記の樹脂板は、溶融成形時に紫外
線吸収剤が揮散しやすく、成形後も紫外線吸収剤が徐々
に揮散し続けるため、耐紫外線性を長期間持続させ難い
という問題があり、しかも紫外線吸収剤を約３重量％以
上含有させると、紫外線吸収剤が樹脂板表面に析出して
外観を著しく損なうという問題があった。However, in the above resin plate containing an ultraviolet absorber, the ultraviolet absorber easily volatilizes during melt molding, and the ultraviolet absorber continues to volatilize gradually even after molding, and There is a problem that it is difficult to maintain the ultraviolet property for a long period of time, and further, when the ultraviolet absorber is contained in an amount of about 3% by weight or more, the ultraviolet absorber is deposited on the surface of the resin plate and the appearance is significantly impaired.
【０００４】一方、アクリル樹脂フィルムを表面にラミ
ネートした前記の樹脂板は、両者の相溶性や親和性が十
分でないため、界面での密着性が不安定でアクリル樹脂
フィルムが剥離しやすいという問題があり、気温の変化
による収縮差で割れやすいという問題があった。On the other hand, the above-mentioned resin plate laminated with an acrylic resin film on the surface has insufficient compatibility and affinity with each other, so that the adhesion at the interface is unstable and the acrylic resin film is easily peeled off. However, there was a problem that it was easily broken due to the difference in shrinkage due to changes in temperature.
【０００５】[0005]
【課題を解決するための手段】上記の問題を解決するた
め、第一の発明に係るポリプロピレン樹脂成形品は、ポ
リプロピレン樹脂のポリマー分子に反応型紫外線吸収剤
及び反応型光安定剤のいずれか一方又は双方を反応させ
てあることを要旨とするものであり、また、第二の発明
に係るポリプロピレン樹脂成形品は、ポリプロピレン樹
脂の成形品本体の表面に、反応型紫外線吸収剤及び反応
型光安定剤のいずれか一方又は双方を配合した電子線硬
化型樹脂塗料の硬化塗膜を形成したことを要旨とするも
のである。In order to solve the above-mentioned problems, a polypropylene resin molded article according to the first invention comprises a polymer molecule of polypropylene resin, which is either a reactive ultraviolet absorber or a reactive light stabilizer. Alternatively, both are made to react with each other, and the polypropylene resin molded product according to the second invention has a reactive ultraviolet absorber and a reactive light stabilizer on the surface of the molded product body of polypropylene resin. The gist is to form a cured coating film of an electron beam curable resin coating material containing either one or both of the agents.
【０００６】[0006]
【作用】第一発明のポリプロピレン樹脂成形品のよう
に、反応型紫外線吸収剤や反応型光安定剤をポリプロピ
レン樹脂のポリマー分子に反応させると、この紫外線吸
収剤や光安定剤が側鎖としてポリマー分子に結合し、固
定化される。そのため、反応した紫外線吸収剤や光安定
剤は、揮散することなくポリプロピレン樹脂成形品中に
含有保持され、紫外線吸収剤や光安定剤が成形品の表面
へ移動して析出することはない。従って、このポリプロ
ピレン樹脂成形品は、内部に長期間保有される多量の紫
外線吸収剤によって紫外線が十分に吸収され、光安定剤
によって劣化時に発生するラジカルが十分に捕捉される
ので、長期間に亘って優れた耐紫外線性を発揮し、紫外
線による強度劣化や黄変化を生じることが殆どない。し
かも、紫外線吸収剤や光安定剤が表面に析出しないの
で、長期間に亘って良好な外観を維持できる。また、こ
の成形品は実質的にポリプロピレン樹脂よりなるもので
あるから表面滑性が大であり、低温になっても割れにく
く、成形時や賦形時の保形性も良好である。When the reactive ultraviolet absorber or the reactive light stabilizer is reacted with the polymer molecule of the polypropylene resin like the polypropylene resin molded article of the first invention, the ultraviolet absorber or the light stabilizer forms a polymer as a side chain. It binds to the molecule and is immobilized. Therefore, the reacted ultraviolet absorber or light stabilizer is contained and retained in the polypropylene resin molded product without being volatilized, and the ultraviolet absorber or light stabilizer does not move to the surface of the molded product to be deposited. Therefore, in this polypropylene resin molded product, a large amount of ultraviolet absorber retained inside for a long time sufficiently absorbs ultraviolet rays, and the light stabilizer sufficiently traps radicals generated at the time of deterioration. And exhibits excellent resistance to ultraviolet rays, and hardly causes strength deterioration or yellowing due to ultraviolet rays. Moreover, since no ultraviolet absorber or light stabilizer is deposited on the surface, a good appearance can be maintained for a long period of time. Further, since this molded product is substantially made of polypropylene resin, it has a large surface smoothness, is hard to crack even at low temperatures, and has good shape retention during molding and shaping.
【０００７】一方、第二発明のようにポリプロピレン樹
脂の成形品本体の表面に電子線硬化型樹脂塗料の硬化塗
膜を形成したポリプロピレン樹脂成形品は、該塗膜中に
含まれる反応型紫外線吸収剤や反応型光安定剤が電子線
硬化時に塗料の樹脂成分と反応して固定化されるため、
上記と同様に長期間に亘って優れた耐紫外線性を発揮
し、紫外線による劣化を生じることが殆どない。しか
も、上記塗料に含まれる反応型紫外線吸収剤、反応型光
安定剤、粘度調整用の反応性モノマー等の一部は塗布時
に成形品本体の表層部に浸透するので、電子線照射によ
り塗膜を硬化させると密着性の良い硬化塗膜が形成さ
れ、剥離の恐れは殆どなくなる。また、成形品本体がポ
リプロピレン樹脂よりなるものであるから、低温になっ
ても割れにくく、成形時や賦形時の保形性も良好であ
る。On the other hand, a polypropylene resin molded article having a cured coating film of an electron beam curable resin paint formed on the surface of a polypropylene resin molded article body as in the second invention, has a reaction type ultraviolet absorption contained in the coating film. Agent and reactive light stabilizer are fixed by reacting with the resin component of the paint during electron beam curing.
Similar to the above, it exhibits excellent ultraviolet resistance over a long period of time and hardly deteriorates due to ultraviolet rays. Moreover, some of the reactive ultraviolet absorbers, reactive light stabilizers, reactive monomers for viscosity adjustment, etc., contained in the above-mentioned paint penetrate into the surface layer of the molded article body during coating, so coating by electron beam irradiation When cured, a cured coating film with good adhesion is formed, and there is almost no risk of peeling. In addition, since the molded product body is made of polypropylene resin, it does not easily crack even at low temperatures, and has good shape retention during molding and shaping.
【０００８】[0008]
【実施例】以下、図面を参照して本発明の実施例を説明
する。Embodiments of the present invention will be described below with reference to the drawings.
【０００９】図１は第一発明の一実施例の断面図で、平
板状に溶融成形したポリプロピレン樹脂成形品１を示し
ている。成形品１の形状は、実施例のような平板状の
他、波板状、シート状、管状、異形状など、所望の形状
とすることができる。FIG. 1 is a cross-sectional view of an embodiment of the first invention, showing a polypropylene resin molded product 1 melt-molded into a flat plate shape. The shape of the molded product 1 can be a desired shape such as a corrugated plate shape, a sheet shape, a tubular shape, or an irregular shape other than the flat plate shape as in the embodiment.
【００１０】この成形品１のポリプロピレン樹脂は、反
応型紫外線吸収剤及び反応型光安定剤のいずれか一方又
は双方を反応させることにより、そのポリマー分子に紫
外線吸収剤や光安定剤を側鎖として結合させ、固定化し
たものである。このように固定化されていると紫外線吸
収剤や光安定剤が揮散せず、また、その含有量が多くて
も成形品１の表面へ移動して析出することはない。従っ
て、上記のようなポリプロピレン樹脂で成形した成形品
１は、その内部に長期間保有される多量の紫外線吸収剤
によって紫外線が十分に吸収され、また光安定剤によっ
て劣化時に発生するラジカルが十分捕捉されるので、長
期間に亘って優れた耐紫外線性を発揮し、紫外線による
強度劣化や黄変化を生じることが殆どない。The polypropylene resin of this molded article 1 is prepared by reacting either one or both of a reactive ultraviolet absorber and a reactive light stabilizer so that the polymer molecule has the ultraviolet absorber and the light stabilizer as a side chain. It is bound and immobilized. When immobilized in this way, the ultraviolet absorber and the light stabilizer do not volatilize, and even if the content is large, they do not migrate to the surface of the molded article 1 and deposit. Therefore, the molded article 1 molded from the polypropylene resin as described above is sufficiently absorbed by a large amount of ultraviolet absorber held therein for a long time, and the light stabilizer sufficiently traps radicals generated at the time of deterioration. Therefore, it exhibits excellent ultraviolet resistance over a long period of time and hardly causes strength deterioration or yellowing due to ultraviolet rays.
【００１１】反応型紫外線吸収剤としては、分子中に不
飽和結合を一つ以上有するベンゾフェノン系又はベンゾ
トリアゾール系の紫外線吸収剤、例えば２−ヒドロキシ
−４−（２′−メタクリロイルオキシエトキシ）ベンゾ
フェノン、２−ヒドロキシ−４−（２′−アクリロイル
オキシエトキシ）ベンゾフェノン、２−（２′−ヒドロ
キシ−３′−アリル−５′−ｔ−ブチルフェニル）ベン
ゾトリアゾール、２−（２′−ヒドロキシ−３′−アリ
ル−５′−ｔ−オクチルフェニル）ベンゾトリアゾー
ル、２−（２′−ヒドロキシ−３′−イソプロペニル−
５′−ｔ−ブチルフェニル）ベンゾトリアゾール、２−
（２′−ヒドロキシ−３′−イソプロペニル−５′−ｔ
−オクチルフェニル）ベンゾトリアゾール、２−（２′
−アクリロイルオキシ−５′−メチル）ベンゾトリアゾ
ールなどが使用される。As the reactive ultraviolet absorber, a benzophenone-based or benzotriazole-based ultraviolet absorber having at least one unsaturated bond in the molecule, for example, 2-hydroxy-4- (2'-methacryloyloxyethoxy) benzophenone, 2-hydroxy-4- (2'-acryloyloxyethoxy) benzophenone, 2- (2'-hydroxy-3'-allyl-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 '-Allyl-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3'-isopropenyl-
5'-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3'-isopropenyl-5'-t
-Octylphenyl) benzotriazole, 2- (2 '
-Acryloyloxy-5'-methyl) benzotriazole and the like are used.
【００１２】また、反応型光安定剤としては、例えば
１，２，２，６，６−ペンタメチル−４−ピペリジルメ
タクリレート、１，２，２，６，６−ペンタメチル−４
−ピペリジルアクリレート、２，２，６，６−テトラメ
チル−４−ピペリジルメタクリレート、２，２，６，６
−テトラメチル−４−ピペリジルアクリレート等が使用
される。Examples of reactive light stabilizers include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4.
-Piperidyl acrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6
-Tetramethyl-4-piperidyl acrylate etc. are used.
【００１３】これらの反応型紫外線吸収剤や反応型光安
定剤は、ラジカル反応開始剤の作用によりポリプロピレ
ン樹脂のポリマー分子中に発生したラジカルに側鎖とし
て結合され固定化されるので、成形品１の表面へ移動し
て析出することはない。従って、これらの反応型紫外線
吸収剤や反応型光安定剤は、ポリプロピレン樹脂に対
し、それぞれ単独で又は合計して約１０重量％程度まで
配合可能である。しかし、あまり多量に配合しても耐紫
外線性がそれほど変わらず、未反応の紫外線吸収剤や光
安定剤が増えるだけであるから、ポリプロピレン樹脂に
対してそれぞれ単独で又は合計して０．０１〜１０重量
％、好ましくは０．０５〜５重量％程度配合して反応さ
せるのがよい。この程度の配合量とすれば、一部揮散す
るものがあっても優れた耐紫外線性を長期間に亘って発
揮するポリプロピレン樹脂成形品１を得ることができ
る。These reactive ultraviolet absorbers and reactive light stabilizers are bonded as side chains to the radicals generated in the polymer molecules of the polypropylene resin by the action of the radical reaction initiator, and are thus fixed. It does not move to the surface of and precipitate. Therefore, these reactive ultraviolet absorbers and reactive light stabilizers can be added to the polypropylene resin either individually or in total up to about 10% by weight. However, even if blended in a too large amount, the UV resistance does not change so much, and only unreacted UV absorbers and light stabilizers increase, so the polypropylene resin alone or in a total amount of 0.01- It is advisable to add about 10% by weight, preferably about 0.05 to 5% by weight, and to react them. With such a blending amount, it is possible to obtain a polypropylene resin molded article 1 that exhibits excellent ultraviolet resistance over a long period of time even if some of it volatilizes.
【００１４】また、この成形品１は上記のようなポリプ
ロピレン樹脂より成るものであるから、従来の合成樹脂
板等に比べると表面の滑性が大きく、低温でも割れにく
い。従って、例えば積雪地域の屋根材等として使用する
と、雪下ろし作業がし易くなり、雪の重み等で破損する
ことも少なくなる。Further, since the molded product 1 is made of the polypropylene resin as described above, it has a larger surface slipperiness than a conventional synthetic resin plate or the like and is less likely to crack even at low temperatures. Therefore, when it is used as a roofing material in a snowy area, for example, it is easy to remove snow, and damage due to the weight of snow is reduced.
【００１５】図２は上記ポリプロピレン樹脂成形品１の
製造法の一例を示す説明図である。これによれば、予め
ポリプロピレン樹脂のペレットにラジカル反応開始剤と
反応型紫外線吸収剤及び／又は反応型光安定剤をドライ
ブレンドし、このブレンド物２を押出成形機３のホッパ
ー３ａから投入して、成形機内部でポリプロピレン樹脂
の融点以上（但し熱分解温度以下）に加熱しながら１〜
１５分程度溶融混練し、先端の押出口３ｂから板状に押
出す。そして、押出した板状成形物１ａを上下の冷却ロ
ール４，４で冷却してから、ベルトコンベア５で切断機
６まで搬送し、所定の長さに切断して平板状のポリプロ
ピレン樹脂成形品１を製造する。尚、ラジカル反応開始
剤としては、過酸化ベンゾイル、アゾ−ｂｉｓ−イソブ
チロニトリル、ｔ−ブチルヒドロパーオキサイド、２，
５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘ
キサン、オクタノイルパーオキサイド等が使用される。FIG. 2 is an explanatory view showing an example of a method of manufacturing the polypropylene resin molded product 1. According to this, a radical reaction initiator and a reactive ultraviolet absorber and / or a reactive light stabilizer are dry-blended in advance with polypropylene resin pellets, and the blend 2 is charged from the hopper 3a of the extrusion molding machine 3. While heating above the melting point of the polypropylene resin (but below the thermal decomposition temperature) inside the molding machine, 1 to
The mixture is melted and kneaded for about 15 minutes, and extruded in a plate shape from the extruding port 3b at the tip. Then, the extruded plate-shaped molded product 1a is cooled by the upper and lower cooling rolls 4 and 4, and then conveyed to the cutting machine 6 by the belt conveyor 5 and cut into a predetermined length to obtain a flat plate-shaped polypropylene resin molded product 1 To manufacture. As the radical reaction initiator, benzoyl peroxide, azo-bis-isobutyronitrile, t-butyl hydroperoxide, 2,
5-Dimethyl-2,5-di (t-butylperoxy) hexane, octanoyl peroxide, etc. are used.
【００１６】上記のようにブレンド物２を成形機３の内
部で溶融混練すると、ラジカル反応によってポリプロピ
レン樹脂のポリマー分子に反応型紫外線吸収剤や反応型
光安定剤が側鎖として結合して固定化されるので、既述
したように長期にわたって耐紫外線性の良好なポリプロ
ピレン樹脂成形品１を得ることができる。When the blend 2 is melt-kneaded inside the molding machine 3 as described above, the reactive ultraviolet absorber or the reactive light stabilizer is bonded as a side chain to the polymer molecules of the polypropylene resin by a radical reaction and immobilized. Therefore, as described above, the polypropylene resin molded product 1 having good ultraviolet resistance can be obtained for a long period of time.
【００１７】この製造法では、押出成形機３の内部で反
応型紫外線吸収剤等をラジカル反応させているが、予め
反応型紫外線吸収剤等をラジカル反応させたポリプロピ
レン樹脂のペレットを準備し、このペレットを押出成形
機３に投入して押出成形してもよい。また、この製造法
では、反応型紫外線吸収剤等を反応させたポリプロピレ
ン樹脂を単層で押出成形しているが、例えば共押出成形
機を用いて、反応型紫外線吸収剤等を反応させたポリプ
ロピレン樹脂を上層とし、該上層よりも反応型紫外線吸
収剤等が少ないか又は全く含まないポリプロピレン樹脂
を中間層又は下層として共押出成形すれば、表面に紫外
線吸収剤等を反応させた耐紫外線性の良好なポリプロピ
レン樹脂層を有する二層ないし三層構造のポリプロピレ
ン樹脂成形品を製造することもできる。In this manufacturing method, the reactive ultraviolet absorber or the like is radically reacted inside the extruder 3. However, polypropylene resin pellets are prepared by radically reacting the reactive ultraviolet absorber or the like in advance. The pellets may be put into the extrusion molding machine 3 and extrusion-molded. In addition, in this production method, a polypropylene resin obtained by reacting a reactive ultraviolet absorber or the like is extruded in a single layer. For example, a polypropylene obtained by reacting a reactive ultraviolet absorber with a coextrusion molding machine is used. If a resin is used as an upper layer, and a polypropylene resin having less or no reactive UV absorber or the like than the upper layer is coextruded as an intermediate layer or a lower layer, the UV resistance of the ultraviolet absorber reacted with the surface can be improved. It is also possible to produce a polypropylene resin molded product having a two-layer or three-layer structure having a good polypropylene resin layer.
【００１８】図３は第二発明の一実施例を示す断面図
で、このものは一般のポリプロピレン樹脂で成形した成
形品本体１０の表面に、前記の反応型紫外線吸収剤及び
反応型光安定剤のいずれか一方又は双方を配合した電子
線硬化型樹脂塗料を塗布し、その塗膜を電子線照射によ
り硬化させて硬化塗膜７を形成したものである。この硬
化塗膜７は成形品本体１の両面に形成してもよい。FIG. 3 is a cross-sectional view showing an embodiment of the second invention, in which the above-mentioned reactive ultraviolet absorber and reactive light stabilizer are formed on the surface of a molded article body 10 molded from a general polypropylene resin. An electron beam curable resin coating composition containing one or both of the above is applied, and the coating film is cured by electron beam irradiation to form a cured coating film 7. The cured coating film 7 may be formed on both sides of the molded article body 1.
【００１９】硬化塗膜７の厚みは５μｍ以上とすること
が肝要で、これより薄くなると、硬化塗膜に含まれる反
応型紫外線吸収剤や反応型光安定剤の含有量が不足して
十分な耐紫外線性を発揮し難くなり、また厚みの制御も
難しくなる。硬化塗膜の厚みについては上限はないが、
あまり厚くしても耐紫外線性がそれほど変わらず、塗料
の無駄使いとなるので、最大限でも１００μｍ程度まで
とするのがよい。好ましい厚み範囲は２０〜５０μｍ程
度であり、この程度の厚みがあれば優れた耐紫外線性を
発揮することができる。It is important that the thickness of the cured coating film 7 is 5 μm or more. If the thickness is smaller than this, the content of the reactive ultraviolet absorber or the reactive light stabilizer contained in the cured coating film is insufficient and sufficient. It becomes difficult to exert ultraviolet resistance, and it becomes difficult to control the thickness. There is no upper limit on the thickness of the cured coating film,
Even if it is made too thick, the UV resistance does not change so much and the paint is wasted. Therefore, it is preferable to set the maximum thickness to about 100 μm. A preferable thickness range is about 20 to 50 μm, and if the thickness is in this range, excellent ultraviolet resistance can be exhibited.
【００２０】硬化塗膜７の形成に用いる電子線硬化型樹
脂塗料は、（メタ）アクリロイル基を含んだポリエステ
ル（メタ）アクリレート、エポキシ（メタ）アクリレー
ト、ポリウレタン（メタ）アクリレートなどのアクリル
変性樹脂のオリゴマー又はプレポリマーをベースレジン
とし、これに粘度調整用の反応性モノマーと反応型紫外
線吸収剤や反応型光安定剤を混合したものであって、そ
の粘度が１０００ｃｐｓ以下、好ましくは１０〜５００
ｃｐｓの範囲に調整されたものが使用される。塗料の粘
度が１０００ｃｐｓを越えると塗布特性や延展性が低下
し、上記厚みの塗膜を形成しにくくなるからである。The electron beam curable resin coating material used for forming the cured coating film 7 is an acrylic modified resin such as polyester (meth) acrylate containing a (meth) acryloyl group, epoxy (meth) acrylate, polyurethane (meth) acrylate. An oligomer or a prepolymer as a base resin, which is mixed with a reactive monomer for viscosity adjustment and a reactive ultraviolet absorber or a reactive light stabilizer, the viscosity of which is 1000 cps or less, preferably 10 to 500.
The one adjusted to the cps range is used. This is because when the viscosity of the coating material exceeds 1000 cps, the coating characteristics and spreadability deteriorate and it becomes difficult to form a coating film of the above thickness.
【００２１】粘度調整用の反応性モノマーとしては、例
えば官能基数が１のアクリル酸、アクリル酸エチル、ア
クリル酸ブチルや、官能基数が２のヘキサンジオールジ
アクリレート、トリプロピレングリコールジアクリレー
ト、ジエチレングリコールジアクリレートや、官能基数
が３のトリメチロールプロパントリアクリレート、グリ
セロールプロポキシトリアクリレート等のアクリレート
系モノマーが使用される。これらの反応性モノマーは、
上記粘度の塗料が得られるように適量配合すればよい。As the reactive monomer for adjusting the viscosity, for example, acrylic acid having a functional group of 1, ethyl acrylate, butyl acrylate, hexanediol diacrylate having a functional group of 2, tripropylene glycol diacrylate, diethylene glycol diacrylate. Alternatively, an acrylate-based monomer having a functional group number of 3 such as trimethylolpropane triacrylate and glycerol propoxytriacrylate is used. These reactive monomers are
It may be added in an appropriate amount so as to obtain a paint having the above viscosity.
【００２２】電子線硬化型樹脂塗料に含まれる反応型紫
外線吸収剤や反応型光安定剤は、既述したように塗料硬
化時に塗料中の樹脂成分、即ち上記のベースレジンや反
応性モノマーと反応して固定化されるため、配合量が多
くても塗膜表面に移行して析出することはない。従っ
て、反応型紫外線吸収剤や反応型光安定剤は、塗料の樹
脂成分に対し、それぞれ単独で又は合計して約５０重量
％程度まで配合可能である。しかし、あまり多量に配合
しても耐紫外線性がそれほど変わらず、未反応の紫外線
吸収剤や光安定剤が増えるだけであるから、樹脂成分に
対してそれぞれ単独で又は合計して１〜３０重量％、好
ましくは２．５〜２０重量％程度配合するのがよい。こ
の程度の配合量とすれば、優れた耐紫外線性を長期間に
亘って発揮することができる。As described above, the reactive ultraviolet absorber and reactive light stabilizer contained in the electron beam curable resin coating material react with the resin component in the coating material, that is, the above-mentioned base resin and reactive monomer when the coating material is cured. Therefore, even if the blending amount is large, it does not migrate to the surface of the coating film and precipitate. Therefore, the reactive ultraviolet absorber and the reactive light stabilizer can be added to the resin component of the coating material individually or in a total amount of up to about 50% by weight. However, even if added in a large amount, the UV resistance does not change so much, and only unreacted UV absorbers and light stabilizers increase. %, Preferably about 2.5 to 20% by weight. With such a blending amount, excellent UV resistance can be exhibited for a long period of time.
【００２３】また、この塗料は電子線硬化型樹脂塗料で
あるから、光の透過を阻害するフィラーであっても電子
線が透過するものであれば、塗料中に配合することがで
きる。従って、必要とあらばガラスマイクロバルーンや
炭酸カルシウムなどのフィラーを塗料中の樹脂成分に対
して３〜５０重量％程度配合し、スリガラスのような半
透明の硬化塗膜を形成することもできる。Further, since this coating material is an electron beam curable resin coating material, even if it is a filler which obstructs the transmission of light, it can be incorporated into the coating material as long as it can transmit the electron beam. Therefore, if necessary, a filler such as glass microballoons or calcium carbonate may be blended in an amount of about 3 to 50% by weight with respect to the resin component in the coating material to form a translucent cured coating film such as frosted glass.
【００２４】このような硬化塗膜７をポリプロピレン樹
脂の成形品本体１０の表面に有する成形品は、該成形品
本体１０の表面に前記の電子線硬化型樹脂塗料を例えば
バーコーター等で塗布し、これをコンベア等で移動させ
ながら電子線加速機で電子線を照射して該塗膜を硬化さ
せることにより、効率良く製造することができる。電子
線照射の条件は塗膜の厚みや成分によって変化するが、
例えば塗膜の厚みが２０〜３０μｍである場合には、加
速電圧を１００〜３００ＫＶ程度、照射量を３〜１５Ｍ
ｒａｄ程度に設定するのが望ましい。加速電圧が１００
ＫＶより低いと、塗膜の表面は反応、硬化するが、塗膜
内部の硬化が不十分となり、逆に加速電圧を上げ過ぎる
と、電子線によってポリプロピレン樹脂成形品１０が劣
化するなどの不都合を生じるからである。また、照射量
が少ない場合も塗膜の硬化が不十分となり、例えば３Ｍ
ｒａｄ以下の照射量では塗膜が殆ど硬化しない。A molded article having such a cured coating film 7 on the surface of a molded article body 10 made of polypropylene resin is obtained by applying the above-mentioned electron beam-curable resin coating material to the surface of the molded article body 10 with a bar coater or the like. The coating can be efficiently produced by irradiating an electron beam with an electron beam accelerator to cure the coating film while moving it with a conveyor or the like. The electron beam irradiation conditions vary depending on the thickness and composition of the coating film,
For example, when the thickness of the coating film is 20 to 30 μm, the acceleration voltage is about 100 to 300 KV, and the irradiation amount is 3 to 15 M.
It is desirable to set it to about rad. Accelerating voltage is 100
If it is lower than KV, the surface of the coating film reacts and cures, but the curing inside the coating film becomes insufficient. Conversely, if the accelerating voltage is increased too much, the polypropylene resin molded article 10 may be deteriorated by the electron beam. Because it will occur. In addition, even if the irradiation amount is small, the curing of the coating film becomes insufficient.
The coating hardly cures at an irradiation dose of rad or less.
【００２５】このように電子線照射により塗膜を硬化さ
せると、塗膜中の反応型紫外線吸収剤や反応型光安定剤
が樹脂成分（前記のベースレジンや反応性モノマー）と
反応して固定化され、硬化塗膜７の表面からの揮散や析
出を生じることなく長期間に亘って塗膜中に含有保持さ
れる。しかも、反応性モノマー、反応型紫外線吸収剤、
反応性光安定剤などの一部が塗布時にポリプロピレン樹
脂の成形品本体１０の表層部に浸透するので、耐剥離強
度（密着性）の大きい硬化塗膜７が形成されることにな
る。従って、このような硬化塗膜７を成形品本体１０の
表面に形成した成形品は、硬化塗膜７の剥離を生じるこ
とが殆どなく、しかも硬化塗膜７中に長期間保有される
多量の紫外線吸収剤によって紫外線が十分に吸収され、
また光安定剤によって劣化時のラジカルが十分に捕捉さ
れるため、長期間に亘って優れた耐紫外線性を発揮し、
強度劣化や黄変化を生じることが殆どない。When the coating film is cured by electron beam irradiation in this way, the reactive ultraviolet absorber or reactive light stabilizer in the coating film reacts with the resin component (the above-mentioned base resin or reactive monomer) to fix it. And is contained in the coating film for a long period of time without being volatilized or deposited from the surface of the cured coating film 7. Moreover, reactive monomers, reactive UV absorbers,
Since a part of the reactive light stabilizer and the like penetrates into the surface layer of the polypropylene resin molded article body 10 during application, a cured coating film 7 having high peel resistance (adhesion) is formed. Therefore, a molded product in which such a cured coating film 7 is formed on the surface of the molded product body 10 hardly causes peeling of the cured coating film 7, and a large amount of the cured coating film 7 retains for a long time. UV light is fully absorbed by the UV absorber,
In addition, since the light stabilizer sufficiently captures radicals at the time of deterioration, it exhibits excellent UV resistance for a long period of time.
Almost no strength deterioration or yellowing occurs.
【００２６】図１に例示した第一発明のポリプロピレン
樹脂成形品１は、その内部にガラス繊維ネットやガラス
繊維マット等の補強繊維を埋入してもよい。このように
補強繊維を埋入すると、成形品１の剛性や耐衝撃強度が
向上し、成形時や賦形時の保形性も良好となる。補強繊
維を埋入した成形品１を製造する場合は、例えば図４に
示すように補強繊維８を供給ロール９から連続供給する
と共に、両側の押出成形機３，３から反応型紫外線吸収
剤等を反応させたポリプロピレン樹脂１ｂ，１ｂを連続
して押出し、これを一対のロール４，４で両側から挟圧
して融着一体化すればよい。同様に、図３に例示した第
二発明のポリプロピレン樹脂成形品も、成形品本体１０
の内部に補強繊維を埋入してもよい。The polypropylene resin molded article 1 of the first invention illustrated in FIG. 1 may have reinforcing fibers such as a glass fiber net or a glass fiber mat embedded therein. By embedding the reinforcing fibers in this way, the rigidity and impact resistance of the molded product 1 are improved, and the shape retention during molding and shaping is also improved. When manufacturing the molded article 1 in which the reinforcing fibers are embedded, for example, as shown in FIG. 4, the reinforcing fibers 8 are continuously supplied from the supply rolls 9 and, at the same time, the reactive ultraviolet absorbers or the like are supplied from the extruders 3 and 3 on both sides. The polypropylene resins 1b and 1b which have reacted with each other may be continuously extruded, and the polypropylene resins 1b and 1b may be fused and integrated by being pinched from both sides by a pair of rolls 4 and 4. Similarly, the polypropylene resin molded product of the second invention illustrated in FIG.
Reinforcing fibers may be embedded inside.
【００２７】次に、具体的な実施例と比較例を説明す
る。 （実施例１）Next, concrete examples and comparative examples will be described. (Example 1)
【００２８】ポリプロピレン樹脂１００重量部に対し、
反応型紫外線吸収剤として２−ヒドロキシ−４−（２′
−メタクリロイルオキシエトキシ）ベンゾフェノンを
１．５重量部と、ラジカル反応開始剤として過酸化ベン
ゾイルを１．０重量部加えてドライブレンドした。この
ブレンド物を押出成形機に投入し、２３０℃に加熱して
溶融混練しながら５分間反応させ、シート状に押出して
ポリプロピレン樹脂成形品を製造した。そして、この成
形品を切断して試験片（５０×１００×１ｍｍ）を作成
した。With respect to 100 parts by weight of polypropylene resin,
2-hydroxy-4- (2 ') as a reactive ultraviolet absorber
1.5 parts by weight of -methacryloyloxyethoxy) benzophenone and 1.0 part by weight of benzoyl peroxide as a radical reaction initiator were added and dry blended. The blended product was put into an extrusion molding machine, heated to 230 ° C., reacted for 5 minutes while being melt-kneaded, and extruded into a sheet to produce a polypropylene resin molded product. Then, this molded product was cut to prepare a test piece (50 × 100 × 1 mm).
【００２９】この試験片について促進耐候性試験を行
い、照射時間と黄変度（ΔＹＩ）、紫外線吸収剤の残存
率との関係を調べた。その結果を表１に示す。尚、促進
耐候試験はキセノンウェザオメーター（アトラス社製）
を用いて１００ｈｒ，５００ｈｒ，１０００ｈｒ照射に
よる促進試験を行い、ΔＹＩはΣ９０カラーメジャーリ
ングシステム（日本電色株式会社製）により測定して求
めたものである。また、残存率は、可視紫外分光光度計
ＵＶ−３１００（株式会社島津製作所製）を用いて、そ
れぞれの照射時間における試験片のキャストフィルムの
紫外線吸光度を測定し、それぞれの紫外線吸収剤の最大
吸収波長の吸光度変化を、照射時間０ｈｒのときの残存
率を１００として計算した値である。An accelerated weathering test was conducted on this test piece to examine the relationship between the irradiation time, the degree of yellowing (ΔYI), and the residual rate of the ultraviolet absorber. The results are shown in Table 1. In addition, the accelerated weather resistance test is a xenon weatherometer (made by Atlas).
The accelerated test by irradiation with 100 hr, 500 hr, and 1000 hr was performed, and ΔYI was obtained by measuring with a Σ90 color measuring system (manufactured by Nippon Denshoku Co., Ltd.). In addition, the residual rate is determined by measuring the ultraviolet absorption of the cast film of the test piece at each irradiation time using a visible ultraviolet spectrophotometer UV-3100 (manufactured by Shimadzu Corporation), and determining the maximum absorption of each ultraviolet absorber. It is a value calculated by calculating the change in the absorbance of the wavelength with the residual rate as 100 when the irradiation time is 0 hr.
【００３０】また、この試験片について、ポリマー分子
と反応して結合している紫外線吸収剤の割合（反応率）
を以下の測定方法で求めたところ、反応率は約９．０×
１０-2モル％であった。 （反応率の測定方法）Further, in this test piece, the ratio (reaction rate) of the ultraviolet absorber which has reacted with the polymer molecules and bound
Was determined by the following measuring method, the reaction rate was about 9.0 ×
It was 10 -2 mol%. (Method of measuring reaction rate)
【００３１】試験片をアセトンで１０時間、ソックスレ
ー抽出を行なって未反応の反応型紫外線吸収剤又は反応
型光安定剤を除去し、抽出後の試験片について赤外分光
光度計（ＦＴ−ＩＲ）を用いて反応率の測定を行う。こ
こでポリプロピレンの１ユニットを１モルとするので、
１モル＝４２として反応型紫外線吸収剤との反応率をモ
ル％で示す。The test piece was subjected to Soxhlet extraction with acetone for 10 hours to remove the unreacted reactive ultraviolet absorber or reactive light stabilizer, and the extracted test piece was subjected to an infrared spectrophotometer (FT-IR). Is used to measure the reaction rate. Since 1 unit of polypropylene is 1 mol here,
When 1 mol = 42, the reaction rate with the reactive ultraviolet absorber is shown in mol%.
【００３２】実施例１において反応型紫外線吸収剤の２
−ヒドロキシ−４−（２′−メタクリロイルオキシエト
キシ）ベンゾフェノンを反応させたポリプロピレンは、
図５に示すように、１７２０ｃｍ-1付近にポリプロピレ
ンには吸収のないエステル（Ｃ＝Ｏ）の伸縮振動のピー
ク（Ａ）が見られる。このピークと８４０ｃｍ-1付近に
ある主鎖のＣ−Ｈの変角振動のピーク（Ｂ）とのピーク
比（Ａ／Ｂ）より、反応型紫外線吸収剤のポリプロピレ
ンに対する反応率を求める。その他の反応型紫外線吸収
剤の反応率を求めるときも同様である。その場合、予め
ポリプロピレンとそれぞれの反応型紫外線吸収剤数種類
の配合をつくり、それぞれのキャストフィルムを作成す
る。そして各フィルムを赤外分光光度計を用いて測定を
行い、縦軸に反応率、横軸にピーク比（Ａ／Ｂ）をとっ
た検量線を作成し、これに基づいて試験片のキャストフ
ィルムの赤外分光光度計を用いて測定したピーク比（Ａ
／Ｂ）を求めることにより、反応率を求める。 （実施例２）In Example 1, 2 of the reactive ultraviolet absorber was used.
The polypropylene reacted with -hydroxy-4- (2'-methacryloyloxyethoxy) benzophenone is
As shown in FIG. 5, a stretching vibration peak (A) of an ester (C═O), which is not absorbed in polypropylene, is seen near 1720 cm −1 . From the peak ratio (A / B) between this peak and the peak (B) of C—H bending vibration of the main chain in the vicinity of 840 cm −1 , the reaction rate of the reactive ultraviolet absorber to polypropylene is determined. The same applies when obtaining the reaction rates of other reactive ultraviolet absorbers. In that case, polypropylene and several types of reactive ultraviolet absorbers are mixed in advance to prepare respective cast films. Then, each film was measured using an infrared spectrophotometer, and a calibration curve was prepared by plotting the reaction rate on the vertical axis and the peak ratio (A / B) on the horizontal axis, and based on this, a cast film of the test piece. Peak ratio (A
The reaction rate is calculated by calculating / B). (Example 2)
【００３３】ポリプロピレン樹脂１００重量部に対し、
反応型光安定剤として１，２，２，６，６−ペンタメチ
ル−４−ピペリジルメタクリレートを２．０重量部と、
ラジカル反応開始剤として過酸化ベンゾイルを１．０重
量部加えてドライブレンドした。このブレンド物を押出
成形機に投入して実施例１と同様に板状のポリプロピレ
ン樹脂成形品を製造し、試験片（５０×１００×１ｍ
ｍ）を作成した。With respect to 100 parts by weight of polypropylene resin,
2.0 parts by weight of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate as a reactive light stabilizer,
1.0 part by weight of benzoyl peroxide was added as a radical reaction initiator and dry blended. This blended product was put into an extrusion molding machine to produce a plate-shaped polypropylene resin molded product in the same manner as in Example 1, and a test piece (50 × 100 × 1 m
m) was created.
【００３４】この試験片について実施例１と同様にして
促進耐候性試験を行い、照射時間と黄変度（ΔＹＩ）と
の関係を調べた結果を表１に示す。また、この試験片に
ついて実施例１と同様の方法で光安定剤の反応率を求め
たところ、反応率は約０．１５７モル％であった。 （実施例３）An accelerated weather resistance test was conducted on this test piece in the same manner as in Example 1, and the results of examining the relationship between the irradiation time and the degree of yellowing (ΔYI) are shown in Table 1. Further, when the reaction rate of the light stabilizer was determined for this test piece by the same method as in Example 1, the reaction rate was about 0.157 mol%. (Example 3)
【００３５】ポリプロピレン樹脂１００重量部に対し、
反応型紫外線吸収剤として２−ヒドロキシ−４−（２′
−アクリロイルオキシエトキシ）ベンゾフェノンを１．
５重量部と、反応型光安定剤として１，２，２，６，６
−ペンタメチル−４−ピペリジルアクリレートを１．０
重量部と、ラジカル反応開始剤として過酸化ベンゾイル
を１．０重量部加えてドライブレンドした。このブレン
ド物を押出成形機に投入して実施例１と同様に板状のポ
リプロピレン樹脂成形品を製造し、試験片（５０×１０
０×１ｍｍ）を作成した。With respect to 100 parts by weight of polypropylene resin,
2-hydroxy-4- (2 ') as a reactive ultraviolet absorber
-Acryloyloxyethoxy) benzophenone
5 parts by weight and 1,2,2,6,6 as a reactive light stabilizer
-Pentamethyl-4-piperidyl acrylate 1.0
By weight, 1.0 part by weight of benzoyl peroxide as a radical reaction initiator was added and dry blended. This blended product was put into an extrusion molding machine to produce a plate-shaped polypropylene resin molded product in the same manner as in Example 1, and a test piece (50 × 10 5
0 × 1 mm) was prepared.
【００３６】この試験片について実施例１と同様にして
促進耐候性試験を行い、照射時間と黄変度（ΔＹＩ）、
紫外線吸収剤の残存率との関係を調べた結果を表１に示
す。また、この試験片について実施例１と同様の方法で
光安定剤の反応率を求めたところ、反応率は約０．１０
７モル％であった。 （比較例１）An accelerated weathering test was conducted on this test piece in the same manner as in Example 1, and the irradiation time and yellowing degree (ΔYI),
Table 1 shows the results of examining the relationship with the residual rate of the ultraviolet absorber. When the reaction rate of the light stabilizer was determined for this test piece by the same method as in Example 1, the reaction rate was about 0.10.
It was 7 mol%. (Comparative Example 1)
【００３７】ポリプロピレン樹脂１００重量部に対し、
従来の非反応型の紫外線吸収剤である２−ヒドロキシ−
４−（２′−メタクリロイルオキシエトキシ）ベンゾフ
ェノンを１．５重量部加えてドライブレンドし、このブ
レンド物を押出成形機に投入して実施例１と同様に板状
のポリプロピレン樹脂成形品の試験片（５０×１００×
１ｍｍ）を作成した。With respect to 100 parts by weight of polypropylene resin,
2-Hydroxy-, a conventional non-reactive UV absorber
1.5 parts by weight of 4- (2'-methacryloyloxyethoxy) benzophenone was added and dry blended. The blended product was put into an extrusion molding machine, and a plate-like polypropylene resin molded article test piece was prepared as in Example 1. (50 x 100 x
1 mm) was created.
【００３８】この試験片について実施例１と同様に促進
耐候性試験を行い、照射時間と黄変度（ΔＹＩ）、紫外
線吸収剤の残存率との関係を調べた結果を表１に示す。An accelerated weather resistance test was conducted on this test piece in the same manner as in Example 1, and the results of examining the relationship between the irradiation time, the degree of yellowing (ΔYI), and the residual rate of the ultraviolet absorber are shown in Table 1.
【００３９】[0039]
【表１】 [Table 1]
【００４０】表１から、実施例１及び３の試験片は、１
０００ｈｒ照射による促進試験後も、紫外線吸収剤の残
存率が比較例のものより遥かに高く、長期間に亘って優
れた耐紫外線性を維持していることが判る。 （実施例４）From Table 1, the test pieces of Examples 1 and 3 were 1
It can be seen that even after the accelerated test by irradiation with 000 hours, the residual rate of the ultraviolet absorber is much higher than that of the comparative example, and excellent ultraviolet resistance is maintained for a long period of time. (Example 4)
【００４１】ベースレジンのポリエステルアクリレート
オリゴマーにヘキサンジオールジアクリレートを添加し
て粘度を５５ｃｐｓ／２５℃に調整し、この樹脂成分９
０重量部に対し反応型紫外線吸収剤として２−ヒドロキ
シ−４−（２′−メタクリロイルオキシエトキシ）ベン
ゾフェノンと、反応型光安定剤として１，２，２，６，
６−ペンタメチル−４−ピペリジルメタクリレートをそ
れぞれ５重量部づつ混合して、電子線硬化型樹脂塗料を
調製した。Hexanediol diacrylate was added to the polyester acrylate oligomer of the base resin to adjust the viscosity to 55 cps / 25 ° C.
2-hydroxy-4- (2'-methacryloyloxyethoxy) benzophenone as a reactive ultraviolet absorber and 1,2,2,6,0 as a reactive light stabilizer to 0 part by weight.
5 parts by weight of 6-pentamethyl-4-piperidyl methacrylate were mixed to prepare an electron beam curable resin coating material.
【００４２】そして、ポリプロピレン樹脂板（１００×
３００×１ｍｍ）の表面に、上記の塗料をバーコーター
で塗膜が２５μｍになるように塗布し、コンベアで５ｍ
／ｍｉｎの速度で移動させながら、電子線加速機を用い
て加速電圧１００ＫＶ、照射量 Ｍｒａｄ、電子流５
ｍＡの条件下に電子線を照射し、表面に電子線硬化型樹
脂塗料の硬化塗膜を有するポリプロピレン樹脂板を製造
した。Then, a polypropylene resin plate (100 ×
(300 x 1 mm), apply the above paint with a bar coater to a coating film of 25 μm, and convey it with a conveyor for 5 m.
While moving at a speed of / min, an accelerating voltage of 100 KV, an irradiation dose of Mrad, and an electron flow of 5 using an electron beam accelerator.
An electron beam was irradiated under the condition of mA to produce a polypropylene resin plate having a cured coating film of an electron beam curable resin coating on its surface.
【００４３】この樹脂板について促進耐候試験（硬化塗
膜を形成した面を暴露面としてキセノンウェザオメータ
ーで５００時間、１０００時間照射）を行い、暴露前と
暴露後の黄色度及び層間密着性（耐剥離性）を調べた。
その結果を表２に示す。This resin plate was subjected to an accelerated weathering test (irradiation with a xenon weatherometer for 500 hours and 1000 hours with the surface on which the cured coating film was formed as the exposed surface), and the yellowness and interlayer adhesion before and after exposure ( The peel resistance) was investigated.
The results are shown in Table 2.
【００４４】尚、黄変度はＪＩＳＫ５４００に基拠した
ものであり、層間密着性は碁盤目テープ剥離試験におけ
る残存マス目数を調べたものである。また、表面硬度は
硬化塗膜を形成した面の暴露前の鉛筆硬度を示したもの
である。 （比較例２）The degree of yellowing is based on JIS K5400, and the interlaminar adhesion is the number of remaining squares in a cross-cut tape peeling test. The surface hardness indicates the pencil hardness of the surface on which the cured coating film is formed before exposure. (Comparative example 2)
【００４５】実施例４の反応型紫外線吸収剤及び反応型
光安定剤に代えて、塗料用として汎用されている非反応
型の紫外線吸収剤であるメチル−３−［３−ｔ−ブチル
−５−（２Ｈ−ベンゾトリアゾール−２−イル）−４−
ヒドロキシフェニル］プロピオネート−ポリエチレング
リコールと、非反応型の光安定剤であるビス（１，２，
２，６，６−ペンタメチル−４−ピペリジル）セバケー
トを配合した以外は同様にして塗料を調製した。そし
て、ポリプロピレン樹脂板（１００×３００×１ｍｍ）
の表面に該塗料を塗布し、実施例４と同様に電子線を照
射して、表面に硬化塗膜を有するポリプロピレン樹脂板
を得た。この樹脂板について実施例４と同様に促進耐候
試験を行い、暴露前と暴露後の黄変度及び層間密着性を
調べた。その結果を表２に示す。 （比較例３）Methyl-3- [3-t-butyl-5], which is a non-reactive UV absorber widely used for paints, is used in place of the reactive UV absorber and reactive light stabilizer of Example 4. -(2H-benzotriazol-2-yl) -4-
Hydroxyphenyl] propionate-polyethylene glycol and non-reactive light stabilizer bis (1,2,2)
A coating material was prepared in the same manner except that 2,6,6-pentamethyl-4-piperidyl) sebacate was blended. And polypropylene resin plate (100 x 300 x 1 mm)
The coating material was applied to the surface of and the electron beam was irradiated in the same manner as in Example 4 to obtain a polypropylene resin plate having a cured coating film on the surface. An accelerated weathering test was performed on this resin plate in the same manner as in Example 4, and the yellowing degree and the interlayer adhesion before and after exposure were examined. The results are shown in Table 2. (Comparative example 3)
【００４６】ベースレジンのポリエステルアクリレート
オリゴマーと反応性モノマーのヘキサンジオールジアク
リレートのみからなる電子線硬化型樹脂塗料を調製し
て、該塗料を実施例４と同様にポリプロピレン樹脂板
（１００×３００×１ｍｍ）の表面に塗布し、電子線を
照射して、表面に硬化塗膜を有するポリプロピレン樹脂
板を得た。このシートについて実施例４と同様に促進耐
候試験を行い、暴露前と暴露後の黄変度及び層間密着性
を調べた。その結果を表２に示す。An electron beam-curable resin coating consisting only of the polyester acrylate oligomer of the base resin and the reactive monomer hexanediol diacrylate was prepared, and the coating was applied to a polypropylene resin plate (100 × 300 × 1 mm) in the same manner as in Example 4. ) And was irradiated with an electron beam to obtain a polypropylene resin plate having a cured coating film on the surface. An accelerated weathering test was performed on this sheet in the same manner as in Example 4, and the yellowing degree before and after exposure and the interlayer adhesion were examined. The results are shown in Table 2.
【００４７】[0047]
【表２】 [Table 2]
【００４８】この表２から、本発明の実施例４の樹脂板
は、５００時間，１０００時間暴露しても黄色度（ΔＹ
Ｉ）が０．０３〜０．０６で暴露前と殆ど変わらない数
値であり、硬化塗膜によって優れた耐紫外線性が発揮さ
れ、黄変化が十分に抑制されていることが判る。これに
対し、反応型紫外線吸収剤も反応型光安定剤も含まない
硬化塗膜を形成した比較例３の樹脂板は、１０００時間
暴露後の黄変度が５．６０で黄変化が著しく進行してお
り、また、非反応型の紫外線吸収剤と光安定剤を含む硬
化塗膜を形成した比較例２の樹脂板は、１０００時間暴
露後の黄変度が２．０４であり、耐紫外線性が経時的に
低下して黄変化の抑制が不十分であることが判る。From Table 2, the resin plate of Example 4 of the present invention has a yellowness (ΔY) even after being exposed for 500 hours and 1000 hours.
I) is a value of 0.03 to 0.06, which is almost the same as that before the exposure, and it is understood that the cured coating film exhibits excellent ultraviolet resistance and the yellowing is sufficiently suppressed. On the other hand, in the resin plate of Comparative Example 3 on which a cured coating film containing neither reactive UV absorber nor reactive light stabilizer was formed, the yellowing degree after exposure for 1000 hours was 5.60 and the yellowing progressed remarkably. The resin plate of Comparative Example 2 having a cured coating film containing a non-reactive ultraviolet absorber and a light stabilizer has a yellowing degree of 2.04 after 1000 hours of exposure, It can be seen that the properties deteriorate with time and the yellowing is not sufficiently suppressed.
【００４９】また、比較例３の樹脂板は１０００時間暴
露後の硬化塗膜の密着性（耐剥離性）が５０／１００と
大幅に低下するのに対し、反応型の紫外線吸収剤及び光
安定剤を含む硬化塗膜を形成した実施例４の樹脂板や、
非反応型の紫外線吸収剤及び光安定剤を含む硬化塗膜を
形成した比較例２の樹脂板は、暴露前も暴露後も硬化塗
膜が優れた密着性を維持し、剥離の恐れが殆どないこと
が判る。Further, in the resin plate of Comparative Example 3, the adhesion (peeling resistance) of the cured coating film after being exposed for 1000 hours was significantly reduced to 50/100, whereas the reaction type ultraviolet absorber and the light stability were improved. A resin plate of Example 4 having a cured coating film containing an agent,
The resin plate of Comparative Example 2 on which a cured coating film containing a non-reactive UV absorber and a light stabilizer was formed maintained excellent adhesion of the cured coating film before and after exposure, and there was almost no risk of peeling. I know there isn't.
【００５０】[0050]
【発明の効果】以上の説明から明らかなように、ポリプ
ロピレン樹脂のポリマー分子に反応型紫外線吸収剤や反
応型光安定剤を反応させた本発明のポリプロピレン樹脂
成形品は、該紫外線吸収剤や光安定剤が殆ど揮散するこ
となく長期間に亘って優れた耐紫外線性を発揮し、外装
用建材等として使用しても紫外線による強度劣化や黄変
化を殆ど生じないといった顕著な効果を奏し、また、該
紫外線吸収剤や光安定剤が析出しないので良好な外観を
維持できるといった効果を奏する。しかも、このような
ポリプロピレン樹脂成形品は表面滑性が大きく、低温に
なっても割れにくいので、例えば積雪地域の屋根材その
他の外装用建材等として好適に使用することができる。As is apparent from the above description, the polypropylene resin molded article of the present invention obtained by reacting the polymer molecule of the polypropylene resin with the reactive ultraviolet absorber or the reactive light stabilizer is The stabilizer exhibits excellent UV resistance for a long period of time with almost no volatilization, and even if it is used as a building material for exteriors, it exhibits a remarkable effect of hardly causing strength deterioration or yellowing due to UV rays. Since the ultraviolet absorber and the light stabilizer are not deposited, a good appearance can be maintained. Moreover, such a polypropylene resin molded article has a large surface smoothness and is unlikely to be broken even at low temperatures, so that it can be suitably used as, for example, a roof material in a snowy area or other exterior building material.
【００５１】また、ポリプロピレン樹脂の成形品本体の
表面に反応型紫外線吸収剤や反応型光安定剤を配合した
電子線硬化型樹脂塗料の硬化塗膜を形成した本発明のポ
リプロピレン樹脂成形品は、該硬化塗膜の密着性（耐剥
離性）が大きく、該硬化塗膜中に保有される紫外線吸収
剤や光安定剤によって優れた耐紫外線性を長期間に亘っ
て発揮するため、同様に紫外線による強度劣化や黄変化
を生じることが殆どないといった顕著な効果を奏し、し
かも成形品本体がポリプロピレン樹脂であるから低温で
も割れにくいといった効果を奏する。Further, the polypropylene resin molded article of the present invention in which a cured coating film of an electron beam curable resin coating containing a reactive ultraviolet absorber or a reactive light stabilizer is formed on the surface of the polypropylene resin molded article body is The cured coating film has high adhesion (peeling resistance), and the ultraviolet absorber and the light stabilizer contained in the cured coating film exhibit excellent ultraviolet resistance for a long period of time. It has a remarkable effect that strength deterioration and yellowing hardly occur due to, and further, it has an effect that it is hard to crack even at low temperature because the molded product body is made of polypropylene resin.
【図１】第一発明のポリプロピレン樹脂成形品の一実施
例を示す断面図である。FIG. 1 is a cross-sectional view showing an embodiment of a polypropylene resin molded product of the first invention.
【図２】同実施例のポリプロピレン樹脂成形品の一製造
法の説明図である。FIG. 2 is an explanatory diagram of a method for manufacturing the polypropylene resin molded article of the same example.
【図３】第二発明のポリプロピレン樹脂成形品の一実施
例を示す断面図である。FIG. 3 is a cross-sectional view showing an example of a polypropylene resin molded product of the second invention.
【図４】補強繊維を埋入した第一発明のポリプロピレン
樹脂成形品の一製造法の説明図である。FIG. 4 is an explanatory view of a method for producing a polypropylene resin molded article of the first invention in which reinforcing fibers are embedded.
【図５】反応型紫外線吸収剤の２−ヒドロキシ−４−
（２′−メタクリロイルオキシエトキシ）ベンゾフェノ
ンを反応させたポリプロピレン樹脂と、反応させていな
いポリプロピレン樹脂について赤外分光光度計で測定し
たグラフである。FIG. 5: Reactive ultraviolet absorber 2-hydroxy-4-
It is the graph which measured with the infrared spectrophotometer about the polypropylene resin which made (2'-methacryloyloxy ethoxy) benzophenone react, and the polypropylene resin which is not made to react.
１ 反応型紫外線吸収剤及び反応型光安定剤の何れか一
方又は双方を反応させたポリプロピレン樹脂成形品 ７ 硬化塗膜 １０ ポリプロピレン樹脂の成形品本体1 Polypropylene resin molded product obtained by reacting one or both of reactive ultraviolet absorber and reactive light stabilizer 7 Cured coating film 10 Polypropylene resin molded product body
Claims (2)
型紫外線吸収剤及び反応型光安定剤のいずれか一方又は
双方を反応させてあることを特徴とするポリプロピレン
樹脂成形品。1. A polypropylene resin molded article characterized in that a polymer molecule of polypropylene resin is reacted with either or both of a reactive ultraviolet absorber and a reactive light stabilizer.
に、反応型紫外線吸収剤及び反応型光安定剤のいずれか
一方又は双方を配合した電子線硬化型樹脂塗料の硬化塗
膜を形成したことを特徴とするポリプロピレン樹脂成形
品。2. A cured coating film of an electron beam curable resin paint containing one or both of a reactive ultraviolet absorber and a reactive light stabilizer is formed on the surface of a polypropylene resin molded article body. Characteristic polypropylene resin molded product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4359789A JPH0711031A (en) | 1992-12-29 | 1992-12-29 | Polypropylene resin molded product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4359789A JPH0711031A (en) | 1992-12-29 | 1992-12-29 | Polypropylene resin molded product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0711031A true JPH0711031A (en) | 1995-01-13 |
Family
ID=18466303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4359789A Pending JPH0711031A (en) | 1992-12-29 | 1992-12-29 | Polypropylene resin molded product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0711031A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001114842A (en) * | 1999-10-21 | 2001-04-24 | Mitsubishi Chemicals Corp | Olefinic resin composition and thermoplastic resin composition containing the same |
-
1992
- 1992-12-29 JP JP4359789A patent/JPH0711031A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001114842A (en) * | 1999-10-21 | 2001-04-24 | Mitsubishi Chemicals Corp | Olefinic resin composition and thermoplastic resin composition containing the same |
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