JP3314273B2 - Adhesive resin - Google Patents
Adhesive resinInfo
- Publication number
- JP3314273B2 JP3314273B2 JP11751792A JP11751792A JP3314273B2 JP 3314273 B2 JP3314273 B2 JP 3314273B2 JP 11751792 A JP11751792 A JP 11751792A JP 11751792 A JP11751792 A JP 11751792A JP 3314273 B2 JP3314273 B2 JP 3314273B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- adhesive
- vinyl chloride
- chloride resin
- steel sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は金属とプラスチックとの
接着、特に鋼板とポリ塩化ビニル樹脂との接着に適し
た、接着性、加工性、耐水性に優れた接着剤用樹脂に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive resin excellent in adhesiveness, workability and water resistance, which is suitable for bonding metal to plastic, particularly for bonding steel plate to polyvinyl chloride resin.
【０００２】[0002]
【従来の技術】鋼板に塩化ビニル樹脂フィルムをラミネ
−トして塩化ビニル樹脂フィルムラミネ−ト鋼板を製造
するとき、或いは鋼板に塩化ビニル樹脂ゾル塗料を塗布
して塩化ビニル樹脂ゾル被覆鋼板を製造するときの接着
用樹脂として、従来よりメチルメタクリレ−トを主成分
とするアクリル樹脂、塩化ビニル−酢酸ビニル−マレイ
ン酸共重合体等の樹脂が使用されているが、接着性、加
工性、耐水性において十分とは言い難い。2. Description of the Related Art When manufacturing a vinyl chloride resin film laminated steel sheet by laminating a vinyl chloride resin film on a steel sheet, or manufacturing a vinyl chloride resin sol coated steel sheet by applying a vinyl chloride resin sol paint to the steel sheet. As the bonding resin used for this purpose, conventionally, resins such as acrylic resin containing methyl methacrylate as a main component and vinyl chloride-vinyl acetate-maleic acid copolymer have been used. It is hard to say that the water resistance is sufficient.
【０００３】この製造の際、接着時の温度を高くして塩
化ビニル樹脂を溶融させることによって、接着剤との親
和性を高めて接着強度を向上させることは可能である
が、熱エネルギ−が増大してコストアップにつながった
り、また鋼板に塩化ビニル樹脂フィルムをラミネ−トす
る場合は、接着時に高温になりすぎると塩化ビニル樹脂
フィルムを熱軟化させるためエンボス模様が消え、不良
製品が発生しやすくなる。[0003] In this production, it is possible to increase the affinity with the adhesive and improve the bonding strength by increasing the temperature at the time of bonding and melting the vinyl chloride resin, but the heat energy is reduced. When laminating a vinyl chloride resin film on a steel sheet, if the temperature is too high at the time of bonding, the embossed pattern disappears due to the thermal softening of the vinyl chloride resin film, resulting in defective products. It will be easier.
【０００４】また、接着温度を低くするためにアクリル
樹脂の共重合成分としてカルボン酸、グリシジル基含有
モノマ−、塩基性モノマ−等を共重合させ接着性を向上
させる手法があるが、塩化ビニル樹脂との接着性をより
向上させるためメチルメタクリレ−トを主成分としてい
るのでＴｇが高く加工性に劣る欠点がある。一方、加工
性を向上させるためにイソフタル酸、テレフタル酸、エ
チレングリコ−ル、ネオペンチルグリコ−ル等を主成分
とした高分子ポリエステル樹脂を主成分とする接着剤用
組成物が提案されているが、耐水性に劣る欠点がある。In order to lower the bonding temperature, there is a method of improving the adhesiveness by copolymerizing a carboxylic acid, a monomer containing a glycidyl group, a basic monomer, etc. as a copolymer component of an acrylic resin. Since methyl methacrylate is used as a main component in order to further improve the adhesiveness with Tg, there is a disadvantage that Tg is high and processability is inferior. On the other hand, in order to improve processability, a composition for an adhesive mainly comprising a high-molecular polyester resin mainly composed of isophthalic acid, terephthalic acid, ethylene glycol, neopentyl glycol or the like has been proposed. However, there is a disadvantage that the water resistance is poor.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、鋼板
と塩化ビニル樹脂との接着に特に適した、低温での接着
力、加工性、耐水性に優れた接着剤用樹脂を提供するこ
とにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a resin for an adhesive which is particularly suitable for bonding a steel plate to a vinyl chloride resin and which has excellent low-temperature adhesion, workability and water resistance. It is in.
【０００６】[0006]
【課題を解決するための手段】本発明は、 （ａ）メチルメタクリレ−ト ７０〜９９．９重量％ （ｂ）イソシアネ−トエチルメタクリレ−ト ０．１〜
５重量％ （ｃ）その他の共重合可能なビニルモノマ− ０〜２
９．９重量％ を共重合させて得られるイソシアネ−ト基含有アクリル
樹脂（Ｉ）に、アルキレンイミン（II）を付加反応させ
て得られる接着剤用樹脂である。According to the present invention, (a) methyl methacrylate 70 to 99.9% by weight (b) isocyanate ethyl methacrylate 0.1 to
5% by weight (c) Other copolymerizable vinyl monomers 0 to 2
An adhesive resin obtained by subjecting an isocyanate group-containing acrylic resin (I) obtained by copolymerizing 9.9% by weight to an alkylene imine (II) to an addition reaction.
【０００７】本発明を詳しく説明する。本発明における
イソシアネ−ト基含有アクリル樹脂（Ｉ）の（ａ）成分
のメチルメタクリレ−トは７０〜９９．９重量％の範囲
で用いられるが、７０重量％以下では塩化ビニル樹脂と
の接着性が劣り、９９．９重量％以上では低温での接着
性、加工性が劣り好ましくなく。より好ましい範囲は８
０〜９９．５重量％である。また、イソシアネ−ト基含
有アクリル樹脂（Ｉ）の（ｂ）成分のイソシアネ−トエ
チルメタクリレ−トは０．１〜５重量％の範囲で用いら
れるが、０．１重量％以下では加工性、耐水性が劣り、
５重量％以上では安定性が悪くゲル化しやすくなるので
好ましくなく、より好ましい範囲は０．１〜３重量％で
ある。イソシアネ−ト基含有アクリル樹脂（Ｉ）の
（ｃ）成分のその他の共重合可能なビニルモノマ−は０
〜２９．９重量％の範囲で使用しても構わないが、２
９．９重量％以上使用すると塩化ビニルとの接着性が低
下するため好ましくない。The present invention will be described in detail. In the present invention, methyl methacrylate as the component (a) of the isocyanate group-containing acrylic resin (I) is used in the range of 70 to 99.9% by weight. If it is not less than 99.9% by weight, the adhesiveness and workability at low temperatures are inferior, which is not preferable. A more preferred range is 8
0 to 99.5% by weight. The isocyanate ethyl methacrylate (b) component of the isocyanate group-containing acrylic resin (I) is used in the range of 0.1 to 5% by weight. , Poor water resistance,
If it is 5% by weight or more, it is not preferable because it is inferior in stability and gelation easily occurs, and a more preferable range is 0.1 to 3% by weight. The other copolymerizable vinyl monomer of the component (c) of the isocyanate group-containing acrylic resin (I) is 0.
Although it may be used in the range of 29.9% by weight,
If it is used in an amount of 9.9% by weight or more, it is not preferable because the adhesion to vinyl chloride is reduced.
【０００８】（ｃ）成分の具体例としては、アクリル酸
メチル、（メタ）アクリル酸エチル、（メタ）アクリル
酸プロピル、（メタ）アクリル酸ブチル、（メタ）アク
リル酸−２−エチルヘキシル、（メタ）アクリル酸ラウ
リル、スチレン、α−メチルスチレン、ｐ−ｔｅｒｔ−
ブチルスチレン、ジメチルスチレン、ビニルトルエン、
（メタ）アクリルアミド、Ｎ−メチロ−ル（メタ）アク
リルアミド、ブトキシ（メタ）アクリルアミド、２−ヒ
ドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシ
プロピル（メタ）アクリレ−ト、３−ヒドロキシブチル
（メタ）アクリレ−ト、４−ヒドロキシブチル（メタ）
アクリレ−ト、３−クロロ−２−ヒドロキシプロピル
（メタ）アクリレ−ト、ジ−２−ヒドロキシエチルフマ
レ−ト、モノ−２−ヒドロキシエチル−モノブチルフマ
レ−ト、ポリエチレングリコ−ルモノ（メタ）アクリレ
−ト、ポリプロピレングリコ−ルモノ（メタ）アクリレ
−ト、「プラクセルＦＭないしはＦＡモノマ−」〔商品
名；ダイセル化学（株）製のカプロラクトン付加モノマ
−〕、ジメチルアミノエチル（メタ）アクリレ−ト、ジ
エチルアミノエチル（メタ）アクリレ−ト、更には（メ
タ）アクリロニトリル、酢酸ビニル、マレイン酸ジエチ
ル、マレイン酸ジブチル、フマル酸ジブチル、イタコン
酸ジエチル又はイタコン酸ジブチル等である。As specific examples of the component (c), methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylate ) Lauryl acrylate, styrene, α-methylstyrene, p-tert-
Butylstyrene, dimethylstyrene, vinyltoluene,
(Meth) acrylamide, N-methylol (meth) acrylamide, butoxy (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) Acrylate, 4-hydroxybutyl (meth)
Acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl-monobutyl fumarate, polyethylene glycol mono (meth) acrylate , Polypropylene glycol mono (meth) acrylate, "Placcel FM or FA monomer" (trade name; caprolactone-added monomer manufactured by Daicel Chemical Industries, Ltd.), dimethylaminoethyl (meth) acrylate, diethylaminoethyl (Meth) acrylate, furthermore, (meth) acrylonitrile, vinyl acetate, diethyl maleate, dibutyl maleate, dibutyl fumarate, diethyl itaconate or dibutyl itaconate.
【０００９】イソシアネ−ト基含有樹脂溶液（Ｉ）は通
常の溶液重合法で製造できる。重合に使用される溶剤
は、トルエン、キシレン等の芳香族系；メタノ−ル、エ
タノ−ル、ｎ−ブタノ−ル、ｉ−ブタノ−ル等のアルコ
−ル系；メチルエチルケトン、メチルイソブチルケト
ン、シクロヘキサノン等のケトン系；酢酸エチル、酢酸
ブチル等のエステル系；メチルセロソルブ、エチルセロ
ソルブ、ブチルセロソルブ等のセロソルブ系の溶剤であ
る。重合に使用される開始剤としてはアゾビスイソブチ
ロニトリル、アゾビスイソバレロニトリル等のアゾ系、
ベンゾイルパ−オキサイド、クメンハイドロパ−オキサ
イド等の過酸化物系が用いられる。さらに、重合度の調
節のために、ｎ−ドデシルメルカプタン、２−メルカプ
トエタノ−ル等が必要に応じ用いられる。イソシアネ−
ト基含有アクリル樹脂（Ｉ）の数平均分子量は接着性、
安定性の点から１０，０００〜１２０，０００の範囲が
好ましい。The isocyanate group-containing resin solution (I) can be produced by a usual solution polymerization method. Solvents used for polymerization include aromatics such as toluene and xylene; alcohols such as methanol, ethanol, n-butanol and i-butanol; methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Ketones such as ethyl acetate and butyl acetate; and cellosolve solvents such as methyl cellosolve, ethyl cellosolve and butyl cellosolve. As the initiator used for the polymerization, azobisisobutyronitrile, azo-based azobisisovaleronitrile and the like,
Peroxides such as benzoyl peroxide and cumene hydroperoxide are used. Further, n-dodecyl mercaptan, 2-mercaptoethanol, and the like are used as needed to adjust the degree of polymerization. Isocyanate
The number average molecular weight of the acrylic resin (I) containing
The range of 10,000 to 120,000 is preferable from the viewpoint of stability.
【００１０】本発明の接着剤用樹脂は、上記の如くして
重合して得たイソシアネ−ト基含有樹脂（Ｉ）溶液にア
ルキレンイミンを添加し、付加反応させるて製造でき
る。このアルキレンイミンとしては、例えばエチレンイ
ミン、プロピレンイミン、ブチレンイミン等が使用でき
る。The resin for an adhesive of the present invention can be produced by adding an alkylene imine to an isocyanate group-containing resin (I) solution obtained by polymerization as described above, followed by an addition reaction. As the alkylene imine, for example, ethylene imine, propylene imine, butylene imine and the like can be used.
【００１１】以上のようにして得られた本発明の接着剤
用樹脂には、接着剤に用いる際に、エポキシ樹脂、フェ
ノ−ル樹脂を用途に応じ適量加えるのが望ましい。エポ
キシ樹脂としては、１分子中に２個以上のエポキシ基を
有する、例えば、ビスフェノ−ルＡ型エポキシ樹脂、ビ
スフェノ−ルＦ型エポキシ樹脂、ノボラック型エポキシ
樹脂、オキシ安息香酸のグリシジルエステルエ−テル型
エポキシ樹脂、ジアミノフェニルメタンのグリシジルエ
−テル型エポキシ樹脂等がある。これらのエポキシ樹脂
は単独、もしくは２種以上混合しても良い。例えば、現
在工業的によく用いられており生産量も多い塩化ビニル
樹脂ラミネ−ト鋼板用接着剤の場合は、比較的低分子量
のエポキシ樹脂、例えばエポン８２８（シェル化学製）
を本発明の接着剤用樹脂に対して固形分比で１〜１０％
程度加えるのが適当である。When the adhesive resin of the present invention obtained as described above is used as an adhesive, it is desirable to add an appropriate amount of an epoxy resin or a phenol resin according to the intended use. Examples of the epoxy resin include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolak type epoxy resin, and a glycidyl ester ether of oxybenzoic acid having two or more epoxy groups in one molecule. Epoxy resin and glycidyl ether type epoxy resin of diaminophenylmethane. These epoxy resins may be used alone or in combination of two or more. For example, in the case of an adhesive for a vinyl chloride resin laminated steel sheet which is currently used industrially and has a large production amount, an epoxy resin having a relatively low molecular weight, for example, Epon 828 (manufactured by Shell Chemical)
1 to 10% by solid content ratio with respect to the adhesive resin of the present invention.
It is appropriate to add a degree.
【００１２】また、フェノ−ル樹脂としては、特にレゾ
−ル型のフェノ−ル樹脂が好適で、その使用量は本発明
の接着剤用樹脂に対して固形分比で１〜１０％程度が適
当である。本発明の接着剤用樹脂には、フタル酸ジオク
チル（ＤＯＰ）、リン酸トリクレジル（ＴＣＰ）等の可
塑剤、タルクシリカ、炭酸カルシウム等の充填剤の添加
も可能である。更に、特に低温接着性をアップするため
には脂肪族ポリアミン、複素環ジアミン等のアミン化合
物、又は２−エチル−４−メチルイミダゾ−ル等のイミ
ダゾ−ル誘導体が硬化剤として必要に応じ加えられる。As the phenolic resin, a resole type phenolic resin is particularly preferable, and the amount of the phenolic resin used is about 1 to 10% as a solid content ratio with respect to the adhesive resin of the present invention. Appropriate. It is also possible to add a plasticizer such as dioctyl phthalate (DOP) and tricresyl phosphate (TCP) and a filler such as talc silica and calcium carbonate to the adhesive resin of the present invention. Further, in order to improve the low-temperature adhesiveness, an amine compound such as an aliphatic polyamine or a heterocyclic diamine, or an imidazole derivative such as 2-ethyl-4-methylimidazole is added as a curing agent as needed. .
【００１３】以上の配合樹脂及び添加剤を適当な有機溶
剤にて溶解させ、液状接着剤を形成する。ここで使用す
る溶剤としては、接着剤の塗工性及び使用用途ごとの適
性により選ばれる。例えば、本発明の主たる用途である
塩化ビニル樹脂ラミネ−ト鋼板用接着剤の場合は、加熱
処理した軟質塩化ビニル樹脂のラミネ−ト時の濡れ効果
増大等を考慮に入れ、高沸点及び低沸点混合溶媒系が望
ましい。高沸点溶剤としては沸点１００℃以上のトルエ
ン、キシレン、シクロヘキサノン、エチルセロソルブ等
であり、低沸点溶剤としては沸点８０℃以下の塩化メチ
レン、酢酸エチル、メチルエチルケトン（ＭＥＫ）等で
ある。The above-mentioned compounded resin and additives are dissolved in a suitable organic solvent to form a liquid adhesive. The solvent used here is selected depending on the coating properties of the adhesive and the suitability for each intended use. For example, in the case of an adhesive for a vinyl chloride resin laminated steel sheet which is a main use of the present invention, a high boiling point and a low boiling point are considered in consideration of an increase in the wetting effect at the time of laminating a heat-treated soft vinyl chloride resin. Mixed solvent systems are preferred. Examples of the high boiling solvent include toluene, xylene, cyclohexanone, and ethyl cellosolve having a boiling point of 100 ° C. or more, and examples of the low boiling solvent include methylene chloride, ethyl acetate, and methyl ethyl ketone (MEK) having a boiling point of 80 ° C. or less.
【００１４】接着剤の塗布量は、各用途ごとに必要最小
限の膜厚になるよう塗布するが、塩化ビニル樹脂ラミネ
−ト鋼板の場合、軟質塩化ビニル樹脂と鋼板を強固に接
着させるための接着剤塗布量は、乾燥樹脂量として１〜
３０ｇ／ｍ2が好ましい。１ｇ／ｍ2未満では十分な接着
性が発現せず、３０ｇ／ｍ2を超えると溶剤揮発時に不
具合を生じ塗布表面状態が劣るようになる。The amount of the adhesive to be applied is set so as to have a minimum required film thickness for each application. In the case of a vinyl chloride resin laminated steel sheet, the adhesive is used to firmly bond the soft vinyl chloride resin and the steel sheet. The amount of adhesive applied is 1 to
30 g / m 2 is preferred. If it is less than 1 g / m 2 , sufficient adhesiveness will not be exhibited, and if it exceeds 30 g / m 2 , a problem will occur when the solvent is volatilized, and the coated surface state will be inferior.
【００１５】[0015]
【実施例】以下、本発明を具体的に説明するため実施例
及び比較例をあげて説明するが、本発明はこれによって
限定されるものではない。尚、各例中の部は重量％であ
る。EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The parts in each example are% by weight.
【００１６】実施例１ 撹拌機、温度計、還流冷却器、窒素導入管および滴下ロ
−トを備えたフラスコにメチルメタクリレ−ト３９０
部、イソシアネ−トエチルメタクリレ−ト１０部、トル
エン１６０部、ｉ−プロピルアルコ−ル１６０部、及び
アゾビスイソブチロニトリル０．４部を入れ、８０℃に
昇温した後、トルエン４００部にアゾビスイソブチロニ
トリル４部を溶解した混合液を４時間かけて滴下し、追
加アゾビスイソブチロニトリルを０．４部づつ３回に分
け添加して重合を終え、次いでトルエンを２１２部加え
固形分３０％の共重合体溶液を得た。この共重合体溶液
を２５℃に冷却後エチレンイミンを２．７７部加え、１
時間撹拌後７０℃に昇温し６時間付加反応させた。反応
終了後、減圧蒸留装置を取り付けｉ−プロプルアルコ−
ルと共に未反応のエチレンイミンを系外へ留出させ、不
揮発分をメチルエチルケトンで３０％に調整し本発明の
接着用樹脂溶液を得た。得られた樹脂はＧＰＣによる数
平均分子量が４２，０００であった。Example 1 Methyl methacrylate 390 was placed in a flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube and dropping funnel.
Parts, 10 parts of isocyanate ethyl methacrylate, 160 parts of toluene, 160 parts of i-propyl alcohol, and 0.4 part of azobisisobutyronitrile. A mixture of 4 parts of azobisisobutyronitrile was added dropwise to the mixture over 4 hours, and additional azobisisobutyronitrile was added in three portions of 0.4 part each to complete the polymerization, and then toluene was added. 212 parts were added to obtain a copolymer solution having a solid content of 30%. The copolymer solution was cooled to 25 ° C., and 2.77 parts of ethyleneimine was added.
After stirring for an hour, the temperature was raised to 70 ° C. and an addition reaction was performed for 6 hours. After completion of the reaction, a vacuum distillation apparatus was attached and i-propyl alcohol
The unreacted ethyleneimine was distilled out of the system together with the solvent, and the nonvolatile content was adjusted to 30% with methyl ethyl ketone to obtain an adhesive resin solution of the present invention. The obtained resin had a number average molecular weight by GPC of 42,000.
【００１７】この樹脂溶液１００部に対しフェノ−ル樹
脂（群栄化学社製：レジトップＰＬ−２８２２）を１．
３部加え接着剤配合物を調製し、これをクロム処理鋼板
に膜厚５μになるように塗布し２１０℃で１分間焼き付
けし、その直後に２５０μ厚の塩化ビニル樹脂シ−トを
貼り合わせ冷却して塩化ビニル樹脂ラミネ−ト鋼板を得
た、この接着性能は表１の実施例１の欄に示す様に良好
であった。To 100 parts of this resin solution, a phenol resin (Regitop PL-2822, manufactured by Gunei Chemical Co., Ltd.) was used.
3 parts were added to prepare an adhesive composition, which was applied to a chromium-treated steel sheet so as to have a thickness of 5 μm and baked at 210 ° C. for 1 minute. Immediately thereafter, a 250 μm-thick vinyl chloride resin sheet was attached and cooled. Thus, a vinyl chloride resin laminated steel sheet was obtained. The adhesive performance was good as shown in the column of Example 1 in Table 1.
【００１８】実施例２〜５ 実施例１と同様の製法で、表１の実施例２〜５の欄に示
す成分を用いて接着用樹脂を製造した。そして実施例１
と同様に接着剤組成物を調製し、実施例１と同様にして
塩化ビニル樹脂ラミネ−ト鋼板を作成し、接着性能の評
価を行った。結果は表１に示すように良好であった。Examples 2 to 5 Adhesive resins were produced in the same manner as in Example 1 using the components shown in the columns of Examples 2 to 5 in Table 1. And Example 1
In the same manner as in Example 1, an adhesive composition was prepared. In the same manner as in Example 1, a vinyl chloride resin-laminated steel sheet was prepared, and the adhesive performance was evaluated. The results were good as shown in Table 1.
【００１９】比較例１ 撹拌機、温度計、還流冷却器、窒素導入管および滴下ロ
−トを備えたフラスコにメチルメタクリレ−ト３９９．
８部、イソシアネ−トエチルメタクリレ−ト０．２部、
トルエン１６０部、ｉ−プロピルアルコ−ル１６０部、
及びアゾビスイソブチロニトリル０．４部を加えて８０
℃に昇温し、次いでトルエン４００部にアゾビスイソブ
チロニトリル４部を溶解した混合液を４時間かけて滴下
し、追加アゾビスイソブチロニトリルを０．４部づつ３
回に分け添加し重合を終え、次いでトルエンを２１２部
加え固形分３０％の共重合体溶液を得た。この共重合体
溶液を２５℃に冷却し、エチレンイミンを０．０６部加
え１時間撹拌し、その後７０℃に昇温し６時間付加反応
させた。反応終了後、減圧蒸留装置を取り付けｉ−プロ
ピルアルコ−ルと共に未反応のエチレンイミンを系外へ
留出させ、不揮発分をメチルエチルケトンで３０％に調
整したアクリル樹脂溶液を得た。得られた樹脂はＧＰＣ
による数平均分子量が３９，０００であった。COMPARATIVE EXAMPLE 1 In a flask equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube and dropping funnel, methyl methacrylate 399.
8 parts, isocyanate ethyl methacrylate 0.2 part,
160 parts of toluene, 160 parts of i-propyl alcohol,
And 0.4 parts of azobisisobutyronitrile were added to give 80
C., and a mixture of 4 parts of azobisisobutyronitrile dissolved in 400 parts of toluene was added dropwise over 4 hours. Additional azobisisobutyronitrile was added in 0.4 parts by 3 parts.
The polymerization was completed by adding in several portions, and then 212 parts of toluene was added to obtain a copolymer solution having a solid content of 30%. The copolymer solution was cooled to 25 ° C., 0.06 parts of ethyleneimine was added, and the mixture was stirred for 1 hour. Thereafter, the temperature was increased to 70 ° C., and an addition reaction was performed for 6 hours. After completion of the reaction, unreacted ethyleneimine was distilled out of the system together with i-propyl alcohol by attaching a vacuum distillation apparatus to obtain an acrylic resin solution in which the nonvolatile content was adjusted to 30% with methyl ethyl ketone. The obtained resin is GPC
According to the number average molecular weight was 39,000.
【００２０】この樹脂溶液１００部に対しフェノ−ル樹
脂（群栄化学社製：レジトップＰＬ−２８２２）を１．
３部加え接着剤配合物を調製し、これをクロム処理鋼板
に膜厚５μになるように塗布し２１０℃で１分間焼き付
けし、その直後に２５０μ厚の塩化ビニル樹脂シ−トを
張り合わせ冷却して塩化ビニル樹脂ラミネ−ト鋼板を得
た。この接着性能は、表１の比較例１の欄に示すように
不十分であった。A phenol resin (Regitop PL-2822 manufactured by Gunei Chemical Co., Ltd.) was added to 100 parts of the resin solution.
3 parts were added to prepare an adhesive composition, which was applied to a chromium-treated steel sheet to a thickness of 5 μm and baked at 210 ° C. for 1 minute. Immediately thereafter, a 250 μm-thick vinyl chloride resin sheet was laminated and cooled. Thus, a vinyl chloride resin laminated steel sheet was obtained. This adhesive performance was insufficient as shown in the column of Comparative Example 1 in Table 1.
【００２１】比較例２〜３ 比較例１と同様の製法で、表１の比較例２〜３の欄に示
す成分を用いて接着用樹脂を製造し、比較例１と同様に
接着剤組成物を調製し、比較例１と同様にして塩化ビニ
ル樹脂ラミネ−ト鋼板を作成し、接着性能の評価を行っ
た。結果は表１に示すように不十分であった。Comparative Examples 2 to 3 An adhesive resin was produced in the same manner as in Comparative Example 1 using the components shown in the columns of Comparative Examples 2 to 3 in Table 1, and an adhesive composition was prepared in the same manner as in Comparative Example 1. Was prepared, and a vinyl chloride resin-laminated steel sheet was prepared in the same manner as in Comparative Example 1, and the adhesion performance was evaluated. The results were inadequate as shown in Table 1.
【００２２】[0022]
【表１】 [Table 1]
【００２３】実施例、比較例で使用した接着性評価方法
は次ぎのとおりである。 初期接着性：塩化ビニル樹脂ラミネ−ト鋼板の塩化ビニ
ル樹脂面を５ｍｍ間隔の井桁にカットし裏面よりエリク
セン押出し試験機で８ｍｍ押出し後の接着状態。 沸水後の接着性：塩化ビニル樹脂ラミネ−ト鋼板を１０
０℃×３時間沸水に浸漬した後エリクセン押し出し試験
機で８ｍｍ押し出し後の接着状態。 低温加工性：塩化ビニル樹脂ラミネ−ト鋼板の塩化ビニ
ル樹脂面をカットし０℃に冷却後カット部を屈曲試験機
で２ｍｍφ、３６０°折り曲げ後カット部の接着状態。 ピ−リング強度：塩化ビニル樹脂ラミネ−ト鋼板を１ｍ
ｍ巾にカットしテンシロン（オリエンテック社製）にて
１８０°ピ−リング強度Ｋｇ／ｃｍ。 なお、初期接着性、沸水後接着性及び低温加工性の判定
は５段階法で行った。そして判定基準は完全ハガレのも
のを１とし、ハガレなしのものを５とした。The methods for evaluating the adhesiveness used in the examples and comparative examples are as follows. Initial adhesiveness: Adhesion state after cutting the vinyl chloride resin surface of the vinyl chloride resin laminated steel sheet into 5 mm spaced crossbeams and extruding 8 mm from the back side with an Erichsen extrusion tester. Adhesion after boiling water: 10 sheets of vinyl chloride resin laminated steel sheet
Bonded state after immersion in boiling water at 0 ° C. × 3 hours and extrusion of 8 mm with an Erichsen extrusion tester. Low-temperature workability: The bonded state of the cut portion after cutting the vinyl chloride resin surface of the vinyl chloride resin laminated steel sheet, cooling it to 0 ° C., bending the cut portion with a bending tester by 2 mmφ, and 360 °. Peeling strength: 1m of vinyl chloride resin laminated steel sheet
Cut to m width and 180 ° peeling strength Kg / cm with Tensilon (manufactured by Orientec). In addition, the initial adhesiveness, the adhesiveness after boiling water, and the low-temperature processability were determined by a five-step method. The criteria were 1 for complete peeling and 5 for no peeling.
【００２４】[0024]
【発明の効果】本発明の接着剤用樹脂は、特に鋼板とポ
リ塩化ビニル樹脂との接着に有用であり、接着性、加工
性、耐水性に優れた特性を発揮する。したがって、本発
明の接着剤用樹脂を用いることにより、優れた塩化ビニ
ル樹脂フィルムラミネ−ト鋼板、塩化ビニル樹脂ゾル被
覆鋼板を製造することができる。The resin for an adhesive of the present invention is particularly useful for bonding a steel plate to a polyvinyl chloride resin, and exhibits excellent properties such as adhesiveness, workability and water resistance. Therefore, by using the resin for an adhesive of the present invention, an excellent vinyl chloride resin film laminated steel sheet and a vinyl chloride resin sol-coated steel sheet can be manufactured.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 木戸 厚一路 愛知県名古屋市東区砂田橋四丁目１番60 号 三菱レイヨン株式会社 商品開発研 究所内 (56)参考文献 特開 平４−4275（ＪＰ，Ａ) 特開 平３−139584（ＪＰ，Ａ) 特開 昭61−145268（ＪＰ，Ａ) 特開 昭58−171459（ＪＰ，Ａ) 特開 昭59−187068（ＪＰ，Ａ) 特開 昭63−12602（ＪＰ，Ａ) 特開 平５−287250（ＪＰ，Ａ) 特開 平５−271635（ＪＰ，Ａ) 特表 昭57−502004（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C09J 133/04,175/04 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Katsuichi Kido 4-160 Sunadabashi, Higashi-ku, Nagoya City, Aichi Prefecture Mitsubishi Rayon Co., Ltd. Product Development Laboratory (56) References JP-A-4-4275 (JP, A) JP-A-3-139584 (JP, A) JP-A-61-145268 (JP, A) JP-A-58-171459 (JP, A) JP-A-59-187068 (JP, A) JP-A-63 -12602 (JP, A) JP-A-5-287250 (JP, A) JP-A-5-271635 (JP, A) Tokushou 57-502004 (JP, A) (58) Fields investigated (Int. . 7, DB name) C09J 133 / 04,175 / 04
Claims (2)
９．９重量％ （ｂ）イソシアネ−トエチルメタクリレ−ト ０．１〜
５重量％ （ｃ）その他共重合可能なビニルモノマ− ０〜２９．
９重量％ を共重合させて得られるイソシアネ−ト基含有アクリル
樹脂（Ｉ）に、アルキレンイミン（II）を付加反応させ
て得られる接着剤用樹脂。(A) methyl methacrylate 70 to 9
9.9% by weight (b) Isocyanate ethyl methacrylate 0.1 to
5% by weight (c) Other copolymerizable vinyl monomers 0 to 29.
An adhesive resin obtained by adding an alkyleneimine (II) to an isocyanate group-containing acrylic resin (I) obtained by copolymerizing 9% by weight of the resin.
（１）の数平均分子量が１０，０００〜１２０，０００
である請求項１記載の接着剤用樹脂。2. The number average molecular weight of the isocyanate group-containing acrylic resin (1) is 10,000 to 120,000.
The resin for an adhesive according to claim 1, which is:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11751792A JP3314273B2 (en) | 1992-05-11 | 1992-05-11 | Adhesive resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11751792A JP3314273B2 (en) | 1992-05-11 | 1992-05-11 | Adhesive resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05311136A JPH05311136A (en) | 1993-11-22 |
| JP3314273B2 true JP3314273B2 (en) | 2002-08-12 |
Family
ID=14713732
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11751792A Expired - Lifetime JP3314273B2 (en) | 1992-05-11 | 1992-05-11 | Adhesive resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3314273B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1125156C (en) * | 2000-08-04 | 2003-10-22 | 顺德市迪邦家具实业有限公司 | Water-soluble liquid adhesive for locating and its preparing process |
| KR100570158B1 (en) * | 2005-11-25 | 2006-04-11 | 주식회사 에스아이켐 | One component adhesive composition for a film laminated steel sheet and the making method thereof |
-
1992
- 1992-05-11 JP JP11751792A patent/JP3314273B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05311136A (en) | 1993-11-22 |
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