JPS61155473A - Surface protective agent - Google Patents
Surface protective agentInfo
- Publication number
- JPS61155473A JPS61155473A JP27457884A JP27457884A JPS61155473A JP S61155473 A JPS61155473 A JP S61155473A JP 27457884 A JP27457884 A JP 27457884A JP 27457884 A JP27457884 A JP 27457884A JP S61155473 A JPS61155473 A JP S61155473A
- Authority
- JP
- Japan
- Prior art keywords
- terpolymer
- maleic anhydride
- isobutylene
- surface protective
- styrene
- 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.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は表面保護剤に関し、詳しくは塗膜形成に要する
時間が短縮され、合成樹脂製品等の表面に充分な硬度を
付与し得る表面保護剤に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a surface protective agent, and more particularly to a surface protective agent that can shorten the time required to form a coating film and impart sufficient hardness to the surface of synthetic resin products.
従来より、比較的軟質の合成樹脂製品の表面に硬度を付
与し、また紙製品、木製品に防水性を付与するために、
エポキシ樹脂やウレタン樹脂をこれら製品の表面にコー
ティングすることが行なわれている。この表面保護剤と
して用いられているエポキシ樹脂やウレタン樹脂は硬度
を付与する点ではある程度満足し得るものであるが、い
ずれも二液反応型の表面保護剤であるため、混合操作を
必要とし、硬化に要する時間が長く、常温下で用いる場
合に不都合であった。Traditionally, in order to add hardness to the surface of relatively soft synthetic resin products, and to add waterproofness to paper products and wooden products,
The surfaces of these products are coated with epoxy resins or urethane resins. Epoxy resins and urethane resins used as surface protective agents are somewhat satisfactory in terms of imparting hardness, but since they are both two-part reaction type surface protective agents, mixing operations are required. It takes a long time to cure, which is inconvenient when used at room temperature.
そこで、上記欠点を解消した表面保護剤を開発すべく鋭
意検討した結果、イソブチレン−無水マレイン酸−スチ
レン三元共重合体が充分な塗膜硬度、防水性等を有して
いることを見い出し、この知見に基づいて本発明を完成
した。Therefore, as a result of intensive research to develop a surface protective agent that eliminates the above drawbacks, we discovered that isobutylene-maleic anhydride-styrene terpolymer has sufficient coating hardness, waterproofness, etc. The present invention was completed based on this knowledge.
すなわち、本発明はイソブチレン−無水マレイン酸−ス
チレン三元共重合体からなる表面保護剤である。That is, the present invention is a surface protective agent comprising an isobutylene-maleic anhydride-styrene terpolymer.
本発明の素材となるイソブチレン−無水マレイン酸−ス
チレン三元共重合体はイソブチレン、無水マレイン酸お
よびスチレンを種々の方法により共重合させることによ
り得られるが、通常は次の如き方法により製造される。The isobutylene-maleic anhydride-styrene terpolymer that is the material of the present invention can be obtained by copolymerizing isobutylene, maleic anhydride, and styrene by various methods, but it is usually produced by the following method. .
各原料の仕込み割合は特に制限はなく、目的とする共重
合体の物性等を考慮して適宜定めれば良い０通常はイソ
ブチレン１モルに対して無水マレイン酸０．５〜１．５
モル、好ましくは０．７〜１．２モル、スチレン０．０
１〜１．５モル、好ましくは０．０５〜１．２モルであ
る。There is no particular limit to the charging ratio of each raw material, and it may be determined as appropriate in consideration of the physical properties of the desired copolymer. Usually, maleic anhydride is 0.5 to 1.5 to 1 mole of isobutylene.
mol, preferably 0.7-1.2 mol, styrene 0.0
The amount is 1 to 1.5 mol, preferably 0.05 to 1.2 mol.
また、共重合に際して触媒が用いられ、この場合の触媒
としては種々の触媒が使用し得るが、通常は過酸化ベン
ゾイル、過酸化ラウロイル、クメンパーヒドロオキシド
、ｔ−ブチルヒドロパーオキシド、ジクミルパーオキシ
ドなどの過酸化物、アゾビスイソブチロニトリルなどの
アゾ化合物、過硫酸塩などが挙げられる。触媒の使用量
は全七ツマー１００重量部に対して０．０１〜１０重量
部、好ましくは０．０５〜５重量部である。触媒はその
まま、または希釈して使用する。その添加時期について
は重合の初期に全てを添加してもよく、または重合中に
分割して添加してもよい。In addition, a catalyst is used during copolymerization, and in this case, various catalysts can be used, but usually benzoyl peroxide, lauroyl peroxide, cumene perhydroxide, t-butyl hydroperoxide, dicumyl peroxide, etc. Examples include peroxides such as oxide, azo compounds such as azobisisobutyronitrile, and persulfates. The amount of the catalyst to be used is 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total number of seven months. The catalyst can be used as is or diluted. Regarding the timing of addition, it may be added in its entirety at the beginning of the polymerization, or it may be added in portions during the polymerization.
次に、共重合反応に使用される溶媒としては接種のもの
を挙げることができ、たとえば共重合反応を沈澱重合法
で行なうときに用いる溶媒としては酢酸イソプロピル、
酢酸エチル等がある。この場合は生成する三元共重合体
が溶媒に溶解せず共重合反応系外に沈澱する。一方、共
重合反応を溶液重合法により行なうときに用いる溶媒と
してはメチルエチルケトン、アセトン、トルエン、ベン
ゼン、Ｎ、Ｎ−ジメチルホルムアミド、ジメチルスルホ
キシド、アセトニトリル、ニトロメタン。Next, examples of the solvent used in the copolymerization reaction include inoculated ones.For example, when the copolymerization reaction is carried out by precipitation polymerization, the solvent used is isopropyl acetate,
Examples include ethyl acetate. In this case, the terpolymer produced does not dissolve in the solvent and precipitates outside the copolymerization reaction system. On the other hand, when the copolymerization reaction is carried out by a solution polymerization method, examples of solvents used include methyl ethyl ketone, acetone, toluene, benzene, N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, and nitromethane.
ニトロエタン等がある。この場合は生成する三元共重合
体は溶媒に溶解する。本発明では、三元共重合体を表面
保護剤として使用するため、該三元共重合体力９容媒溶
液として得られれば、そのまま使用できるので、溶液重
合方法が好ましく、特にメチルエチルケトン、アセトン
などが溶媒として好適である。Examples include nitroethane. In this case, the resulting terpolymer is dissolved in the solvent. In the present invention, since the terpolymer is used as a surface protective agent, if the terpolymer is obtained as a 9-volume solution, it can be used as it is, so a solution polymerization method is preferred. In particular, methyl ethyl ketone, acetone, etc. Suitable as a solvent.
上記の如き原料、触媒および溶媒を用いて行なう共重合
反応条件はいずれの方法で行なう場合も反応温度３０〜
２００℃、好ましくは４５〜１５０℃、反応圧力常圧〜
３０ｋｇ／ｃｉＧ、好ましくは常圧〜１０ｋｇ／ｃｄＧ
、反応時間０．５〜２０時間、好ましくは１〜１０時間
が適当である。次いで、溶媒や未反応原料等を除去する
等の通常の後処理を行なうことによりイソブチレン−無
水マレイン酸−スチレン共重合体が得られる。このもの
はイソブチレン繰り返し単位
無水マレイン酸繰り返し単位
スチレン繰り返し単位
からなり、数平均分子量が３０００〜４０００００、好
ましくは５ｏｏｏ〜２０００００程度である。また、繰
り返し単位比はイソブチレン：無水マレイン酸：スチレ
ン＝１：０．５〜１．５：０．０１〜１．５（モル比）
、好ましくはｌ：ｏ、７〜ｔ、ｚ：ｏ、ｏｓ〜１．２（
モル比）である。The conditions for the copolymerization reaction using the above raw materials, catalysts and solvents are as follows:
200°C, preferably 45 to 150°C, reaction pressure normal pressure to
30kg/ciG, preferably normal pressure to 10kg/cdG
A suitable reaction time is 0.5 to 20 hours, preferably 1 to 10 hours. Next, an isobutylene-maleic anhydride-styrene copolymer is obtained by performing usual post-treatments such as removing the solvent and unreacted raw materials. This product consists of repeating isobutylene units, repeating maleic anhydride units, and repeating styrene units, and has a number average molecular weight of about 3,000 to 400,000, preferably about 500 to 200,000. Also, the repeating unit ratio is isobutylene: maleic anhydride: styrene = 1:0.5-1.5:0.01-1.5 (molar ratio)
, preferably l:o, 7~t, z:o, os~1.2(
molar ratio).
このようにして得られるイソブチレン−無水マレイン酸
−スチレン三元共重合体を合成樹脂製品。The isobutylene-maleic anhydride-styrene terpolymer thus obtained is used as a synthetic resin product.
紙、木等の表面に塗布する場合は、該共重合体が可溶な
溶媒に溶解して溶媒溶液として使用される。When applying to the surface of paper, wood, etc., the copolymer is dissolved in a soluble solvent and used as a solvent solution.
溶媒としてはアセトン、メチルエチルケトン、アセトニ
トリル、トルエンなどが挙げられる。上記三元共重合体
の製造方法において、三元共重合体が可溶な溶媒を用い
ている場合は、得られた溶媒溶液をそのまま使用するこ
とができる。塗布方法ははけを用いる方法、スプレ一方
式等いずれでもよい。溶媒溶液中の三元共重合体の濃度
は塗布表面、塗膜厚さ等により適宜決定すれば良いが、
通常１０〜８０重量％、好ましくは２０〜７０重量％で
ある。Examples of the solvent include acetone, methyl ethyl ketone, acetonitrile, and toluene. In the above method for producing a terpolymer, when a solvent in which the terpolymer is soluble is used, the obtained solvent solution can be used as it is. The application method may be any method such as using a brush or spraying. The concentration of the terpolymer in the solvent solution may be determined as appropriate depending on the coating surface, coating thickness, etc.
It is usually 10 to 80% by weight, preferably 20 to 70% by weight.
塗布後、溶媒を揮発させることにより、表面に塗膜が形
成される。塗膜厚さは塗布表面、用途などにより異なる
が、通常０．０１〜１． Ｏｕ程度である。After application, a coating film is formed on the surface by volatilizing the solvent. The coating film thickness varies depending on the coating surface, application, etc., but is usually 0.01 to 1. It is about Ou.
以上の如く、本発明の表面保護剤は二液反応型でないた
め、混合操作を必要とせず、硬化も溶媒除去により容易
に進行する。さらに、得られる表面保護膜は充分な表面
硬度および防水性を有しており、種々の合成樹脂製品２
紙製品９合板などの木等の表面を有効に保護し得るもの
である。As described above, since the surface protective agent of the present invention is not a two-component reaction type, no mixing operation is required, and curing proceeds easily by solvent removal. Furthermore, the surface protective film obtained has sufficient surface hardness and waterproof properties, and can be used for various synthetic resin products.
Paper Product 9 The surface of wood such as plywood can be effectively protected.
したがって、本発明に係るイソブチレン−無水マレイン
酸−スチレン三元共重合体は表面保護剤として極めて有
用である。Therefore, the isobutylene-maleic anhydride-styrene terpolymer of the present invention is extremely useful as a surface protection agent.
次に、本発明を実施例により詳しく説明する。Next, the present invention will be explained in detail with reference to examples.
実施例１
無水マレイン酸６０ｇ、スチレン３１．８ｇ、ｉＭ酸化
ベンゾイル０．６ｇおよびアセトン４６０ ｃｃを１１
オートクレーブに伏込δ、充分に冷却、脱気を行なった
。Example 1 60 g of maleic anhydride, 31.8 g of styrene, 0.6 g of iM benzoyl oxide and 460 cc of acetone were added to 11
It was submerged in an autoclave, sufficiently cooled, and degassed.
次いで、イソブチレン３７ｇを加え、４００ｒ、ｐ、ｍ
、にて攪拌しながら１１０℃で２時間重合反応を行ない
、イソブチレン−無水マレイン酸−スチレン三元共重合
体アセトン溶液を得た。このものの数平均分子量は９３
０００であった。Next, add 37 g of isobutylene and add 400 r, p, m.
A polymerization reaction was carried out at 110° C. for 2 hours with stirring, to obtain an acetone solution of isobutylene-maleic anhydride-styrene terpolymer. The number average molecular weight of this product is 93
It was 000.
得られたアセトン溶液をガラス板上に塗布し、アセトン
を揮発させ、厚さ０．５ Ｋｍの塗膜を形成した。この
塗膜の２０〜１２０℃の動的貯蔵弾性率（表面硬度の指
標）は５〜６ Ｘ １０ ｑｄｙｎｅ／ｃａｌであった
。The obtained acetone solution was applied onto a glass plate, and the acetone was evaporated to form a coating film with a thickness of 0.5 km. The dynamic storage modulus (indicator of surface hardness) of this coating film at 20 to 120°C was 5 to 6 X 10 qdyne/cal.
さらに、得られたアセトン溶液を厚さ５Ｈのポリプロピ
レンシート、ダンボール紙および厚さ２ｎのベニヤ合板
に各々塗布し、アセトンを揮発させて０．５ｍｍの塗膜
を形成した。塗膜の接着性は良好であった。Further, the obtained acetone solution was applied to a polypropylene sheet having a thickness of 5H, cardboard paper, and plywood having a thickness of 2N, respectively, and the acetone was evaporated to form a coating film of 0.5 mm. The adhesion of the coating film was good.
防水性について次の試験を行なった。The following test was conducted regarding waterproofness.
上記で得られたアセトン溶液をトルエンで脱脂処理した
金属試験片（０，８龍×７０龍×１５０寵：５ＰＣＣ−
３Ｄ）にはけで塗布し、室温で充分に乾燥した。このも
のを１０％塩化ナトリウム水溶液に１０日間浸漬した。A metal test piece obtained by degreasing the acetone solution obtained above with toluene (0.8 x 70 x 150: 5PCC-
3D) was applied with a brush and thoroughly dried at room temperature. This product was immersed in a 10% aqueous sodium chloride solution for 10 days.
さびの発生は見られなかった。塗布を行なわなかった試
験片は同様の条件下でさびが発生した。No rust was observed. The test pieces that were not coated developed rust under similar conditions.
Claims (1)
からなる表面保護剤。A surface protection agent consisting of an isobutylene-maleic anhydride-styrene terpolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27457884A JPS61155473A (en) | 1984-12-28 | 1984-12-28 | Surface protective agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27457884A JPS61155473A (en) | 1984-12-28 | 1984-12-28 | Surface protective agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61155473A true JPS61155473A (en) | 1986-07-15 |
| JPH0354145B2 JPH0354145B2 (en) | 1991-08-19 |
Family
ID=17543692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27457884A Granted JPS61155473A (en) | 1984-12-28 | 1984-12-28 | Surface protective agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61155473A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087572A (en) * | 2012-12-18 | 2013-05-08 | 芜湖恒坤汽车部件有限公司 | Surface silanization protection treatment agent for hard aluminum alloy and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5189591A (en) * | 1974-12-23 | 1976-08-05 | ||
| JPS52937A (en) * | 1975-06-24 | 1977-01-06 | Kuraray Co Ltd | Water-soluble coating composition |
-
1984
- 1984-12-28 JP JP27457884A patent/JPS61155473A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5189591A (en) * | 1974-12-23 | 1976-08-05 | ||
| JPS52937A (en) * | 1975-06-24 | 1977-01-06 | Kuraray Co Ltd | Water-soluble coating composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087572A (en) * | 2012-12-18 | 2013-05-08 | 芜湖恒坤汽车部件有限公司 | Surface silanization protection treatment agent for hard aluminum alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0354145B2 (en) | 1991-08-19 |
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