JPS5922934A - Method for curing ultraviolet curing composition - Google Patents

Abstract

PURPOSE:To cure a composition instantaneously without thermally deforming a material to be irradiated, by irradiating the material to be irradiated and coated with an ultraviolet curing type composition with a high load type low- pressure mercury lamp radiating spectrum lines of specific wavelengths with a high efficiency at a low ultraviolet light dose. CONSTITUTION:An ultraviolet curing type composition is cured by irradiating a material to be irradiated, e.g. vinyl chloride film, and coated with the ultraviolet curing type composition with ultraviolet light from a low-pressure mercury lamp at >=4 W/cm lamp load at 5X10<2> W/cm<2> peak ultraviolet light intensity and 1X10<3> joules/m<2> ultraviolet light dose. EFFECT:The method is applicable to the printing and curing of coating on plastic films, and the application range of the material is extended with great industrial advantages.

Description

【発明の詳細な説明】 本発明は紫外線硬化形組成物、特に熱に弱い材宵の物品
（以下被照射物と云う〕に塗布されＴこ紫外線硬化形組
成物を硬化させるにあ１コリ、被照射物を熱変形させる
ことなく前記組成物を硬化させる照射方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention provides an ultraviolet curable composition, particularly a method for curing an ultraviolet curable composition applied to a heat-sensitive article (hereinafter referred to as an irradiated object). The present invention relates to an irradiation method for curing the composition without thermally deforming the irradiated object.

紫外線硬化形組成物を硬化させるのに通常使用される紫
外線ランプは高圧水銀灯、メタルハライドランプ等であ
る。こ第１らのランプはアーク長当りのう゛／ノブ力（
以下ランプ負荷と称す）が３０〜１６０Ｗ／ｃＷＩ　　
と高負荷型であり、紫外線放射効率は１５〜２０％程度
で、残りは可視光、赤外線および対流、伝導によって消
費される熱である。従ってプラスチックフィルム等熱に
弱い被照射物に塗布し１こ紫外線硬化型組成物を、Ｃれ
らのランプを用いて紫外線硬化させる場合、被照射物が
熱変形を起すという問題が発生し１こ。Ultraviolet lamps commonly used to cure ultraviolet curable compositions include high-pressure mercury lamps and metal halide lamps. The first and second lamps have the following power per arc length:
(hereinafter referred to as lamp load) is 30 to 160 W/cWI
It is a high-load type, and its ultraviolet radiation efficiency is about 15 to 20%, with the remainder being heat consumed by visible light, infrared rays, convection, and conduction. Therefore, when an ultraviolet curable composition is applied to an object to be irradiated that is sensitive to heat, such as a plastic film, and then cured by ultraviolet light using such a lamp, the problem arises that the object to be irradiated is thermally deformed. .

このような被照射物の熱変形を防止するには二重ガラス
管の内部に水を流す水冷ジャケット内に直圧水銀う゛ノ
ブま１こはメタルハライドランプを設置しｆコ水冷式照
射装置を用いるのが一般的である。To prevent such thermal deformation of the irradiated object, a direct-pressure mercury lamp or metal halide lamp is installed in a water-cooled jacket that allows water to flow inside a double glass tube, and a water-cooled irradiation device is used. is common.

しかじ、この装置においては二重ガラス管内の水の層に
より２５０　ｎｍ以下の短波長の紫外線が吸収され、紫
外線硬化型組成物の硬化が不充分となって表面粘着が残
りやすく、かつ設備が複雑で高価である等の欠点があつ
ｆこ。However, in this device, the water layer in the double glass tube absorbs ultraviolet rays with a short wavelength of 250 nm or less, resulting in insufficient curing of the ultraviolet curable composition, which tends to leave surface adhesion, and the equipment. It has drawbacks such as being complicated and expensive.

本発明はこれらの欠点を除去するｆこめ、赤外線の放射
効率が低く波長２５８．７　ｎｒｎのスペクトル線を高
効率で放射する高負荷形低圧水銀灯を用い、紫外線硬化
型組成物を塗−ｒｌｉ　Ｌ　ｆｖ被照射物を高い紫外線
風でｊ照射することにより、被照射物を熱変形させるこ
となく組成物を瞬間的に硬化させるもので、その要旨は
う′／ブ負荷が４Ｗ／ｃｒＸ以上の低降水銀灯を用い、
紫外線硬化性組成物が塗布され１こ被照射物表面におい
て波長２５８．７　ｎｍのスペクトル線からなる紫外線
のピーク強度が５ｘ　１ｏ　２　Ｗ／　２以上でかつ紫
外線量を１　×１０８Ｊｏｕｌｅ　／　＋ｎ２　以上照
射することを特徴とするものである。In order to eliminate these drawbacks, the present invention uses a high-load type low-pressure mercury lamp that has low infrared radiation efficiency and emits spectral lines with a wavelength of 258.7 nrn with high efficiency, and coats an ultraviolet curable composition. By irradiating the object to be irradiated with high ultraviolet rays, the composition is instantly cured without thermally deforming the object. Using a precipitation silver lamp,
The surface of the object to be irradiated with the ultraviolet curable composition is irradiated so that the peak intensity of ultraviolet rays consisting of spectral lines with a wavelength of 258.7 nm is 5x 1o 2 W/ 2 or more and the amount of ultraviolet rays is 1 x 108 Joule / +n2 or more. It is characterized by this.

水銀蒸気圧が低い低圧水銀ランプは２５３．７　ｎｍの
紫外線を効率よく放射し、赤外線放射の少／、（いう／
ブとして知られている。Low-pressure mercury lamps with low mercury vapor pressure efficiently emit 253.7 nm ultraviolet rays and emit very little infrared radiation.
It is known as bu.

しかし、従来市販され・ている低降水銀灯（一般に殺菌
灯と称されている）は管内に過剰の水銀が封入され、室
温で２５８．７　ｎｍの紫外線放射効率が最大となる水
銀蒸気圧になるように角荷は０１〜０．５Ｗ／２　、出
力は数Ｗ〜４０Ｗ稈度に設計されており、住 高伯荷、高出片フ困帷であつｆコ。その理由はランプ負
荷を大きくすると管壁温度が＾くなり、それに応じて過
剰に封入しである水銀が多く蒸発し、負荷が０．５　ｗ
／ｍ程度以上になると水銀蒸気圧が最適値を紹え、２５
８．７　ｎ　ｍのスペクトル放射効率が急激に低下する
１こめである。即ち水銀蒸気千が昼くなると波長２５３
．７ｏｍのスペクトル放射強度は自己吸収の１こめ、か
左って減少し、紫外線は２００〜４００旧ｎの範囲に広
がり、可視光、特に赤外線の放射効率が訓くなる。この
１こめ従来の低降水銀灯は被照射物表面での紫外線照射
量を増加させることができず、紫外線硬化形組成物を硬
化させるランプとしては不適当でほとんど（要用されて
いなかつ１こ。わずかに紫外線硬化型塗料を硬化する照
射装置として低降水銀灯と高圧水銀灯を併用し１こ公知
例が米国特許第８８４０４４８号明細書に示されている
がこのときの低降水銀灯は５　Ｗ／　１ｎｃｈ　（２Ｗ
／（７）ノ以下の従来の低い負荷のものであり、照射装
置は低千水帳灯弔独便用まｆコは高圧水銀灯との併用で
、装置内部を窒素ガス雰囲気方式としｆこものである。However, conventionally commercially available low-precipitation silver lamps (commonly referred to as germicidal lamps) have an excess of mercury sealed inside the tube, and the mercury vapor pressure reaches the maximum 258.7 nm UV radiation efficiency at room temperature. The square load is designed to be 01~0.5W/2, the output is designed to be several W to 40W, and the output is designed to be high-quality, high-density, and high-density. The reason for this is that when the lamp load is increased, the tube wall temperature increases, and accordingly, a large amount of the excess mercury evaporates, reducing the load to 0.5 W.
/m or more, the mercury vapor pressure reaches its optimum value, and 25
This is the first point where the spectral radiation efficiency of 8.7 nm drops sharply. In other words, when 1,000 mercury vapors reach daytime, the wavelength is 253.
．． The spectral radiation intensity of 7 ohm is reduced by a fraction of the self-absorption, and the ultraviolet rays are expanded to the range of 200 to 400 old nm, and the radiation efficiency of visible light, especially infrared rays, is improved. Conventional low-precipitation silver lamps cannot increase the amount of ultraviolet irradiation on the surface of the irradiated object, and are therefore unsuitable as lamps for curing ultraviolet curable compositions, and are rarely used. A known example of a combination of a low-precipitation silver lamp and a high-pressure mercury lamp is shown in US Pat. No. 8,840,448 as an irradiation device for slightly curing ultraviolet-curable paint, and the low-precipitation silver lamp in this case has a 5 W/1 nch. (2W
The irradiation device is a conventional low load type (7) or less, and the irradiation device is a low water lamp.The irradiation device is used in conjunction with a high pressure mercury lamp, and the inside of the device is set to a nitrogen gas atmosphere. be.

本発明に用いられる低ｆ王水銀灯はランプ管内に過剰の
水銀が封入さｔｚ、管壁温度によって蒸気王が変化する
飽和蒸気圧タイプであるが、ランプに最冷部をつくって
水銀を凝縮さ惣この部分を風冷ま１こは水冷方式によっ
て冷却し水銀蒸気圧をコ゛ノドロールするとともに、ア
ーク全体にわ１こって均一発光するように全体の冷却を
工夫し１こ高負荷型のものである。紫外線硬化型塗料（
組成物〕の硬化に関する我々の実験では、波長ａｏｏｎ
ｍ以下のスペクトルを除去し１こ紫外線で照射し１こ場
合、いわゆる酸素明害により塗料の表面が硬化しにくく
なり表面粘着としていつまでも残る。The low-f mercury lamp used in the present invention is a saturated vapor pressure type in which excess mercury is sealed in the lamp tube and the vapor pressure changes depending on the temperature of the tube wall. This part is air-cooled, one is cooled by water cooling, and the mercury vapor pressure is controlled, and the entire arc is cooled so that light is emitted uniformly over the entire arc.This is a high-load type. . UV-curable paint (
In our experiments on the curing of compositions], the wavelength aoon
If the spectrum of less than m is removed and irradiated with ultraviolet rays, the surface of the paint will be difficult to harden due to so-called oxygen damage and will remain as a surface adhesive forever.

紫外線の放射波長が短いほど酸素妨害は少なくなり、表
面硬化が良好と１．（ろ。ま１こ紫外線のピーク１伸度
が弱いと塗膜厚みとの関係で塗料内部まで紫直線が透過
せず内部の硬化が充分でなく表面だけ硬化して長時間照
射しても内部が未硬化の壬＼となり密着性が悪くなるこ
となどがわかっている。1. The shorter the ultraviolet radiation wavelength, the less oxygen interference and the better the surface hardening. (lol) If the peak 1 elongation of ultraviolet rays is weak, the purple straight line will not penetrate into the interior of the paint due to the thickness of the paint film, and the interior will not be cured sufficiently, and only the surface will harden, even if irradiated for a long time. It is known that the adhesive becomes uncured and the adhesion deteriorates.

そこで種々の試験の結果、ランプ負荷４Ｗ／ＣＭ以上の
低鄭水銀灯を用いて、波長２５３．７　ｎ　ｍのスペク
トル線から成る紫外線のピーク強度が５　Ｘ　Ｉ　Ｑ　
２Ｗ、／　＋ｎ’以ヒでかつ紫外線量が照射物表面でＩ
　Ｘ　ＩＱ　、Ｉｏ＋＋Ｉｅ／ｍｆｆ１以ｔあれば塗膜
の表向粘着もなく　１ｆｆｉ常の塗料の膜厚１０〜２０
μの内部まで充分硬化することがオ〕かつｆこ。As a result of various tests, using a low Zheng mercury lamp with a lamp load of 4 W/CM or more, the peak intensity of ultraviolet light consisting of a spectral line with a wavelength of 253.7 nm was 5 X IQ.
2W, / +n' or higher, and the amount of ultraviolet rays is I on the surface of the irradiated object.
If X IQ, Io++Ie/mff1 or more, there is no surface adhesion of the paint film.1ffiThe normal paint film thickness is 10-20
Make sure that the inside of μ is sufficiently cured.

欠に不発明に使用しｆこ照射装置について説明する。高
目背型低降水銀灯の構造は第１図に示すように）１１ｄ
端に熱陰陰型に＆ｔｎを設はアーク長は５００１１１７
ｍ　で、内部に過剰の水銀と始動用ガスを封入している
。ガラスＶｉ質は紫外線を良く透過する石英がラスまｔ
こは紫外線透過ガラスを使用する。The irradiation device that will be used inadvertently will be explained below. The structure of the high eye-back type low precipitation silver lamp is shown in Figure 1)11d
The arc length is 5001117 when &tn is set in the hot and negative type at the end.
m, with excess mercury and starting gas sealed inside. The glass Vi quality is made of quartz that transmits ultraviolet rays well.
This uses UV-transparent glass.

ランプ管径は外径２３φでランプ両端部に最冷部（２）
をつくり過剰の水銀を留め風冷で点灯中のう゛／プ管内
の水銀蒸気圧をコ゛／　ｌ−ロールする。（３）は’Ｊ
　−ド線である。ランプは交流点灯でラップ電力１００
Ｗから５００Ｗまで変化させ１こ。The lamp tube has an outer diameter of 23φ and has the coldest parts (2) at both ends of the lamp.
The mercury vapor pressure in the lit pipe is reduced by wind cooling, and the excess mercury is retained. (3) is 'J
- line. The lamp is powered by AC and has a lap power of 100
Change it from W to 500W.

照射器具は第２図および第３図に示すようにランプ（４
）は単光型アルミ反射板（５）にう゛ノブ最冷部のが反
射板（５）の外側に位置するように取付け、ブロワ（図
示せず）によって器具のダクト取付口（６）から排気冷
却する構造である。The irradiation equipment is a lamp (4) as shown in Figures 2 and 3.
) is attached to the single-light aluminum reflector plate (5) so that the coldest part of the knob is located on the outside of the reflector plate (5), and the blower (not shown) is used to exhaust air from the duct installation port (6) of the appliance. It has a cooling structure.

本発明を適用する紫外線硬化形組成物は特に制限はなく
、通常の重合性二重結合をもつ樹脂、光増（［有］剤１
重合性甲慮体、顔料、その他光填剤から構成されるもの
で、イッキ、塗料、接揄剤、その他：１多光性轍脂とし
て使用されるものが範囲に含まれる。The ultraviolet curable composition to which the present invention is applied is not particularly limited, and includes ordinary resins having polymerizable double bonds, photosensitizers, etc.
It is composed of polymerizable shells, pigments, and other optical fillers, and includes those used as paints, paints, adhesives, and other multiphoton fillers.

欠に実他例をあげて本発明を４体的に説明する。The present invention will be explained in detail by giving specific examples.

組成物は不飽和ポリエステル樹脂、ベンシイ゛ツメチル
エーテル、ベンジル、酢酸ブチルその他改質剤などを分
散させて得られ１こクリヤ塗料である。The composition is a one-piece clear paint obtained by dispersing unsaturated polyester resin, benzyl methyl ether, benzyl, butyl acetate, and other modifiers.

該組成物を０．２ｍ／ｍ厚みの塩ヒ゛フィルムにバーコ
ーターで約ｌＯμ塗布し、第１表に示すように各種・Ｐ
）照射装置で硬化させ１こ、 素化後の塗膜の観察結果を第１表に示す。The composition was coated on a salt film with a thickness of 0.2 m/m using a bar coater, and coated with various types of P as shown in Table 1.
) After curing with an irradiation device, the observation results of the coating film after plating are shown in Table 1.

高！王水牛灯を使用し１こ照射装置では紫外線とともに
赤外線の放射量も多くて塩ビフィルムの熱変形が大きく
使用できない。High! A single irradiation device using a king buffalo lamp cannot be used because it emits a large amount of infrared rays as well as ultraviolet rays, and the PVC film is severely deformed by heat.

水冷式高王水覗灯を用いｒ：　ＩＫ１射装置ではフィル
ムの熱変形は少ないが塗膜の表面粘着がいつまでも残り
、この組成物の硬化用装置としては不適当であつ１こ。Using a water-cooled high aqua regia sight lamp: Although thermal deformation of the film is small in the IK direct irradiation device, the surface adhesion of the coating film remains indefinitely, making it unsuitable as a device for curing this composition.

従来の低圧水銀灯（殺菌灯〕はう゛ノブ負荷が低くて照
射面での紫外線のピーク強度が弱く硬化後の塗膜の密着
度が悪い。Conventional low-pressure mercury lamps (germicidal lamps) have low knob loads, weak peak intensity of ultraviolet rays on the irradiated surface, and poor adhesion of the paint film after curing.

本発明によるランプ負荷４Ｗ／１以上の誦負葭型低圧水
：ＩＭ灯を使用しｆこ照射装置では塩ビフィルムの熱変
形もなく表面硬化、密着とも良好な結果を得丁こ。更に
第２表に示すように第１表にｆ要用し１こと同じ組成物
を塗膜厚み２０μで塗布しＴコ場合でも、ランプ負荷４
　Ｗ　／　ｃｍ以上の高負荷型イル圧水銀灯による照射
装置で紫外線のピーク強度が５Ｘ１０Ｗ／ｍ２　　以上
でかつ紫外線照射量がＩ　Ｘ　１０８Ｊｏｕｌｅ／ｍ２
　　以」二であれば同様な結果が得られろことがわかつ
１こ。尚、第１表および第２表において紫外線噴とは組
成物表面（被照射面〕における紫外線照射風を示−Ｃ０ （Ｌ支Ｔ−金色） 本発明ｆこよる１愼射方法で照射゛すれば、従来の硬化
方法に比べて被照射物の熱変形がなく（至）めで瞬間的
に硬化でき、従来便用できながっｆこプラスチックフィ
ルムへの印刷および塗装の硬化に適用できるなど素材の
適用範囲が広がり工業的メリットが多い。Using the low-pressure water IM lamp of the present invention with a lamp load of 4 W/1 or more, the irradiation device achieved good results in terms of surface hardening and adhesion without thermal deformation of the PVC film. Furthermore, as shown in Table 2, even if the same composition as shown in Table 1 is applied to a coating thickness of 20μ, the lamp load is 4.
The peak intensity of ultraviolet rays is 5 x 10 W/m2 or more and the amount of ultraviolet irradiation is I x 108 Joule/m2 using an irradiation device using a high-load pressure mercury lamp of W / cm or more.
It can be seen that similar results can be obtained if the following is done. In addition, in Tables 1 and 2, ultraviolet jet refers to the ultraviolet irradiation wind on the surface of the composition (surface to be irradiated) -C0 (L branch T-gold) Irradiation is performed by one injection method according to the present invention. For example, compared to conventional curing methods, there is no thermal deformation of the irradiated object and it can be cured instantaneously, making it suitable for printing on plastic films and curing paints that cannot be used conventionally. The range of application has expanded and there are many industrial benefits.

灯の概略説明図、第２図および第８図は本発明方法に使
用する照射装置の横断面図および縦断曲回である。The schematic illustrations of the lamp, FIGS. 2 and 8, are cross-sectional views and longitudinal turns of the irradiation device used in the method of the invention.

４・・・・・・ランプ、　　　　　５・・白反射板。4...Lamp, 5...White reflector.

６・・・・・・ダク１、取付口。6...Duc 1, installation port.

片　１　囚 省　２　図 オ　５　凹 手続祁Ｌｌ巳書（執墾） 昭和５７年　９月３日 特許庁長官殿 １、車外の表示 昭和５７８Ｔ　特許願　第　１３２８９２号２、発明の
名称 紫外線硬化形組成物の硬化方法 代表者　　那須信雄 ６、補正の内容 （１）明細書箱１頁５行目〜同１１行目の「特許請求の
範囲」の欄を次の通り訂正する。Fragment 1 Ministry of Prisons 2 Diagram O 5 Recessed Procedure Qi Ll's Book (Execution) September 3, 1980 To the Commissioner of the Patent Office 1 Display outside the car 1985 Patent Application No. 132892 2 Name of the invention Ultraviolet curable composition Method for Curing Products Representative Nobuo Nasu 6 Contents of Amendment (1) The "Claims" column on page 1, lines 5 to 11 of the specification box is corrected as follows.

「紫外線硬化形組成物を硬化させるにあたり、単位アー
ク長当りのランプ電ノコが４Ｗ／Ｃｌ１１以上の低圧水
銀灯を用い、前記組成物表面において波長が２５３，７
ｎｍのスペクトル線からなる紫外線のピーク強度が５×
１０２Ｗ／　Ｉｌｌ’以上でかつ紫外線ｍを１ｘｌＯ’
　Ｊｏｕｌｅ／　ｍ２以上照制することを特徴とする紫
外線硬化形組成物の硬化方法。」（２）明細書第９頁の
第１表にお（プるＮＯ７の「光源」欄の「高出力低圧水
銀灯」を「高負荷型低圧水銀灯」ど訂正づ−る。"In curing the ultraviolet curable composition, a low-pressure mercury lamp with a lamp power of 4 W/Cl11 or more per unit arc length is used, and a wavelength of 253,7
The peak intensity of ultraviolet light consisting of nm spectral lines is 5×
102W/Ill' or more and ultraviolet ray m 1xlO'
1. A method for curing an ultraviolet curable composition, characterized by controlling irradiation of Joule/m2 or more. (2) In Table 1 on page 9 of the specification, "High output low pressure mercury lamp" in the "Light source" column of Pull No. 7 has been corrected to "High load type low pressure mercury lamp".

（３）明細書第１０頁の第２表におけるＮＯ９の「光源
」欄の「高出力低圧水銀灯」を「高負荷型低圧水銀灯Ｊ
と訂正する。(3) "High output low pressure mercury lamp" in the "Light source" column of No. 9 in Table 2 on page 10 of the specification has been changed to "High load type low pressure mercury lamp J
I am corrected.

（４）明細書第１０真の第２表にお【プるＮＯ９の「ラ
ンプ負荷Ｊ欄のｒ　２．ＯＷ／ｃｍＪをｒ　２Ｗ／ｃｍ
ｊと訂正する。(4) In Table 2 of No. 10 of the specification, set r 2.OW/cmJ in the lamp load J column of No. 9 to r 2W/cm.
Correct it as j.

以上that's all

Claims (1)

【特許請求の範囲】[Claims] 紫外線硬化１１今組成物を硬化させるにあ１こり、単位
アーク長当りのう゛／ブ電千が４　Ｗ　／　ｎｍ以下の
低降水銀灯を用い、前記組成物表面において波長が２５
３．７　ｎｍのスペクトル線からなる紫外線のピーク強
Ｉｆｆが５　Ｘ　１（ｌ　Ｗ／ｉｎ　　以上でかつ紫外
線層を１×１０８、Ｉｏｕｌｅ／ｍ　　以上照射するこ
とを特徴とする紫外線硬化形組成物の硬化方法。Ultraviolet Curing 11 To cure the composition, a low precipitation silver lamp with a UV/V power per unit arc length of 4 W/nm or less is used, and a wavelength of 25 W/nm is used on the surface of the composition.
An ultraviolet curable composition characterized in that the peak intensity Iff of ultraviolet rays consisting of a spectral line of 3.7 nm is 5 x 1 (l W/in or more) and the ultraviolet layer is irradiated with 1 x 108 Ioule/m or more. Curing method.