JPS59166534A - Coating agent - Google Patents
Coating agentInfo
- Publication number
- JPS59166534A JPS59166534A JP58041317A JP4131783A JPS59166534A JP S59166534 A JPS59166534 A JP S59166534A JP 58041317 A JP58041317 A JP 58041317A JP 4131783 A JP4131783 A JP 4131783A JP S59166534 A JPS59166534 A JP S59166534A
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- maleic anhydride
- coating agent
- chlorinated
- polymer
- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はコーティング剤に関する。さらに詳しくはポリ
オレフィンに適したコーティング剤に関するものである
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coating agent. More specifically, it relates to coating agents suitable for polyolefins.
近年、自動車部品や家庭用電化製品のギヤビネット類に
各種プラスチックが幅広く使用さnるようになってきた
が、ポリオレフィン特にポリプロピレンは安価、軽量、
良好な耐溶剤性などのメリットからその応用開発が盛ん
である。しかし左から、ポリプロピレンは極性に乏しい
ため各種被覆剤が密着しにくい。このため最近、塩素化
ポリプロピレンに不飽和化合物?反応させたものや無水
マレイン酸グラフトポリプロピレンを塩素化したものが
ポリプロピレンの下塗り剤として提案さnている。しか
しながら、これらはもともと高分子量のポリプロピレン
を変性したもので、ポリプロピレン基材および」二塗り
塗料双方への密着性はある程度あるものの、より性能を
向上(たとえば、」二塗り塗料との密着1ヰ、耐油性、
耐候性などの向」二)させるために他のビヒクル成分、
たとえばエポキシ系・ウレタン系・アクリル系、アルキ
ッド系などの樹脂と併用ないし混合した場合、こnらの
樹脂と相溶性が悪く均一な配合物になシにくい。In recent years, various plastics have come to be widely used for gear vignettes in automobile parts and home appliances, but polyolefins, especially polypropylene, are cheap, lightweight,
Due to its advantages such as good solvent resistance, its applications are being developed extensively. However, from the left, polypropylene has poor polarity, making it difficult for various coating materials to adhere to it. For this reason, unsaturated compounds have recently been added to chlorinated polypropylene? Reactions and chlorinated maleic anhydride-grafted polypropylene have been proposed as primers for polypropylene. However, these are originally modified polypropylene with a high molecular weight, and although they have some degree of adhesion to both the polypropylene base material and the two-coat paint, they have improved performance (for example, adhesion to the two-coat paint, Oil resistance,
2) Other vehicle components to improve weatherability, etc.
For example, when used in combination with or mixed with epoxy, urethane, acrylic, or alkyd resins, it has poor compatibility with these resins and is difficult to form into a uniform blend.
その結果、配合物を有機溶剤に溶解し溶液にした場合・
その安定性が悪い、塗装作業性に欠ける、塗布して得ら
牡るコーテイング膜の外観、平滑性、密着性が低下する
などという問題点がある。As a result, when the compound is dissolved in an organic solvent and made into a solution,
There are problems such as poor stability, poor coating workability, and decreased appearance, smoothness, and adhesion of the resulting coating film.
本発明者らは、これらの問題点を解消すべく鋭意検討し
た結果、低分子量のプロピレン系重合体特に熱分解で得
られるもの全出発原料にして得らnるプロピレン系低重
合体の変性物ないし誘導体が」二記問題点を解消しうろ
ことを見い出し、本発明に到達した。As a result of intensive studies to solve these problems, the inventors of the present invention found that low molecular weight propylene polymers, especially those obtained by thermal decomposition, are modified products of propylene low polymers obtained from all starting materials. The inventors have discovered that the above two problems can be solved by the use of derivatives or derivatives thereof, and have arrived at the present invention.
すなわち、本発明は、無水マレイン酸付加プロピレン系
低重合体の塩素化物(但し、無水マレイン酸付加前のプ
ロピレン系低重合体の平均分子量無水マレイン酸付加プ
ロピレン系低重合体の塩素化物において、プロピレン系
低重合体の平均分子量は2. OOOないし80,00
0、好ましくは3、500ないし25.000である。That is, the present invention provides a chlorinated product of a propylene-based low polymer to which maleic anhydride has been added (however, the average molecular weight of the propylene-based low polymer before addition of maleic anhydride) The average molecular weight of the low polymer is 2.00 to 80,00.
0, preferably 3,500 to 25,000.
平均分子量が2、 OO0未満では最終塩素化物が脆弱
で粘着性がありコーティング剤として適さない。平均分
子量が30.OOO’i超えると混合される他のビヒク
ル樹脂との相溶性が悪く、得らnるコーティング用配合
物の安定性が十分でないため塗装作業性に欠けるのみな
らず、平滑性、密着性の良好な塗膜が得らnない。平均
分子量は、たとえば、プロピレン系低重合体をオルソ−
ジ−クロルベンゼンに約0.3重量/容量係の濃度に溶
解し、185’Cの条件下ゲルパーミイエーションクロ
マトグラフにより測定することができる。また、プロピ
レン系低重合体のメルトフローレートは通常500以上
、好ましくは1. OO0以上である。メルトフローレ
ートが500未満では他の樹脂との相溶性が低下し易い
。If the average molecular weight is less than 2,000, the final chlorinated product will be brittle and sticky, making it unsuitable as a coating agent. Average molecular weight is 30. If it exceeds OOO'i, it will have poor compatibility with other vehicle resins to be mixed, and the resulting coating compound will not have sufficient stability, resulting in not only poor coating workability but also poor smoothness and adhesion. A good coating film cannot be obtained. For example, the average molecular weight of propylene-based low polymers is
It can be dissolved in di-chlorobenzene at a concentration of about 0.3 weight/volume and measured by gel permeation chromatography at 185'C. Further, the melt flow rate of the propylene-based low polymer is usually 500 or more, preferably 1. It is OO0 or more. If the melt flow rate is less than 500, compatibility with other resins tends to decrease.
プロピレン低重合体としては、プロピレン単独重合体ま
たはプロピレンとエチレン、ブテン−1、ペンテン−1
、ヘキセン−1、ヘプテン−1など他のα−オレフィン
(炭素数通常2以上、好ましくは2〜6)コーモノマー
との共重合体(共重合体は好ましくはコーモノマー含有
量が20モ)v %以下のもの)があげられる。プロピ
レン系低重合体はアイツタクチイック、アタクティック
、シンジオタフティックのいずnの欄造のものでもよい
。Propylene low polymers include propylene homopolymers, propylene and ethylene, butene-1, pentene-1
, copolymer with other α-olefin (carbon number usually 2 or more, preferably 2 to 6) comonomer such as hexene-1, heptene-1 (copolymer preferably has a comonomer content of 20 moles) v % or less ) can be given. The propylene-based low polymer may be one of the following types: atactic, atactic, and syndiotactic.
プロピレン系低重合体は高分子量プロピレン系重合体を
熱分解(熱減成)する方法で得ら扛るものでもよく、通
常のテロメリゼーション(プロピレンを単独または共像
重合させる)で得られるものでもよい。こ扛らのうち、
無水マレイン酸の付加反応が速く、高品質のものが得ら
nる利点から熱分解して得られるものが好ましい。熱分
解する方法は、たとえば高分子量プロピレン単独または
共重合体(分子量通常10万〜200万)を不活性ガス
存在下また必要により水蒸気存在下通常300〜450
℃で数時間程度加熱することにより行なう方法があげら
nる。熱分解法はたとえばUS2928797.282
8296,2885659.Br’1t−110829
5、特公昭43−!11168などに記載さしている。Propylene-based low polymers may be those obtained by thermal decomposition (thermal degradation) of high molecular weight propylene-based polymers, or those obtained by normal telomerization (single or co-image polymerization of propylene). But that's fine. Among these,
Those obtained by thermal decomposition are preferred because the addition reaction of maleic anhydride is fast and high quality products can be obtained. For example, a method of thermally decomposing high molecular weight propylene alone or a copolymer (molecular weight usually 100,000 to 2,000,000) in the presence of an inert gas or, if necessary, in the presence of steam,
One example is a method of heating at .degree. C. for several hours. For example, the pyrolysis method is described in US2928797.282.
8296,2885659. Br'1t-110829
5.Special public school 1977-! 11168 etc.
無水マレイン酸付加プロピレン系低重合体において化学
的に結合した無水マレイン酸の量は通常0.5ないし1
0重量%、好ましくは1ないし7重量%である。無水マ
レイン酸の量が0.5重量%未満では混合する他のビヒ
クルとの相溶性が低下し、また上塗り剤との密着性が十
分でない。10重量%ヲ超えると耐水性および可撓性が
低下する。The amount of chemically bonded maleic anhydride in the maleic anhydride-added propylene low polymer is usually 0.5 to 1.
0% by weight, preferably 1 to 7% by weight. If the amount of maleic anhydride is less than 0.5% by weight, the compatibility with other vehicles to be mixed will decrease, and the adhesion with the top coat will be insufficient. If it exceeds 10% by weight, water resistance and flexibility will decrease.
無水マレイン酸付加プロピレン系低重合体は不活性ガス
雰囲気中、プロピレン系低重合体を芳香族系および/ま
たは塩素系などの溶剤の存在下または不存在下に、また
ラジカル発生触媒(パーオキサイド類、アゾ逼トリル類
など)の存在下または不存在下に通常120℃ないし2
20℃に加熱溶解し、無水マレイン酸を分割してまたは
一括に投入して反応(グラフト重合)させることによシ
得ることができる。Maleic anhydride-adducted propylene-based low polymers are prepared by adding propylene-based low polymers in an inert gas atmosphere in the presence or absence of aromatic and/or chlorine-based solvents, and in the presence or absence of radical-generating catalysts (peroxides). , azotolyles, etc.), usually at 120°C to 2°C.
It can be obtained by heating and dissolving at 20° C., adding maleic anhydride in portions or all at once, and causing a reaction (graft polymerization).
無水マレイン酸付加プロピレン系低重合体の塩素化物に
おいて塩素化物中の結合塩素量は通常5ないし50重量
係、好ましくは10ないし35重量係である。結合塩素
量が5重量係未満では溶剤への溶解性が不十分であり、
50重量係を超えると耐候性が低下する。無水マレイン
酸付加プロピレン系低重合体の塩素化物1d公知の方法
、たとえば無水マレイン酸付加プロピレン系低重合体を
四塩化炭素などの塩素系溶剤に加熱溶解し、塩素化を促
進させる温度、たとえば60℃ないし120℃にて塩素
ガスを反応液中に導入、反応させることにより得ること
ができる。反応の速度を大きくする目的で光を照射して
行なってもよいし、また加圧下で行なってもよい。In the chlorinated maleic anhydride-added propylene low polymer, the amount of bound chlorine in the chlorinated product is usually 5 to 50 parts by weight, preferably 10 to 35 parts by weight. If the amount of combined chlorine is less than 5% by weight, the solubility in the solvent is insufficient,
If it exceeds 50% by weight, weather resistance will decrease. Chlorinated product of maleic anhydride-added propylene-based low polymer 1d By a known method, for example, a maleic anhydride-added propylene-based low polymer is heated and dissolved in a chlorinated solvent such as carbon tetrachloride, and the chlorination is accelerated at a temperature of, for example, 60°C. It can be obtained by introducing chlorine gas into a reaction solution and reacting at a temperature of 120°C to 120°C. The reaction may be carried out by irradiating light for the purpose of increasing the reaction rate, or may be carried out under pressure.
得られた無水マレイン酸付加プロピレン系低重合体の塩
素化物は淡黄色〜黄色の固体で、軟化、欝(環球式)は
通常130℃〜170℃、溶融粘度(160℃)は通常
50〜50000cpsである。The obtained chlorinated product of maleic anhydride-added propylene-based low polymer is a pale yellow to yellow solid, and its softening and cooling (ring and ball type) are usually 130°C to 170°C, and the melt viscosity (160°C) is usually 50 to 50,000 cps. It is.
本発明のコーティング剤は、無水マレイン酸付加プロピ
レン系低重合体の塩素化物を含有してなるものであり・
通常芳香族系溶剤(トルエン、キシレン、クメンなど)
、塩素系溶剤(シフa yvエチレン、パークロルエチ
レン、ジクロルベンゼンなど)などの溶剤に適当な濃度
(通常1〜30重量%)で溶解した溶液として使用され
る。安全衛生り溶剤の使用が好ましくない場合には、無
水マレイン酸付加プロピレン系低重合体の塩素化物をノ
卆オン、アニオン、カチオンなどの界面活性剤(ノニル
フェノ=7レオキシアルキVンエーテル。The coating agent of the present invention contains a chlorinated maleic anhydride-added propylene-based low polymer.
Usually aromatic solvents (toluene, xylene, cumene, etc.)
It is used as a solution in a suitable concentration (usually 1 to 30% by weight) in a solvent such as a chlorinated solvent (Schiff ethylene, perchlorethylene, dichlorobenzene, etc.). If the use of solvents is undesirable for safety and hygiene reasons, use a chlorinated maleic anhydride-adducted propylene-based low polymer as a surfactant such as a nonionic, anionic, or cationic surfactant (nonylphenol 7-leoxyalkyne ether).
高級アルコールオキシアルキレンエーテル、アルギルベ
ンゼンスルホン酸ソーダなど)を用い水性エマルジョン
(固型分濃度通常1〜20重量%)としてもよい。An aqueous emulsion (solid content usually 1 to 20% by weight) may be prepared using a higher alcohol oxyalkylene ether, sodium argylbenzenesulfonate, etc.).
本発明のコーティング剤にはコーテイング膜の耐溶剤性
、耐水性、耐熱性、平滑性などを向上させる目的でエポ
キシ系、ウレタン系、アクリル系、アルキッド系などの
一般的に塗料用ビヒクルとして使用さ几る樹脂を適宜混
合することが好ましい。The coating agent of the present invention includes epoxy-based, urethane-based, acrylic-based, and alkyd-based coating agents commonly used as paint vehicles for the purpose of improving the solvent resistance, water resistance, heat resistance, smoothness, etc. of the coating film. It is preferable to appropriately mix a cooling resin.
これらの樹脂は「合成樹脂塗料」 (株式会社高分子刊
行会・昭和41年12月10日発行)に記載されている
。混合時の塩素化物と他樹脂との重量比は通常3:97
〜97:8.好ましくは5:95〜95:5である。These resins are described in "Synthetic Resin Paints" (Kobunshi Publishing Co., Ltd., published on December 10, 1960). The weight ratio of chlorinated material and other resins during mixing is usually 3:97.
~97:8. Preferably it is 5:95 to 95:5.
また、これらのコーティング剤には顔料、分散剤などの
通常の塗料用添加剤を配合してもよい。Further, these coating agents may be blended with ordinary paint additives such as pigments and dispersants.
その量はコーティング剤中で通常10重量%以下である
。Its amount is usually less than 10% by weight in the coating agent.
本発明のコーティング剤の対鈴物(コーティング用基材
)としてはポリオレフィン(特にプロピレン系重合体)
が好ましく、その他にも他のプラスチック、木材、紙、
金属などにも使用することができる。The material (coating base material) for the coating agent of the present invention is polyolefin (especially propylene polymer).
is preferred, as well as other plastics, wood, paper,
It can also be used for metals, etc.
コーティング剤の基材への適用は通常の方法でよく、た
とえばコーティング剤を対象物に対しへヶ塗り、スプレ
ー、浸漬などの通常の塗装方法でコーティングすnばよ
い。塗布量は乾燥膜厚で通常5〜40μである。乾燥は
通常室温で5〜20分セツティングののち、70〜13
0℃で10〜45分加熱して行なう。適用は基材に直接
適用する他(1回塗り)、適用し乾燥した膜にさらに適
用(2回塗9以上)することもできる。この様にして塗
布さtたコーテイング膜には必要によシ上塗9剤が適用
される。この上塗り剤としては熱可塑性のものでも、ま
た熱硬化性のものでもよく、たとえばアルキッド系、ア
クリル系・エポキシ系、ウレタン系、アクリルウレタン
系−1どの一般に用いら牡る塗料があげられる。これら
の塗料も前記「合成樹脂塗料」に記載されている。The coating agent may be applied to the substrate by a conventional method, for example, the coating agent may be applied to the object by a conventional coating method such as dipping, spraying, or dipping. The coating amount is usually 5 to 40 microns in terms of dry film thickness. Drying is usually done at room temperature for 5 to 20 minutes, then 70 to 13 minutes.
This is done by heating at 0°C for 10 to 45 minutes. In addition to applying directly to the substrate (one coat), it is also possible to further apply the applied and dried film (two coats or more). If necessary, a topcoat is applied to the coating film thus applied. The top coating agent may be thermoplastic or thermosetting, and includes commonly used paints such as alkyd, acrylic/epoxy, urethane, and acrylic urethane-1. These paints are also described in the above-mentioned "synthetic resin paints".
本発明のコーティング剤は下記の効果を奏する。The coating agent of the present invention has the following effects.
(1) 本発明のコーティング剤は他の樹脂を混合し
た場合、そnらの樹脂に相溶性が良好であり、貯蔵安定
性の優れたコーティング剤が得られる。(1) When the coating agent of the present invention is mixed with other resins, it has good compatibility with those resins, and a coating agent with excellent storage stability can be obtained.
(2) 本発明のコーティング剤を基材とくにポリオ
レフィン成形品にコーティングした場合、ポリオレフィ
ン成形品表面に強固に密着し、耐油性、耐候性、防錆性
などの諸性能に優れた塗膜が得られる。また上塗シ剤を
さらにコーティングした場合、上塗り剤に対しても優f
した密着性を持つ。特に本発明のコーティング剤を他の
樹脂と配合した場合は上記性能は向上する。(2) When the coating agent of the present invention is coated on a base material, particularly a polyolefin molded product, a coating film that firmly adheres to the surface of the polyolefin molded product and has excellent properties such as oil resistance, weather resistance, and rust prevention can be obtained. It will be done. In addition, when the top coat agent is further coated, it is also superior to the top coat agent.
It has excellent adhesion. In particular, when the coating agent of the present invention is blended with other resins, the above performance is improved.
(3) 本発明のコーティング剤は従来品にくらべて
溶剤に溶解″!、たけ水に分散して得たコーティング剤
の粘度が低く、特にスプレーなどによる塗装作業性が優
れている。また塩素化ポリプロピレンに無水マレイン酸
を反応させたものにくらべても、溶剤に対し溶解性が向
上する。(3) Compared to conventional products, the coating agent of the present invention is soluble in solvents, and the viscosity of the coating agent obtained by dispersing it in bamboo water is low, making it particularly easy to apply by spraying.Also, chlorinated It has improved solubility in solvents compared to polypropylene reacted with maleic anhydride.
本発明のコーティング剤はポリオレフィン成形品特にプ
ロピレン系重合体成形品の塗布剤として好ましく使用す
ることができる。またポリオレフィン成形品の接着剤、
印刷インキとしても使用することができる。The coating agent of the present invention can be preferably used as a coating agent for polyolefin molded articles, particularly propylene polymer molded articles. Also, adhesives for polyolefin molded products,
It can also be used as a printing ink.
以下、製造例、比較製造例、実施例および試験例により
本発明をさらに説明するが、本発明はと牡に限定さnる
ものではない。なお、製造例、比較製造例、実施例およ
び試験例中の部は特記しない限り重量部を示す。Hereinafter, the present invention will be further explained with reference to production examples, comparative production examples, examples, and test examples, but the present invention is not limited to chickens. In addition, parts in production examples, comparative production examples, examples, and test examples indicate parts by weight unless otherwise specified.
製造例1
高分子量のプロピレン単独重合体(平均分子量1250
00)を熱分解して得ら牡る平均分子量10000のプ
ロピレン単独重合体300部、および無水マレイン酸3
0部を還流管つきの装置に仕込み・キシレン700部を
加えたあと系を窒素置換した。攪拌下、窒素を少量導入
しながら150℃に昇湿し、系を均一に溶解したあとジ
クミルパーオキザイド165部を3時間で添加し、さら
に4時間反応を続けたあと最初常圧で、ついで180℃
、8msHgの減圧下2時間かけてキシレンおよび未反
応の無水マレイン酸を留去した。得らnた無水マレイン
酸付加プロピレン低重合体は160℃での溶融粘度16
00CI)S%環球式軟化点154℃の黄色の固体で、
無水マレイン酸付7Jl″1景は3.8重量部であった
。Production Example 1 High molecular weight propylene homopolymer (average molecular weight 1250
300 parts of a propylene homopolymer having an average molecular weight of 10,000 obtained by thermally decomposing 00), and 3 maleic anhydride.
0 part was charged into a device equipped with a reflux tube, 700 parts of xylene was added, and the system was purged with nitrogen. While stirring, the temperature was raised to 150°C while introducing a small amount of nitrogen, and after uniformly dissolving the system, 165 parts of dicumyl peroxide was added over 3 hours. After continuing the reaction for another 4 hours, initially at normal pressure, Then 180℃
, xylene and unreacted maleic anhydride were distilled off over 2 hours under reduced pressure of 8 msHg. The obtained maleic anhydride-added propylene low polymer had a melt viscosity of 16 at 160°C.
00CI) S% A yellow solid with a ring and ball softening point of 154°C,
7Jl''1 volume with maleic anhydride was 3.8 parts by weight.
次に上記無水マレイン酸付加プロピレン低重合体200
部、および四塩化炭素800部を蓬流管つきの装置に仕
込み、65℃〜70℃に加熱して均一に溶解後、1時間
当り35部の塩素ガスを反応液中に4時間導入した。塩
素化後、反応液中の残存塩素および四塩化炭素を最初常
圧で次いで160℃、8ypHgの減圧下2時間かけて
留去した。得られた無水マレイン酸付加プロピレン低重
合体の塩素化物1d、160℃での溶融粘度112゜c
ps、i球式軟化点150℃の黄色の固体で、結合塩素
量は21.5重量部であった。Next, the maleic anhydride-added propylene low polymer 200
1 part, and 800 parts of carbon tetrachloride were charged into an apparatus equipped with a flow tube, heated to 65°C to 70°C to uniformly dissolve them, and then 35 parts of chlorine gas per hour was introduced into the reaction solution for 4 hours. After chlorination, residual chlorine and carbon tetrachloride in the reaction solution were first distilled off at normal pressure and then at 160°C and under reduced pressure of 8ypHg over 2 hours. The obtained chlorinated maleic anhydride propylene low polymer 1d, melt viscosity at 160°C 112°C
ps, i It was a yellow solid with a ball softening point of 150°C, and the amount of combined chlorine was 21.5 parts by weight.
製造例2
プロピレン系低重合体として高分子量のプロピレン系重
合体(平均分子量165000)を熱分解して得ら乳た
平均分子量6500.エチレン含有量10モル係のプロ
ピレン−エチレンブロック共重合体を用いる他は製造例
1と同様の方法で、無水マレイン酸付加量52重量%、
結合塩素i 24 B重量%の無水マレイン酸付加プロ
ピレン系低重合体の塩素化物を得た。この変性低重合体
の160℃での溶融粘度は580 C98% 環球式軟
化点は146℃であった。Production Example 2 Propylene-based low polymer was obtained by thermally decomposing a high molecular weight propylene-based polymer (average molecular weight: 165,000). The same method as in Production Example 1 was used except that a propylene-ethylene block copolymer with an ethylene content of 10 moles was used, and the amount of maleic anhydride added was 52% by weight.
A chlorinated product of a maleic anhydride-added propylene-based low polymer having a combined chlorine i 24 B weight % was obtained. This modified low polymer had a melt viscosity of 580 C98% at 160°C and a ring and ball softening point of 146°C.
製造例3
プロピレン系低重合体として高分子量のプロピレン系重
合体(平均分子量112000)を熱分解して得られた
平均分子Ji28000、ブテン−1含有量20モルチ
のプロピレン−ブテン−1ブロック共重合体を用いる他
は製造例1と同様の方法で無水マレイン酸付加量2.8
重量部、結合塩素量32.2重量部の無水マレイン酸付
加プロピレン系低重合体の塩素化物を得た。この変性低
重合体の160℃での溶融粘度は41000cps、環
球式軟化点は158℃であった。Production Example 3 A propylene-butene-1 block copolymer with an average molecular weight Ji of 28,000 and a butene-1 content of 20 moles obtained by thermally decomposing a high molecular weight propylene polymer (average molecular weight 112,000) as a propylene-based low polymer. The amount of maleic anhydride added was 2.8 in the same manner as in Production Example 1 except that
A chlorinated product of a maleic anhydride-adducted propylene-based low polymer having a combined chlorine content of 32.2 parts by weight was obtained. This modified low polymer had a melt viscosity of 41,000 cps at 160°C and a ring and ball softening point of 158°C.
比較製造例1
プロピレン系重合体として平均分子量97000のプロ
ピレン単独重合体を用いる他は製造例1と同様の方法で
無水マレイン酸付加量35重量%、結合塩素量19.8
重量部の無水マレイン酸付加プロピレン単独重合体の塩
素化物を得た。この変性重合体の160℃での溶融粘度
は550万cps、環球式軟化点は162℃であった。Comparative Production Example 1 The same method as Production Example 1 was used except that a propylene homopolymer with an average molecular weight of 97,000 was used as the propylene polymer, with an amount of maleic anhydride added of 35% by weight and an amount of bound chlorine of 19.8.
Part by weight of a chlorinated maleic anhydride-added propylene homopolymer was obtained. This modified polymer had a melt viscosity of 5.5 million cps at 160°C and a ring and ball softening point of 162°C.
実施例1
製造例1〜3および比較製造例1で得ら乳た無水マレイ
ン酸付加プロピレン系重合体の塩素化物を用い次の二連
シのコーティング剤を作成した。Example 1 The following two series of coating agents were prepared using the chlorinated maleic anhydride-added propylene polymers obtained in Production Examples 1 to 3 and Comparative Production Example 1.
A 無水マレイン酸グラフトプロピレン系重合体の塩素
化物を、固型分濃度が5・、:重量部になるように1−
ルエンに溶解した溶液。A. Chlorinated maleic anhydride-grafted propylene polymer was added to 1-1% of the solid content so that the solid content was 5 parts by weight.
Solution in toluene.
B 無水マレイン酸付加プロピレン系重合体の塩素化物
71部、ダイマー酸系エポキシ樹脂(エピコー)871
、シェル化学製)43部詮よびダイマー酸系ポリアミド
樹脂(ポリマイドH−2270.アミン価144、三洋
化成工業製)28部と混合し、固型分濃度が5重量係に
なるようにトルエンに溶解した溶液。B 71 parts of chlorinated maleic anhydride-added propylene polymer, 871 parts of dimer acid-based epoxy resin (Epicor)
, manufactured by Shell Chemical Co., Ltd.) and 28 parts of dimer acid polyamide resin (Polymide H-2270. Amine value 144, manufactured by Sanyo Chemical Industries, Ltd.) and dissolved in toluene so that the solid content concentration becomes 5% by weight. solution.
試験例1
ポリプロピレン(宇部ポリプロピレンJ−309G)を
射出成形により成形し、100maX 100rnx×
2 ffJl+のシートを得た。この各シートをイソプ
ロピルアルコールに室懸で1分間浸漬後5分間室副乾燥
し脱脂処理した。そのちとこの脱脂シートに実施例1に
よるA、Bのコーティング剤ヲスプレー塗布し、5分間
室温乾燥後衛風乾燥機で90℃、30分間乾燥、硬化し
た。この下塗りした各シートに二液型無黄変アクリルウ
レタン樹脂系塗料(サンブレンTC−Q7、王洋化成工
業製)を主剤、および硬化剤を2:1の割合で混合、ス
プレー塗布し、1o分間室温乾燥後循風乾燥機で90C
aO分間乾ml、硬化した。こうして得られた各塗装シ
ートを室温で7日後放置後次の各試験をイ斤なった。結
果を第1表に示す。Test Example 1 Polypropylene (Ube Polypropylene J-309G) was molded by injection molding, 100 maX 100rnx
A sheet of 2 ffJl+ was obtained. Each of the sheets was immersed in isopropyl alcohol for 1 minute in a room, and then dried in a room for 5 minutes for degreasing. Thereafter, coating agents A and B according to Example 1 were spray applied to the degreased sheet, dried at room temperature for 5 minutes, and then dried and cured in a garnish dryer at 90° C. for 30 minutes. A two-component non-yellowing acrylic urethane resin paint (Sunbren TC-Q7, manufactured by Ohyo Kasei Kogyo Co., Ltd.) was mixed with a base agent and a curing agent at a ratio of 2:1, and sprayed on each of the primed sheets for 10 minutes. After drying at room temperature, use a circulation dryer at 90C.
Dry for a0 ml and cure. Each coated sheet thus obtained was left at room temperature for 7 days and then subjected to the following tests. The results are shown in Table 1.
(1) コーティング剤の外観
A、Bのコーティング剤の作成直後の外観を肉眼観察し
た。(1) Appearance of coating agents The appearance of coating agents A and B immediately after preparation was observed with the naked eye.
(2) コーティング剤の貯蔵安定性A、 Bのコ
ーティング剤をガラスビンに入れ、6ケ月間室温放置し
たあとの外観を肉眼観察した。(2) Storage Stability of Coating Agents Coating agents A and B were placed in a glass bottle, and after being left at room temperature for 6 months, the appearance was visually observed.
(3)初期密着性
各塗装シートの塗膜面についてJ工5K5400のゴバ
ン目セロハンテープ試験を行なった。(3) Initial adhesion A cellophane tape test using J-K5K5400 was conducted on the coating surface of each coated sheet.
(4)耐水性
各塗装シー)’i40℃の温水に240時間浸漬後、1
時間室温乾燥しゴバン日セロハンテープ試験を行なった
。(4) Water resistance Each coating sheet) After 240 hours immersion in 40℃ warm water, 1
After drying at room temperature for an hour, a cellophane tape test was conducted.
(5)耐揮発油性
各塗装シートをn−ヘキサン/n−へブタン−1/1の
混合溶剤に20℃、24時間浸漬後、1時間室温乾燥し
ゴバン目セロハンテープ試験を行なった。(5) Volatile oil resistance Each coated sheet was immersed in a 1/1 mixed solvent of n-hexane/n-hebutane at 20° C. for 24 hours, dried at room temperature for 1 hour, and then subjected to a cellophane tape test.
(6)耐候性
各塗装シートをJISK5400に基づき、サンシャイ
ンカーボン型つェザオメーターに1000時間かけたあ
と1時間室温放置しゴバン日セロハンテープ試験を行な
った。(6) Weather resistance Each coated sheet was subjected to a Sunshine Carbon Type Tweezerometer for 1,000 hours and then left at room temperature for 1 hour to conduct a Govan cellophane tape test based on JIS K5400.
Claims (1)
化物(但し無水マレイン酸付加前のプロピレン系低重合
体の平均分子量は2.0002 無水マレイン酸付加前
のプロピレン系低重合体が熱分解型プロピレン単独重合
体または共重合体である特許請求の範囲第1項記載のコ
ーティング剤。 λ 該低重合体中の化学的に結合した無水マレイン酸の
含有量が0.5ないし10重量%である特許請求の範囲
第1項または第2項記載のコーティング剤。 4、 塩素化物中の結合塩素量が5ないし5ON量係で
ある特許請求の範囲第1項〜第3項のいずれかに記載の
コーティング剤。 5、 無水マレイン酸付加前のプロピレン系低重合体の
メルトフローレートが500以上である特許請求の範囲
第1項〜第4項のいず乳かに記載のコーティング剤。[Claims] 1. Chlorinated propylene-based low polymer with maleic anhydride added (however, the average molecular weight of the propylene-based low polymer before addition of maleic anhydride is 2.0002; The coating agent according to claim 1, wherein the polymer is a pyrolyzable propylene homopolymer or copolymer.λ The content of chemically bonded maleic anhydride in the low polymer is 0.5 to 10% by weight of the coating agent according to claim 1 or 2. 4. The coating agent according to claims 1 to 3, wherein the amount of combined chlorine in the chloride is in the range of 5 to 5ON. 5. The coating according to any one of claims 1 to 4, wherein the propylene-based low polymer has a melt flow rate of 500 or more before addition of maleic anhydride. agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58041317A JPS59166534A (en) | 1983-03-11 | 1983-03-11 | Coating agent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP58041317A JPS59166534A (en) | 1983-03-11 | 1983-03-11 | Coating agent |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS59166534A true JPS59166534A (en) | 1984-09-19 |
Family
ID=12605129
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP58041317A Pending JPS59166534A (en) | 1983-03-11 | 1983-03-11 | Coating agent |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59166534A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6099138A (en) * | 1983-11-02 | 1985-06-03 | Mitsui Petrochem Ind Ltd | Undercoating agent for coating of polyolefin molded article |
US4863988A (en) * | 1986-03-18 | 1989-09-05 | Mitsui Petrochemical Industries, Ltd. | Composition for curable paints |
JPH04136042A (en) * | 1990-09-28 | 1992-05-11 | Ube Ind Ltd | Surface treatment of polyolefin molding to be coated |
US5491191A (en) * | 1992-04-06 | 1996-02-13 | E. I. Du Pont De Nemours And Company | Stable chlorosulfonated resin latex |
JP2010137415A (en) * | 2008-12-10 | 2010-06-24 | Mitsubishi Rayon Co Ltd | Acrylic resin-based laminate film, laminate, and method of manufacturing laminate |
-
1983
- 1983-03-11 JP JP58041317A patent/JPS59166534A/en active Pending
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6099138A (en) * | 1983-11-02 | 1985-06-03 | Mitsui Petrochem Ind Ltd | Undercoating agent for coating of polyolefin molded article |
JPS6336624B2 (en) * | 1983-11-02 | 1988-07-21 | Mitsui Petrochemical Ind | |
US4863988A (en) * | 1986-03-18 | 1989-09-05 | Mitsui Petrochemical Industries, Ltd. | Composition for curable paints |
JPH04136042A (en) * | 1990-09-28 | 1992-05-11 | Ube Ind Ltd | Surface treatment of polyolefin molding to be coated |
US5491191A (en) * | 1992-04-06 | 1996-02-13 | E. I. Du Pont De Nemours And Company | Stable chlorosulfonated resin latex |
US5559182A (en) * | 1992-04-06 | 1996-09-24 | E. I. Du Pont De Nemours And Company | Stable chlorosulfonated resin latex |
US5559181A (en) * | 1992-04-06 | 1996-09-24 | E. I. Du Pont De Nemours And Company | Stable chlorosulfonated resin latex |
US5594063A (en) * | 1992-04-06 | 1997-01-14 | E. I. Du Pont De Nemours And Company | Stable chlorosulfonated resin latex related applications |
JP2010137415A (en) * | 2008-12-10 | 2010-06-24 | Mitsubishi Rayon Co Ltd | Acrylic resin-based laminate film, laminate, and method of manufacturing laminate |
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