JPS6130566A - Urethane acrylate - Google Patents
Urethane acrylateInfo
- Publication number
- JPS6130566A JPS6130566A JP59151408A JP15140884A JPS6130566A JP S6130566 A JPS6130566 A JP S6130566A JP 59151408 A JP59151408 A JP 59151408A JP 15140884 A JP15140884 A JP 15140884A JP S6130566 A JPS6130566 A JP S6130566A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- urethane acrylate
- acrylate
- group
- urethane
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
「発明の目的」
（産業上の利用分野）
本発明は塗料・印刷インキ・プリント回路板等の画像形
成材料・接着剤・電気電子部品の絶縁性封止材料等に有
用な放射線硬化型の新規な無黄変型ウレタンアクリＶ−
）に関するものである。Detailed Description of the Invention "Object of the Invention" (Industrial Application Field) The present invention is applicable to paints, printing inks, image forming materials such as printed circuit boards, adhesives, insulating sealing materials for electrical and electronic components, etc. Useful radiation-curable new non-yellowing urethane acrylic V-
).
（従来の技術及びその問題点）
紫外線（ＵＶ）や電子線（ｇＢ）等により硬化する樹脂
は常温下短時間で硬化する、無溶剤系が可能である、画
像形成時の解像力が高い等、従来の溶剤系・熱硬化型樹
脂に比し著しい特徴を有する為に注目′ｔ−あつめてい
る。(Conventional technology and its problems) Resins that are cured by ultraviolet rays (UV) or electron beams (gB), etc. cure in a short time at room temperature, can be made without solvents, have high resolution during image formation, etc. It is attracting attention because it has remarkable characteristics compared to conventional solvent-based and thermosetting resins.
これら放射線硬化樹脂のうち、インシアネート成分と水
酸基を有する（メタ）・アクリレート成分との反応物で
あるいわゆるウレタンアクリレート類は硬化性に優れ１
強じんな塗膜を得る事が可能であり、かつ酸素濃度が高
くても硬化する等の特徴を有している。Among these radiation-curable resins, so-called urethane acrylates, which are reaction products of an incyanate component and a (meth)acrylate component having a hydroxyl group, have excellent curability.
It is possible to obtain a strong coating film, and it has the characteristics of curing even in high oxygen concentrations.
とれらウレタンアクリレート類のインシアネート成分と
しては従来トリレンジイソシアネート（ＴＤＩ）が多く
用いられてきたが、ＴＤＩの如き芳香族インシアネート
を用いた樹脂は、硬化過程で、また硬化後の経時変化に
より黄変し、更には密着性・可撓性等の物性が低下する
という欠点を有していた。Traditionally, tolylene diisocyanate (TDI) has been widely used as the incyanate component of Torera urethane acrylates, but resins using aromatic incyanates such as TDI are susceptible to damage during the curing process and due to changes over time after curing. It has the disadvantage of yellowing and further deterioration of physical properties such as adhesion and flexibility.
この様な黄変及び硬化後の樹脂物性の経年変化は、イン
シアネート成分として脂肪族系インシアネートを用いる
事により基本的には解決可能である。このような例とし
て例えばヘキサメチレンジインシアネート（ＨＭＤＩ）
やイソホロンジイソシアネー） （ＩＰＤＩ）の如き脂
肪族もしくは脂環族ジイソシアネートモノマーと水酸基
を有するアクリル系化合物との反応生成物や、ＨＭＤＩ
やＩＰＤＩをベースとして、ビユレット結合、インシア
ヌレート結合、ウレタン結合等によりオリゴマー化した
プレポリマーと水酸基を有するアクリル系化合物との反
応生成物等が考えられる、。Such yellowing and aging changes in the physical properties of the resin after curing can basically be solved by using an aliphatic incyanate as the incyanate component. Examples of this include hexamethylene diinsyanate (HMDI).
Reaction products of aliphatic or alicyclic diisocyanate monomers such as (IPDI) and isophorone diisocyanate (IPDI) and acrylic compounds having hydroxyl groups, HMDI
A reaction product of a prepolymer oligomerized by biuret bond, incyanurate bond, urethane bond, etc., and an acrylic compound having a hydroxyl group based on IPDI or IPDI may be considered.
しかしながらＨＭＤ ＩやＩＰＤＩ七ツマ−な用いた系
は硬化後の樹脂の硬度が出しにくい欠点が有り。However, systems using HMD I and IPDI have the disadvantage that it is difficult to obtain hardness of the resin after curing.
更に毒性・刺激性の強いＨＭＤ ＩやＩＰＤＩモノマー
を扱う必要が有る為に安全性の面での問題点も大きい、
。Furthermore, there are major safety issues as it is necessary to handle HMD I and IPDI monomers, which are highly toxic and irritating.
.
一方、 ）ＩＭＤＩ−？ ＩＰＤＩのプレポリマーをイ
ソシアネート成分として用いる場合は上記の如き毒性・
刺激性の問題は解決し得るが、生成するウレタン −ア
クリレートの粘度が高い、他の重合性アクリレート類と
の相溶性が悪い等の欠点を生じる。On the other hand, )IMDI-? When using IPDI prepolymer as an isocyanate component, the toxicity and
Although the problem of irritation can be solved, there are disadvantages such as high viscosity of the urethane-acrylate produced and poor compatibility with other polymerizable acrylates.
（目 的）
従って当業界ではＨＭＤ ＩやＴＰＪ）Ｉモノマー等の
毒性、刺激性の問題が無く、かつ硬化硬度に優れ、また
低粘度であり他の重合性アクリレートとの相溶性に優れ
た無黄変型のウレタンアクリレートの出現が待たれてい
た。(Purpose) Therefore, there is a need in the industry to develop monomers that do not have the toxicity and irritation problems of HMD I and TPJ) I monomers, have excellent curing hardness, are low in viscosity, and have excellent compatibility with other polymerizable acrylates. The appearance of yellowing urethane acrylate has been awaited.
本発明は、この様な要求にこたえ得る新規なウレタンア
クリレートを提供することを目的とするものである。The object of the present invention is to provide a novel urethane acrylate that can meet these demands.
「発明の構成」
（問題点を解決するための手段）
本発明者らは上記問題点を克服すべく鋭意研究を重ねた
結果、１．８−ジイソシアナト−４−インシアナトメチ
ルオクタン（ＴＩ）と水酸基を有する（メタ）アクリル
系化合物とを反応させた化合物が、上記目的を達成し得
る事を見出し本発明を完成するに至った。"Structure of the Invention" (Means for Solving the Problems) As a result of intensive research to overcome the above problems, the present inventors found that 1,8-diisocyanato-4-incyanatomethyloctane (TI) The inventors discovered that a compound obtained by reacting with a (meth)acrylic compound having a hydroxyl group can achieve the above object, and completed the present invention.
即ち、本発明は
一般式（Ｉ）：
〔式（Ｉ）中のＩ（、の１〜３個は一般式（ｕ）−ＮＨ
−Ｃｏ−０４４−０−ＣＯ−Ｃ＝ ＣＨ，（Ｉｆ）几Ｓ
を表わし、１個又は２個のＲが上記一般式（ＩＩ）を表
わす場合、残りの基Ｒは−ＮＣＯを表わし、かつ一般式
（ｎＪ中のＲ４は炭素数２〜６のアルキレン基を示し、
またＲ５は水素又はメチル基を示す。〕で示される新規
な無黄変型ウレタンアクリレートを提供するものである
。That is, the present invention provides general formula (I): [1 to 3 of I(, in formula (I) are general formula (u)-NH
-Co-044-0-CO-C=CH, (If) represents S, and when one or two R represents the above general formula (II), the remaining group R represents -NCO, and General formula (R4 in nJ represents an alkylene group having 2 to 6 carbon atoms,
Further, R5 represents hydrogen or a methyl group. The present invention provides a novel non-yellowing urethane acrylate represented by the following.
本発明による新規ウレタンアクリレートは下記式（［［
ｆ）に示す１．８−ジイソシアナト−４−イソシアナト
メチルオクタン（以下ＴＩと記す）と下記一般式（Ｍ）
で示される水酸基を有する（メタ）アクリレート（以下
単にアクリレートと略記する）の反応により得られる。The novel urethane acrylate according to the present invention has the following formula ([[
f) 1,8-diisocyanato-4-isocyanatomethyloctane (hereinafter referred to as TI) and the following general formula (M)
It is obtained by the reaction of (meth)acrylate (hereinafter simply abbreviated as acrylate) having a hydroxyl group represented by:
。
〔一般式（ＩＶ）中ノＲ’ 、 Ｒ’ ｉｊ 一般式
（１） 中（ＤＲ’ 。. [R' in general formula (IV), R' ij in general formula (1) (DR').
几５と同じものを示す。〕
式（１）にて示されるＴｌ１ｉ例えば特開昭５６−１２
７３４１にみられる如く、１．８−ジアミノ−４−アミ
ノメチルオクタンもしくはその塩をホスゲンと反応させ
る事により得られる。Shows the same thing as 几5. ] Tl1i shown in formula (1), for example, JP-A-56-12
7341, by reacting 1,8-diamino-4-aminomethyloctane or a salt thereof with phosgene.
一般式（ｉＶ）に示される水酸基を有する（メタ）アク
リレートとしては例えばアクリル酸−２−ヒドロキシエ
チル、メタクリル醒−２−ヒドロキシエチル、アクリル
緻−２−ヒドロキシプロピル、メタクリル酸−２−ヒド
ロキシプロピル、アクリル酸−３−ヒドロキシプロピル
、メタクリル酸−３−ヒドロキシプロピル、アクリルば
−３−クロロ−２−ヒドロキシプロピル、メタクリル酸
−３−クロロ−２−ヒドロキシプロピル、アクリル酸−
６−ヒドロキシヘキシル、メタクリル１１２−６−ヒド
ロキシヘキシル等が挙げられる。これらは適宜混合して
用いる事も可能である。Examples of the (meth)acrylate having a hydroxyl group represented by the general formula (iV) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate
Examples include 6-hydroxyhexyl, methacryl 112-6-hydroxyhexyl, and the like. It is also possible to mix and use these as appropriate.
囲で行われる。反応温度が′高すぎるとアクリレートの
二重結合が熱重合を起こし高分子化する為好ましくない
。It is done in a circle. If the reaction temperature is too high, the double bonds of the acrylate will thermally polymerize and become a polymer, which is not preferable.
反応の際、心安に応じて例えばベンゼン、トルエン、キ
シレンの如き芳香族炭化水素、酢酸ブチル、酢酸エチル
、エチレングリコールモノエチルエーテルアセテートの
如きエステル類、２−ブタノン、４−メチル−２−ペン
タノンの如きケトン類等のような不活性溶剤や１例えば
スチレンや活性水素を持たない（メタ）アクリレート類
等の光重合性単量体を溶媒として用いる事が出来る１、
更に必要であれば１反応時の熱重合を抑制する為のラジ
カル重合禁止剤や、例えば錫系化合物や第三級アミン系
化合物の如き活性水素化合物とインシアネートとの反応
を促進する触媒を加えても良い。During the reaction, aromatic hydrocarbons such as benzene, toluene, xylene, esters such as butyl acetate, ethyl acetate, ethylene glycol monoethyl ether acetate, 2-butanone, 4-methyl-2-pentanone, etc. Inert solvents such as ketones such as 1 and photopolymerizable monomers such as styrene and (meth)acrylates that do not have active hydrogen can be used as solvents.
Furthermore, if necessary, a radical polymerization inhibitor to suppress thermal polymerization during one reaction and a catalyst to promote the reaction between an active hydrogen compound such as a tin-based compound or a tertiary amine-based compound and incyanate are added. It's okay.
反応に供するＴＩのインシアネート基とアクリレートの
水酸基との当量比は生成するウレタンアクリレートの物
性に大きな影響を及ぼすため目的に応じて慎重に選択す
る必要が有るが、ＮＣＯ／水酸基当量比で３／１〜１７
１．５ より選択される。この当量比が３／１より大
きい場合、生成するウレタンアクリレート中の（メタ）
アクリル基濃度が低くい為硬化性に乏しくなり、また当
量比が１／１．５より小さい場合は未反応のＢ成分が多
くなり経済的でなく、トちらも好ましくない。The equivalent ratio of the incyanate group of the TI to the hydroxyl group of the acrylate to be subjected to the reaction has a great effect on the physical properties of the urethane acrylate produced, so it must be carefully selected depending on the purpose, but the equivalent ratio of NCO/hydroxyl group is 3/ 1-17
1.5 Selected from. When this equivalent ratio is greater than 3/1, (meth) in the urethane acrylate produced
Since the acrylic group concentration is low, the curability is poor, and if the equivalent ratio is less than 1/1.5, there will be a large amount of unreacted component B, which is not economical, and both are not preferred.
（作 用）
かくして得られたウレタンアクリレートは適当な光重合
開始剤（例えばベンゾイン系・アゾ系・有機パーオキサ
イド系・ジフェニルジサルファイド系等の化合物）の共
存下に紫外線を照射する事により強じんな樹脂塗膜を形
成する機能を有する。(Function) The urethane acrylate thus obtained can be made tougher by irradiating it with ultraviolet rays in the coexistence of a suitable photopolymerization initiator (for example, benzoin-based, azo-based, organic peroxide-based, diphenyl disulfide-based compounds, etc.). It has the function of forming a resin coating film.
この際、例えばアントラキノン。５−二トロフルオレノ
ン、５−ニトロアセナフテン等の光増感剤や他の重合性
不飽和樹脂・オリゴマー及びモノマーを添加する事が出
来、また必要に応じて顔料やフィシ−等信の充凋剤を加
える事も可能である。In this case, for example, anthraquinone. Photosensitizers such as 5-nitrofluorenone and 5-nitroacenaphthene and other polymerizable unsaturated resins, oligomers and monomers can be added, and if necessary, pigments and fissuring agents can be added. It is also possible to add agents.
本発明になるウレタンアクリレートは上記紫外腺硬化イ
・１１脂として配合する際に、他の重合性不飽和（１７
４脂・オリゴマーと優れた相溶性を発揮する点て従来の
ウレタンアクリレートに見られない優れた特徴をイテし
ている７゜
以下害施例により本発明を具体的に説明する。When the urethane acrylate of the present invention is blended as the above-mentioned ultraviolet gland-curing A.11 fat, other polymerizable unsaturated (17
The present invention will be specifically explained using a 7° or less example, which exhibits excellent compatibility with urethane acrylates and oligomers, which is an excellent feature not found in conventional urethane acrylates.
実施例中のヂはすべて重、！Ｊ！′チを示し、また用い
た測定機器及び測定方法は以下の通りである１゜（測定
機器）
粘 度：エミ２回転粘度計
赤外線吸収スペクトル（Ｉｎ、） ：
日本分光工業ｅ１）製 ＩＲ−１型
（測定方法）
ＮＣＯ含有率： ＪＩＳ Ｋ−１５，５６に準じて行
った。All も in the examples are heavy! J! The measuring equipment and method used are as follows.1° (Measuring equipment) Viscosity: Emi 2-rotation viscometer Infrared absorption spectrum (In): IR-1 manufactured by JASCO Corporation e1) Type (Measurement method) NCO content: Measured according to JIS K-15,56.
実施例１
２−ヒドロキシエチルアクリレ−） （２−ＨＢＡ）１
６６ｒとＴＩ １００Ｆ （ＮＣＯ１０Ｈ当を比ｔ、ｚ
）とをジプチル錫ジラウレー） （ＤＢＴＤＬ）０．１
ｔを触媒として５０℃２時間反応させた。この際熱重
合禁止剤としてハイドロキノンモノメチルエーテル（Ｍ
Ｑ） ｏ、ｏ２ｙを添加した。Example 1 2-Hydroxyethyl acrylate (2-HBA)1
66r and TI 100F (comparison of NCO10H)
) and dibutyltin dilaure) (DBTDL) 0.1
The reaction was carried out at 50° C. for 2 hours using t as a catalyst. At this time, hydroquinone monomethyl ether (M
Q) o and o2y were added.
得られたウレタンアクリレートは２５℃における粘度が
７００ｃｐｓの流動性の高い透明液体であった。このも
のの■几スペクトルを第１図に示す。The obtained urethane acrylate was a highly fluid transparent liquid with a viscosity of 700 cps at 25°C. The solid spectrum of this product is shown in Figure 1.
実施例２〜４
実施例１の手法に準じウレタンアクリレートの合成を行
った。配合処決１灰応条件及び得られたウレタンアクリ
レートの物性値を第１表に示す。Examples 2 to 4 Urethane acrylates were synthesized according to the method of Example 1. Table 1 shows the mixing conditions and physical properties of the urethane acrylate obtained.
伺第１表中の略号は以下のものを示す。The abbreviations in Table 1 indicate the following.
２−ＨＨＡ ： ２−ヒドロキシエチルアクリレート２
−ＨＰＡ： ２−ヒドロキシエチルアクリレート２−Ｈ
ＥＭＡ ： ２−ヒドロキシエチルメタクリレート
ＭＦｉＫ ：メチルエチルヶトン
比較例！
ＴＩの代りにＨＭＤＩのビユレットオリゴ？ −（ＮＣ
Ｏ含有量２３．３ ％、粘度１８００ ｃｐｓ／２５℃
）を用いて、実施例１と同様に反応を行った。配合処決
、 反応条ｆＩｉｉび得られたウレタンアクリレートの
物性値を第１表に示す。2-HHA: 2-hydroxyethyl acrylate 2
-HPA: 2-hydroxyethyl acrylate 2-H
EMA: 2-Hydroxyethyl methacrylate MFiK: Methyl ethyl comparison example! HMDI's Biulet Oligo instead of TI? -(NC
O content 23.3%, viscosity 1800 cps/25℃
), the reaction was carried out in the same manner as in Example 1. Table 1 shows the compounding treatment, reaction conditions fIiii, and physical properties of the obtained urethane acrylate.
第１図、第２図、第３図、第４図及び第５図はウレタン
アクリレートのＩＲスペクトル図である。FIGS. 1, 2, 3, 4, and 5 are IR spectra of urethane acrylate.
Claims (1)
化学式、表等があります▼（II） を表わし、１個又は２個のＲが上記一般式（II）を表わ
す場合、残りの基Ｒは−ＮＣＯを表わし、かつ一般式（
II）中のＲ＾４は炭素数２〜６のアルキレン基を示し、
またＲ＾５は水素又はメチル基を示す。〕で示されるウ
レタンアクリレート(1) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [1 to 3 of R in formula (I) are general formula (II)▲Mathematical formula,
There are chemical formulas, tables, etc. ▼ (II) When one or two R represents the above general formula (II), the remaining group R represents -NCO, and the general formula (
R^4 in II) represents an alkylene group having 2 to 6 carbon atoms,
Moreover, R^5 represents hydrogen or a methyl group. ] Urethane acrylate
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59151408A JPH0788347B2 (en) | 1984-07-23 | 1984-07-23 | Urethane acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59151408A JPH0788347B2 (en) | 1984-07-23 | 1984-07-23 | Urethane acrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6130566A true JPS6130566A (en) | 1986-02-12 |
| JPH0788347B2 JPH0788347B2 (en) | 1995-09-27 |
Family
ID=15517941
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59151408A Expired - Lifetime JPH0788347B2 (en) | 1984-07-23 | 1984-07-23 | Urethane acrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788347B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6248849B1 (en) | 1994-10-24 | 2001-06-19 | Amcol Corporation | Precipitation polymerization process for producing an oil adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| EP1736492A1 (en) * | 2005-06-24 | 2006-12-27 | Bayer MaterialScience LLC | Low viscosity, ethylenically-unsaturated polyurethanes |
| WO2007130816A1 (en) | 2006-05-01 | 2007-11-15 | Colgate-Palmolive Company | Oral care composition with silicone composite |
| US8540971B2 (en) | 2004-08-27 | 2013-09-24 | Colgate-Palmolive Company | Oral care composition with cross-linked polymer peroxide |
| US8591868B2 (en) | 2005-09-27 | 2013-11-26 | Colgate-Palmolive Company | Single phase whitening dentifrice |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5792016A (en) * | 1980-12-01 | 1982-06-08 | Toray Ind Inc | Polyurethane resin and composition for coating material |
-
1984
- 1984-07-23 JP JP59151408A patent/JPH0788347B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5792016A (en) * | 1980-12-01 | 1982-06-08 | Toray Ind Inc | Polyurethane resin and composition for coating material |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6248849B1 (en) | 1994-10-24 | 2001-06-19 | Amcol Corporation | Precipitation polymerization process for producing an oil adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| US6387995B1 (en) | 1994-10-24 | 2002-05-14 | Amcol International Corporation | Precipitation polymerization process for producing an oil adsorbent polymer capable of entrapping solid particles and liquids and the product thereof |
| US8540971B2 (en) | 2004-08-27 | 2013-09-24 | Colgate-Palmolive Company | Oral care composition with cross-linked polymer peroxide |
| US9517194B2 (en) | 2004-08-27 | 2016-12-13 | Colgate-Palmolive Company | Oral care composition with cross-linked polymer peroxide |
| US9895304B2 (en) | 2004-08-27 | 2018-02-20 | Colgate-Palmolive Company | Oral care composition with cross-linked polymer peroxide |
| US10758472B2 (en) | 2004-08-27 | 2020-09-01 | Colgate-Palmolive Company | Oral care composition with cross-linked polymer peroxide |
| US10959936B2 (en) | 2004-08-27 | 2021-03-30 | Colgate-Palmolive Company | Oral care composition with cross-linked polymer peroxide |
| US11596593B2 (en) | 2004-08-27 | 2023-03-07 | Colgate-Palmolive Company | Oral care composition with cross-linked polymer peroxide |
| EP1736492A1 (en) * | 2005-06-24 | 2006-12-27 | Bayer MaterialScience LLC | Low viscosity, ethylenically-unsaturated polyurethanes |
| US8591868B2 (en) | 2005-09-27 | 2013-11-26 | Colgate-Palmolive Company | Single phase whitening dentifrice |
| WO2007130816A1 (en) | 2006-05-01 | 2007-11-15 | Colgate-Palmolive Company | Oral care composition with silicone composite |
| US8568695B2 (en) | 2006-05-01 | 2013-10-29 | Colgate-Palmolive Company | Oral care composition with silicone composite |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0788347B2 (en) | 1995-09-27 |
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| EXPY | Cancellation because of completion of term |