JP3158527B2 - Bending material with cured coating by radiation-curable coating agent - Google Patents
Bending material with cured coating by radiation-curable coating agentInfo
- Publication number
- JP3158527B2 JP3158527B2 JP23797291A JP23797291A JP3158527B2 JP 3158527 B2 JP3158527 B2 JP 3158527B2 JP 23797291 A JP23797291 A JP 23797291A JP 23797291 A JP23797291 A JP 23797291A JP 3158527 B2 JP3158527 B2 JP 3158527B2
- Authority
- JP
- Japan
- Prior art keywords
- cured
- prepolymer
- radiation
- coating
- coating film
- 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 - Fee Related
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、放射線硬化型塗工剤に
よる硬化塗膜を有する屈曲用素材に関する。The present invention relates to a radiation-curable coating agent .
The present invention relates to a bending material having a cured coating film .
【０００２】[0002]
【従来の技術】近年、放射線硬化型塗工剤は、プラスチ
ックや紙、金属等への印刷インキのバインダーおよび表
面保護コーティング剤として、あらゆる分野において利
用されるに至っている。広く利用されている理由とし
て、瞬時硬化特性により生産性に優れている、有機溶剤
を必ずしも必要としないため環境保全に役立つ、耐水・
耐薬品性等の化学的耐性に優れている、そして表面耐擦
傷性等の物理的耐性に優れている、などがあげられる。2. Description of the Related Art In recent years, radiation-curable coating agents have been used in various fields as binders for printing inks on plastics, papers, metals and the like and surface protective coating agents. It is widely used because it has excellent productivity due to its instant curing properties, and because it does not necessarily require an organic solvent, it is useful for environmental protection,
Excellent in chemical resistance such as chemical resistance, and excellent in physical resistance such as surface scratch resistance.
【０００３】表面保護性に優れた硬い塗膜を得る場合、
硬化塗膜の架橋密度を上げるために放射線硬化型塗工剤
の官能基濃度を高くすることが通常行われている。官能
基濃度を高くする方法として、ペンタエリスリトールト
リ（メタ）アクリレート、トリメチロールプロパントリ
（メタ）アクリレート、ジペンタエリスリトールヘキサ
（メタ）アクリレート、等の多官能モノマーを用いるこ
とが考えられる。In order to obtain a hard coating having excellent surface protection properties,
It is common practice to increase the functional group concentration of the radiation-curable coating agent in order to increase the crosslink density of the cured coating. As a method for increasing the functional group concentration, it is conceivable to use a polyfunctional monomer such as pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate.
【０００４】しかしながら、これら多官能モノマーによ
り硬化時の収縮が大きくなり、塗膜に蓄積される内部応
力が大きくなる。そのため硬化塗膜の可撓性および強靱
性に劣り、塗膜にクラックが入りやすくなる欠点があ
る。However, the shrinkage during curing is increased by these polyfunctional monomers, and the internal stress accumulated in the coating film is increased. Therefore, the cured coating film is inferior in flexibility and toughness, and has a defect that the coating film is easily cracked.
【０００５】[0005]
【発明が解決しようとする課題】本発明はこのような問
題点を解決するためになされたもので、その課題とする
ところは、表面保護性に優れ、可撓性および強靱性に優
れた放射線硬化型塗工剤による硬化塗膜を有する屈曲用
素材を提供することにある。SUMMARY OF THE INVENTION The present invention has been made to solve such problems, and it is an object of the present invention to provide a radiation source having excellent surface protection and excellent flexibility and toughness. For bending with a cured coating by a curable coating agent
To provide materials .
【０００６】[0006]
【課題を解決するための手段】本発明はこの課題を解決
するために、可撓性の素材に、プレポリマー分子の両末
端にそれぞれ１つ以上の（メタ）アクリロイル基を有
し、かつ、プレポリマー主鎖の繰り返しユニット中に
（メタ）アクリロイル基を側鎖として有する化合物を少
なくとも１種含む放射線硬化型塗工剤による硬化塗膜を
設けてなることを特徴とする屈曲用素材を提供するもの
である。According to the present invention, there is provided a flexible material having one or more (meth) acryloyl groups at both ends of a prepolymer molecule, and A cured film formed by a radiation-curable coating agent containing at least one compound having a (meth) acryloyl group as a side chain in a repeating unit of the prepolymer main chain is formed.
It is intended to provide a bending material characterized by being provided.
【０００７】以下、本発明を詳細に説明する。プレポリ
マー分子の両末端にそれぞれ１つ以上の（メタ）アクリ
ロイル基を有し、かつ、プレポリマー主鎖の繰り返しユ
ニット中に（メタ）アクリロイル基を側鎖として有する
多官能の化合物は、以下のような分子構造のものがあ
る。Hereinafter, the present invention will be described in detail. A polyfunctional compound having one or more (meth) acryloyl groups at both ends of a prepolymer molecule and having a (meth) acryloyl group as a side chain in a repeating unit of the prepolymer main chain is as follows: Some have such a molecular structure.
【０００８】 n≧２ ａ；（メタ）アクリロイル基 ｂ；２塩基酸、または、ジイソシアネート[0008] n ≧ 2 a; (meth) acryloyl group b; dibasic acid or diisocyanate
【０００９】２塩基酸としては、琥珀酸、グルタール
酸、アジピン酸、スベリン酸、フタル酸、イソフタル
酸、テレフタル酸、等があげられる。The dibasic acids include succinic acid, glutaric acid, adipic acid, suberic acid, phthalic acid, isophthalic acid, terephthalic acid and the like.
【００１０】ジイソシアネートとしては、ヘキサメチレ
ン・ジイソシアネート、２・４−トリレン・ジイソシア
ネート、２・６−トリレン・ジイソシアネート、４・
４’−ジフェニルメタン・ジイソシアネート、ナフチレ
ン・ジイソシアネート、トリジン・ジイソシアネート、
イソホイロン・ジイソシアネート、キシリレン・ジイソ
シアネート、ジシクロヘキシル・ジイソシアネート、リ
ジン・ジイソシアネート、等があげられる。As the diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4.
4'-diphenylmethane diisocyanate, naphthylene diisocyanate, tolidine diisocyanate,
Examples include isofilone diisocyanate, xylylene diisocyanate, dicyclohexyl diisocyanate, and lysine diisocyanate.
【００１１】[0011]
【作用】本発明は、放射線硬化型塗工剤に含まれる以上
のような化合物がプレポリマーであることにより、モノ
マーと比較して、架橋硬化によりポリマー化したときの
収縮が低く抑えられる。かつ、プレポリマー分子の主鎖
の繰り返しユニット中に（メタ）アクリロイル基を側鎖
として有することにより、モノマーと比較して、放射線
硬化型塗工剤としての官能基濃度は同程度に高く、硬化
塗膜の架橋密度も同程度に高くなる。According to the present invention, since the above-mentioned compounds contained in the radiation-curable coating agent are prepolymers, shrinkage when polymerized by crosslinking and curing is suppressed as compared with monomers. In addition, by having a (meth) acryloyl group as a side chain in the repeating unit of the main chain of the prepolymer molecule, the functional group concentration of the radiation-curable coating agent is as high as that of the monomer, and The crosslink density of the coating also increases to the same extent.
【００１２】[0012]
＜実施例１＞厚さ４００μｍの塩ビシートの片面にウレ
タンアクリレート（ダイセル・ＵＣＢ（株）製、「ＥＢ
ＥＣＲＹＬ ２８４」）が５０重量部と、プレポリマー
として、Example 1 A urethane acrylate (manufactured by Daicel UCB Co., Ltd., “EB
ECRYL 284 ") is 50 parts by weight, and as a prepolymer,
【００１３】[0013]
【化１】 Embedded image
【００１４】が５０重量部と、光開始剤（メルク社製、
「ダロキュアー１１７３」）が５重量部よりなる放射線
硬化型塗工剤を、ドライオフセット方式にて硬化後の膜
厚が約２μｍ程度となるように塗工する。And 50 parts by weight of a photoinitiator (Merck,
A radiation-curable coating agent comprising 5 parts by weight of “Darocur 1173”) is applied by a dry offset method so that the film thickness after curing becomes about 2 μm.
【００１５】塗工後引き続き、紫外線照射装置（アイグ
ラフィックス（株）製：メタルハライドランプ１２０W/
cm、２灯）の照射下を通過させ、照射線量約４００mJ/c
m2のエネルギーで塗膜を硬化させた。After the coating, an ultraviolet irradiation apparatus (manufactured by Eye Graphics Co., Ltd .: metal halide lamp 120 W /
cm, 2 lamps), and the irradiation dose is about 400mJ / c
The coating film was cured with an energy of m 2.
【００１６】＜実施例２＞実施例１において、光開始剤
を含まない以外は同様のものを電子線照射装置（日新ハ
イボルテージ（株）製：「キュアトロン」）の照射下を
通過させ、照射線量約４．０Ｍｒａｄのエネルギーで塗
膜を硬化させた。<Example 2> In Example 1, except that the photoinitiator was not contained, the same thing was passed under irradiation of an electron beam irradiation apparatus ("Curetron" manufactured by Nissin High Voltage Co., Ltd.). The coating was cured with an energy of about 4.0 Mrad.
【００１７】＜実施例３＞実施例２において、プレポリ
マーの組成が以下のものであること以外は実施例２と同
様の方法で塗膜を硬化させた。Example 3 A coating film was cured in the same manner as in Example 2 except that the composition of the prepolymer was as follows.
【００１８】[0018]
【化２】 Embedded image
【００１９】＜実施例４＞実施例２において、プレポリ
マーの組成が以下のものであること以外は実施例２と同
様の方法で塗膜を硬化させた。Example 4 A coating film was cured in the same manner as in Example 2 except that the composition of the prepolymer was as follows.
【００２０】[0020]
【化３】 Embedded image
【００２１】＜実施例５＞実施例２において、プレポリ
マーの組成が以下のものであること以外は実施例２と同
様の方法で塗膜を硬化させた。Example 5 A coating film was cured in the same manner as in Example 2 except that the composition of the prepolymer was as follows.
【００２２】[0022]
【化４】 Embedded image
【００２３】＜実施例６＞実施例２において、プレポリ
マーの組成が以下のものであること以外は実施例２と同
様の方法で塗膜を硬化させた。Example 6 A coating film was cured in the same manner as in Example 2 except that the composition of the prepolymer was as follows.
【００２４】[0024]
【化５】 Embedded image
【００２５】＜実施例７＞実施例２において、プレポリ
マーの組成が以下のものであること以外は実施例２と同
様の方法で塗膜を硬化させた。Example 7 A coating film was cured in the same manner as in Example 2 except that the composition of the prepolymer was as follows.
【００２６】[0026]
【化６】 Embedded image
【００２７】＜比較例１＞実施例１において、プレポリ
マーの代わりに以下の組成のものを用いたこと以外は実
施例１と同様の方法で塗膜を硬化させた。Comparative Example 1 A coating film was cured in the same manner as in Example 1, except that the following composition was used instead of the prepolymer.
【００２８】(CH2=CHCOOCH2)3-CCH2OH(CH 2 = CHCOOCH 2 ) 3 -CCH 2 OH
【００２９】＜比較例２＞実施例１において、プレポリ
マーの代わりに以下の組成のものを用いたこと以外は実
施例１と同様の方法で塗膜を硬化させた。Comparative Example 2 A coating film was cured in the same manner as in Example 1 except that the following composition was used instead of the prepolymer.
【００３０】(CH2=CHCOOCH2)3-CCH2CH3 (CH 2 = CHCOOCH 2 ) 3 -CCH 2 CH 3
【００３１】＜比較例３＞実施例１において、プレポリ
マーの代わりに以下の組成のものを用いたこと以外は実
施例１と同様の方法で塗膜を硬化させた。Comparative Example 3 A coating film was cured in the same manner as in Example 1, except that the following composition was used instead of the prepolymer.
【００３２】((CH2=CHCOOCH2)3-CCH2)2-O((CH 2 = CHCOOCH 2 ) 3 -CCH 2 ) 2 -O
【００３３】＜比較例４＞実施例２において、プレポリ
マーの代わりに比較例１の組成のものを用いたこと以外
は実施例２と同様の方法で塗膜を硬化させた。Comparative Example 4 A coating film was cured in the same manner as in Example 2 except that the composition of Comparative Example 1 was used instead of the prepolymer.
【００３４】＜比較例５＞実施例２において、プレポリ
マーの代わりに比較例２の組成のものを用いたこと以外
は実施例２と同様の方法で塗膜を硬化させた。Comparative Example 5 A coating film was cured in the same manner as in Example 2 except that the composition of Comparative Example 2 was used instead of the prepolymer.
【００３５】＜比較例６＞実施例２において、プレポリ
マーの代わりに比較例３の組成のものを用いたこと以外
は実施例２と同様の方法で塗膜を硬化させた。Comparative Example 6 A coating film was cured in the same manner as in Example 2 except that the composition of Comparative Example 3 was used instead of the prepolymer.
【００３６】実施例１〜６、比較例１〜６にて得られた
硬化塗膜をテーバー摩耗試験機（東洋精機製作所（株）
製）を用いて、ＣＳ−１０、加重500g、100 回転の条件
下にて摩耗試験を行い、摩耗の程度はヘーズで評価し
た。また、∠360 に屈曲したときの塗膜の状態をクラッ
クの有無で評価した。The cured coating films obtained in Examples 1 to 6 and Comparative Examples 1 to 6 were applied to a Taber abrasion tester (Toyo Seiki Seisakusho Co., Ltd.)
Was performed under the conditions of CS-10, a load of 500 g, and 100 rotations, and the degree of wear was evaluated by haze. Further, the state of the coating film when bent to # 360 was evaluated by the presence or absence of cracks.
【００３７】[0037]
【表１】 [Table 1]
【００３８】[0038]
【発明の効果】以上に示したように、本発明は、可撓性
の素材に、プレポリマー分子の両末端にそれぞれ１つ以
上の（メタ）アクリロイル基を有し、かつ、プレポリマ
ー主鎖の繰り返しユニット中に（メタ）アクリロイル基
を側鎖として有する化合物を少なくとも１種含む放射線
硬化型塗工剤による硬化塗膜を設けることにより、射線
硬化型塗工剤の硬化時の収縮が低く抑えられ、なおかつ
硬化塗膜の架橋密度は低下しないので、フレキシブルな
柔軟性が要求される屈曲用素材において、表面保護のた
めの印刷およびコーティングを施すことに対する制限を
受けることなく、表面保護性、可撓性、強靱性、耐屈曲
性に優れた硬化塗膜を有する屈曲用素材を得ることがで
きるという、顕著な効果を奏するものである。 As described above, the present invention provides a flexible
One or more at each end of the prepolymer molecule
Having the above (meth) acryloyl group and a prepolymer
-(Meth) acryloyl group in the main chain repeating unit
Containing at least one compound having a side chain
By providing a cured coating with a curable coating agent,
Shrinkage during curing of the curable coating agent is kept low, and
Since the crosslink density of the cured coating does not decrease,
In bending materials that require flexibility,
Restrictions on printing and coating
No surface protection, flexibility, toughness, bending resistance
It is possible to obtain a bending material having a cured coating film with excellent
This has a remarkable effect.
フロントページの続き (56)参考文献 特開 昭60−143993（ＪＰ，Ａ) 特公 昭54−1758（ＪＰ，Ｂ１) 米国特許4371566（ＵＳ，Ａ) Ｌａｋｏｋｒａｓ．Ｍａｔｅｒ．Ｉｋ ｈ Ｐｒｉｍｅｎ．ｖｏｌ．５ ｐ．40 −41 1974 (58)調査した分野(Int.Cl.7，ＤＢ名) C09D 4/00 - 4/06 C08F 299/02 - 299/08 C08G 18/67 - 18/69 C09D 175/16 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)Continuation of front page (56) References JP-A-60-149393 (JP, A) JP-B-54-1758 (JP, B1) US Patent 4,371,566 (US, A) Lakokras. Mater. Ikh Primen. vol. 5 p. 40 −41 1974 (58) Field surveyed (Int. Cl. 7 , DB name) C09D 4/00-4/06 C08F 299/02-299/08 C08G 18/67-18/69 C09D 175/16 CA ( STN) REGISTRY (STN)
Claims (1)
端にそれぞれ１つ以上の（メタ）アクリロイル基を有
し、かつ、プレポリマー主鎖の繰り返しユニット中に
（メタ）アクリロイル基を側鎖として有する化合物を少
なくとも１種含む放射線硬化型塗工剤による硬化塗膜を
設けてなることを特徴とする屈曲用素材。 1. A flexible material having one or more (meth) acryloyl groups at both ends of a prepolymer molecule and a (meth) acryloyl group in a repeating unit of the prepolymer main chain. A cured coating film formed by a radiation-curable coating agent containing at least one compound having a side chain
A bending material characterized by being provided.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23797291A JP3158527B2 (en) | 1991-09-18 | 1991-09-18 | Bending material with cured coating by radiation-curable coating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23797291A JP3158527B2 (en) | 1991-09-18 | 1991-09-18 | Bending material with cured coating by radiation-curable coating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0578597A JPH0578597A (en) | 1993-03-30 |
| JP3158527B2 true JP3158527B2 (en) | 2001-04-23 |
Family
ID=17023203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23797291A Expired - Fee Related JP3158527B2 (en) | 1991-09-18 | 1991-09-18 | Bending material with cured coating by radiation-curable coating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3158527B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2544726B2 (en) * | 1986-06-14 | 1996-10-16 | 松下電工株式会社 | Manufacturing method of multilayer printed wiring board |
| JP5817295B2 (en) * | 2011-07-28 | 2015-11-18 | Dic株式会社 | Active energy ray-curable resin composition, cured product thereof, and film |
-
1991
- 1991-09-18 JP JP23797291A patent/JP3158527B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Ｌａｋｏｋｒａｓ．Ｍａｔｅｒ．Ｉｋｈ Ｐｒｉｍｅｎ．ｖｏｌ．５ ｐ．４０−４１ １９７４ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0578597A (en) | 1993-03-30 |
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