JP2004300406A - Ultraviolet ray-curable resin composition, method of forming coating film - Google Patents
Ultraviolet ray-curable resin composition, method of forming coating film Download PDFInfo
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Abstract
Description
本発明は、紫外線硬化性樹脂組成物及び塗膜形成方法に関し、特に光の届き難い部分において安定した塗膜を形成する技術に関する。 The present invention relates to an ultraviolet-curable resin composition and a coating film forming method, and more particularly to a technique for forming a stable coating film in a portion where light does not easily reach.
従来、光照射による硬化を利用した樹脂塗膜の形成方法が知られている。光照射により硬化する樹脂として、例えば可視光照射により硬化する光硬化性樹脂が知られているが、この場合、可視光用光重合開始剤が非常に高価であること、可視光で反応するため塗布前の樹脂組成物の保存に遮光が必要なこと、複雑な形状をした木材導管深部等の光の届き難い部分では硬化し難いこと等の問題がある。 Conventionally, a method for forming a resin coating film using curing by light irradiation has been known. As a resin that is cured by light irradiation, for example, a photocurable resin that is cured by irradiation with visible light is known, but in this case, the photopolymerization initiator for visible light is very expensive, and reacts with visible light. There are problems such as the necessity of shading for preservation of the resin composition before application, and the difficulty of hardening in a portion where light does not easily reach, such as a deep portion of a complicatedly shaped wood conduit.
そこで、可視光では反応せず、紫外線照射により反応する紫外線硬化性樹脂を用いて塗膜を形成する技術が、例えば特許文献１に開示されている。
上記特許文献１に記載されたような従来の紫外線硬化性樹脂組成物では、重合開始剤若しくは重合促進剤として金属系の化合物を含んでいるため、硬化後に得られる塗膜において該金属系化合物に基づく着色が見られる場合がある。また、このような金属系化合物の重合開始剤若しくは重合促進剤と紫外線硬化性樹脂との系では、反応速度が非常に速いため、２液配合型の系とする必要があり、塗膜形成作業に手間が掛かる場合がある。さらに、紫外線照射により硬化反応が生じものであるため、紫外線の届き難い箇所では塗膜を形成し難いといった問題もある。 The conventional ultraviolet curable resin composition as described in Patent Document 1 contains a metal-based compound as a polymerization initiator or a polymerization accelerator. Based coloring may be seen. In addition, in the case of such a system of a polymerization initiator or a polymerization accelerator of a metal compound and an ultraviolet curable resin, the reaction speed is extremely high, so that it is necessary to use a two-component compound system, May take time. Further, since a curing reaction is caused by the irradiation of ultraviolet rays, there is a problem that it is difficult to form a coating film in a place where the ultraviolet rays hardly reach.
本発明は、上記のような事情に鑑みてなされたもので、紫外線を照射し難い箇所においても反応が促進され、得られる塗膜にも着色が生じ難く、塗布時の扱いも簡便な塗膜形成用の紫外線硬化性樹脂組成物と、これを用いた塗膜形成方法とを提供することを目的とする。 The present invention has been made in view of the above circumstances, the reaction is promoted even in places where it is difficult to irradiate ultraviolet light, the resulting coating film is hardly colored, and the coating film is easy to handle during coating. An object of the present invention is to provide an ultraviolet-curable resin composition for forming and a coating film forming method using the same.
上記課題を解決するために、本発明の紫外線硬化性樹脂組成物は、紫外線硬性樹脂と、有機過酸化物系硬化剤とを含有する。この有機過酸化物系硬化剤には、ケトンパーオキサイド系、ハイドロパーオキサイド系、ジアシルパーオキサイド系、ジアルキルパーオキサイド系、パーオキシケタール系、アルキルパーエステル系、パーカーボネート系の硬化剤の１種又は２種以上を用いることが好ましく、なかでもジアシルパーオキサイド系、パーオキシケタール系、アルキルパーエステル系、パーカーボネート系の硬化剤の１種又は２種以上を用いることがさらに好ましい。さらに、有機過酸化物系硬化剤は、１時間半減期温度が１３０℃以下であることが望ましい。 In order to solve the above-mentioned problems, the ultraviolet-curable resin composition of the present invention contains an ultraviolet-curable resin and an organic peroxide-based curing agent. The organic peroxide-based curing agents include one of ketone peroxide-based, hydroperoxide-based, diacyl peroxide-based, dialkyl peroxide-based, peroxyketal-based, alkyl perester-based, and percarbonate-based curing agents. Alternatively, it is preferable to use two or more kinds, and it is more preferable to use one or more kinds of a diacyl peroxide-based, peroxyketal-based, alkyl perester-based, and percarbonate-based curing agent. Further, the one-period half-life temperature of the organic peroxide-based curing agent is desirably 130 ° C. or lower.
本発明によれば、塗膜形成主体をなす紫外線硬化性樹脂の硬化を促進させる添加剤として有機過酸化物系硬化剤を用いているため、コバルト化合物等の金属系硬化促進剤を用いた場合に比して、硬化後の塗膜において着色の問題が生じ難くなる。
また、同じく金属系硬化促進剤を用いた場合に比して、常温で紫外線硬化性樹脂を硬化を促進させる効率が低いため、ポットライフの長い安定な１液型塗料として用いることが可能となり、そのままこれを塗膜形成対象物に塗布し紫外線照射を行うことで、簡便に塗膜形成を行うことができるようになる。
さらに、従来のように有機過酸化物系促進剤を含有しない場合では、紫外線照射のみにより硬化反応を促進する効果が得られるのであるが、本発明では有機過酸化物系硬化剤を用いることにより、紫外線照射に伴う発熱によっても硬化反応を促進する効果が得られる。このため、例えば紫外線を照射し難い厚膜深部分や木材の導管深部等においても硬化を促進することができ、その塗膜形成用途が非常に広範となり、硬化ムラ等も生じ難くなるため信頼性の高い塗膜を形成することが可能となる。
According to the present invention, since an organic peroxide-based curing agent is used as an additive for accelerating the curing of the ultraviolet-curable resin forming the coating film, a metal-based curing accelerator such as a cobalt compound is used. As a result, the problem of coloring is less likely to occur in the cured coating film.
Also, compared to the case where a metal-based curing accelerator is used, the efficiency of accelerating the curing of the ultraviolet curable resin at room temperature is low, so that it can be used as a stable one-pack coating having a long pot life. By directly applying this to a coating film forming target and irradiating with ultraviolet rays, a coating film can be easily formed.
Furthermore, in the case where the organic peroxide-based accelerator is not contained as in the conventional case, the effect of accelerating the curing reaction can be obtained only by ultraviolet irradiation, but in the present invention, by using the organic peroxide-based accelerator, Also, the effect of accelerating the curing reaction can be obtained by the heat generated by the irradiation of ultraviolet rays. For this reason, for example, curing can be promoted even in a thick film deep portion or a wood conduit deep portion where it is difficult to irradiate ultraviolet rays, the coating film forming application becomes very wide, and uneven curing and the like hardly occur. It is possible to form a coating film having a high value.
本発明の紫外線硬化性樹脂組成物は、紫外線硬化性樹脂を溶解又は分散させる溶剤中に上記有機過酸化物系硬化剤が溶解又は分散されたものであることが好ましく、この場合、例えば当該紫外線硬化性樹脂組成物を塗膜形成対象物に塗布し、これに対して紫外線を照射することで極めて簡便に、着色の少なく、硬化ムラ等も少ない安定した塗膜を形成することができるのである。 The ultraviolet-curable resin composition of the present invention is preferably one in which the organic peroxide-based curing agent is dissolved or dispersed in a solvent that dissolves or disperses the ultraviolet-curable resin. By applying the curable resin composition to a film-forming object and irradiating it with ultraviolet light, it is possible to extremely easily form a stable coating film with less coloring and less curing unevenness. .
本発明に言う紫外線硬化性樹脂とは、紫外線照射により硬化反応を生じ得る樹脂のことであって、例えば不飽和ポリエステル等の重合性多重結合を有した化合物を例示することができる。 The ultraviolet curable resin referred to in the present invention is a resin capable of causing a curing reaction upon irradiation with ultraviolet light, and examples thereof include compounds having a polymerizable multiple bond such as unsaturated polyester.
有機過酸化物系硬化剤として、具体的には、ケトンパーオキサイド系、ハイドロパーオキサイド系、ジアシルパーオキサイド系、ジアルキルパーオキサイド系、パーオキシケタール系、アルキルパーエステル系、パーカーボネート系の硬化剤の１種又は２種以上の混合物を例示することができ、なかでもジアシルパーオキサイド系、パーオキシケタール系、アルキルパーエステル系、パーカーボネート系の硬化剤の１種又は２種以上のものが熱による硬化促進効率が高いので好ましい。また、有機過酸化物系硬化剤は、１時間半減期温度が１３０℃以下のものを使用することが望ましい。
この有機過酸化物系硬化剤の添加量は、紫外線硬化性樹脂１００重量部に対して０．０５〜１０重量部、とされ、０．０５重量部未満では、硬化が不十分となり、１０重量部を超えても効果の上昇が得られない。
Specific examples of organic peroxide-based curing agents include ketone peroxide-based, hydroperoxide-based, diacyl peroxide-based, dialkyl peroxide-based, peroxyketal-based, alkyl perester-based, and percarbonate-based curing agents. And one or more of diacyl peroxide-based, peroxyketal-based, alkyl perester-based, and percarbonate-based curing agents. This is preferred because the curing acceleration efficiency is high. It is desirable to use an organic peroxide-based curing agent having a one-hour half-life temperature of 130 ° C. or lower.
The addition amount of the organic peroxide-based curing agent is 0.05 to 10 parts by weight with respect to 100 parts by weight of the ultraviolet curable resin. No effect can be obtained even if the number exceeds the limit.
本発明の塗膜形成方法は、上記紫外線硬化性樹脂組成物を用いることを特徴とし、具体的には、塗膜形成対象物に前記紫外線硬化性樹脂組成物を塗布する工程と、塗布した紫外線硬化性樹脂組成物に対して紫外線照射を行う工程とを含み、前記紫外線照射工程において、紫外線照射に伴う発熱により前記有機過酸化物系硬化剤を分解し、該分解物により前記紫外線硬化性樹脂の硬化を促進させることを特徴とする。 The coating film forming method of the present invention is characterized in that the above-mentioned ultraviolet-curable resin composition is used, and specifically, a step of applying the ultraviolet-curable resin composition to a coating film forming object, A step of irradiating the curable resin composition with ultraviolet light, wherein in the ultraviolet light irradiation step, the organic peroxide-based curing agent is decomposed by heat generated by the irradiation of ultraviolet light, and the ultraviolet curable resin is decomposed by the decomposed product. Is characterized by promoting curing.
このような方法により、極めて簡便に、着色の少なく、硬化ムラ等も少ない安定した塗膜を形成することが可能となる。特に、紫外線を照射し難い厚膜深部分や木材の導管深部等に前記紫外線硬化性樹脂組成物を塗布した場合にも、極めて良好に硬化反応を促進させることができ、その塗膜適用範囲が極めて広範囲に及ぶこととなる。なお、紫外線硬化性樹脂組成物の塗布工程においては、例えばワイピング法の他、スプレー法、スピンコート法等を採用することができ、紫外線照射工程においては、例えば高圧水銀灯を用い波長２００ｎｍ〜４００ｎｍ程度の紫外線を、光量１００〜２０００ｍＪ／ｃｍで照射することができる。 According to such a method, it is possible to extremely easily form a stable coating film with less coloring and less curing unevenness. In particular, even when the ultraviolet curable resin composition is applied to a deep part of a thick film or a deep part of a conduit of wood where it is difficult to irradiate the ultraviolet light, the curing reaction can be promoted very well, and the application range of the coating film can be improved. It will be very extensive. In the application step of the ultraviolet-curable resin composition, for example, in addition to a wiping method, a spray method, a spin coating method, or the like can be adopted. In the ultraviolet irradiation step, for example, a high-pressure mercury lamp is used and a wavelength of about 200 nm to 400 nm is used. UV light with a light amount of 100 to 2000 mJ / cm.
つぎに、本発明に係る紫外線硬化性樹脂組成物を用いた塗膜形成方法の実施形態について説明する。
本実施の形態の塗膜形成方法は、１．下塗り工程、２．中塗り工程、３．穴埋め工程、４．上塗り工程（仕上げ工程）の４つの工程の必ず１つを含むものであり、各工程に用いる塗料として、紫外線により硬化反応を生じるＵＶ塗料（紫外線硬化性樹脂）と、該硬化を促進する有機過酸化物系の硬化剤とを、スチレン等の反応性希釈剤に溶解ないし分散させた組成物（紫外線硬化性樹脂組成物）を用いる。
Next, an embodiment of a coating film forming method using the ultraviolet curable resin composition according to the present invention will be described.
The coating film forming method according to the present embodiment includes: 1. undercoating step; 2. intermediate coating step; 3. Filling process; It includes at least one of the four steps of the overcoating step (finishing step). As a coating used in each step, a UV coating (ultraviolet curable resin) that causes a curing reaction by ultraviolet rays and an organic coating that accelerates the curing are used. A composition (ultraviolet curable resin composition) in which an oxide curing agent is dissolved or dispersed in a reactive diluent such as styrene is used.
下塗り工程では、上記組成物を塗布した後、ＵＶ照射を行い、その後表面研削を行うものとしている。また、中塗り工程においても、研削した下塗装膜上に、上記組成物を塗布した後、ＵＶ照射を行い、その後表面研削を行うものとしている。さらに、穴埋め工程においても、中塗り塗膜に対して上記組成物を塗布した後、ＵＶ照射を行い、その後表面研削を行うことで穴埋めを行うものとしており、その後、上塗りにより仕上げ工程が行われる。 In the undercoating step, the composition is applied, UV irradiation is performed, and then surface grinding is performed. Also, in the intermediate coating step, the above composition is applied onto the ground undercoat film, UV irradiation is performed, and then surface grinding is performed. Furthermore, also in the filling process, after applying the composition to the intermediate coating film, UV irradiation is performed, and then the surface is ground to perform filling, and thereafter, the finishing process is performed by overcoating. .
上記各工程中、下塗り工程と穴埋め工程において、上述した紫外線硬化性樹脂組成物を用いることが、木材の導管、欠点等の深部、塗膜の穴の深部などのＵＶ光が届き難い部分まで十分に硬化させることができるため好ましく、また、中塗り工程では、必ずしも上記紫外線硬化性樹脂組成物を用いる必要はないが、塗装面に大きな凹凸がある場合には、部分的に塗膜が厚くなるため厚膜深部を硬化させる目的で該紫外線硬化性樹脂組成物を用いることが好ましい。 In each of the above steps, in the undercoating step and the hole filling step, the use of the above-mentioned ultraviolet-curable resin composition is sufficient for a portion where UV light is difficult to reach, such as a deep portion of a conduit of wood, a defect, or a deep portion of a hole of a coating film. It is preferable because it can be cured, and in the intermediate coating step, it is not always necessary to use the ultraviolet-curable resin composition, but if there are large irregularities on the painted surface, the coating film is partially thickened Therefore, it is preferable to use the ultraviolet curable resin composition for the purpose of curing the deep part of the thick film.
以下、上記実施の形態で示した塗膜形成方法を用いた幾つかの実施例を、比較例とともに説明する。 Hereinafter, some examples using the coating film forming method described in the above embodiment will be described together with comparative examples.
（実施例１）
紫外線硬化性樹脂としての光開始剤を含んだ下塗り用不飽和ポリエステルをスチレン等の反応性希釈剤に溶解させた溶液に対し、有機過酸化物系硬化剤として１時間半減期温度が６０℃であるパーカーボネート系硬化剤（商品名：パーカドックス１６、化薬アクゾ社製）を０．３重量％添加したＵＶ塗料１を用意した。このＵＶ塗料１をマホガニー板にワイピング塗布し、これにＵＶ照射（光量約８００ｍＪ／ｃｍ２）を行うことで下塗装膜を得た。このとき、ＵＶ照射によりマホガニー板の表面温度は５７℃まで上昇した。ＵＶ照射後、Ｐ１８０ペーパーにて研削しても樹脂の染み出し等が発生せず、硬化ムラ、色付き等の問題も生じなかった。
(Example 1)
A solution prepared by dissolving an unsaturated polyester for undercoating containing a photoinitiator as an ultraviolet curable resin in a reactive diluent such as styrene is used as an organic peroxide-based curing agent at a half-life temperature of 60 ° C. for 1 hour. A UV paint 1 to which 0.3% by weight of a certain percarbonate-based curing agent (trade name: Percadox 16, manufactured by Kayaku Akzo) was added was prepared. This UV paint 1 was applied to a mahogany plate by wiping, and this was irradiated with UV (light amount about 800 mJ / cm 2 ) to obtain an undercoat film. At this time, the surface temperature of the mahogany plate rose to 57 ° C. due to the UV irradiation. After UV irradiation, no resin exudation or the like occurred even when ground with P180 paper, and no problems such as uneven curing and coloring occurred.
（比較例１）
下塗り工程として、硬化剤を添加せず、光開始剤を含んだ不飽和ポリエステルをスチレン等の反応性希釈剤に溶解させた溶液（比較塗料１）を、実施例１と同様にマホガニー板にワイピング塗布し、これにＵＶ照射（光量約８００ｍＪ／ｃｍ２）を行った。ＵＶ照射後、Ｐ１８０ペーパーにて研削すると、導管より未硬化樹脂の染み出しが発生した。
(Comparative Example 1)
As an undercoating step, a solution in which an unsaturated polyester containing a photoinitiator was dissolved in a reactive diluent such as styrene without adding a curing agent (Comparative Paint 1) was wiped on a mahogany plate in the same manner as in Example 1. It was applied and UV-irradiated (light amount about 800 mJ / cm 2 ). After UV irradiation, when grinding with P180 paper, uncured resin exuded from the conduit.
（実施例２）
実施例１と同様の下塗りをした上に、紫外線硬化性樹脂としての光開始剤を含んだ中塗り用不飽和ポリエステルをスチレン等の反応性希釈剤に溶解させた溶液に対し、有機過酸化物系硬化剤として１時間半減期温度が６０℃であるパーカーボネート系硬化剤（商品名：パーカドックス１６、化薬アクゾ社製）を１．０重量％添加したＵＶ塗料２を用意した。このＵＶ塗料２をマホガニー板にスプレー塗布し、これにＵＶ照射（光量約８００ｍＪ／ｃｍ２）を行うことで中塗り塗膜を得た。このとき、ＵＶ照射によりマホガニー板の表面温度は６２℃まで上昇した。また、硬化後の膜厚は約４００μｍであった。このような実施例２の中塗り塗膜について、塗装前後の色変化ΔＥと、硬化後の膜硬度（振稈硬度）とを測定した。なお、色変化ΔＥは、塗装前後の明度、色度をMicroflash分光測色機（da
ta color社製）にて測定した値の差である。結果を表１に示す。
(Example 2)
A solution prepared by dissolving an unsaturated polyester for intermediate coating containing a photoinitiator as an ultraviolet-curable resin in a reactive diluent such as styrene was applied to the undercoating in the same manner as in Example 1, and an organic peroxide was used. A UV coating material 2 was added to which 1.0% by weight of a percarbonate-based curing agent (trade name: Percadox 16, manufactured by Kayaku Akzo Co., Ltd.) having a one-hour half-life temperature of 60 ° C. was added as a system curing agent. The UV coating material 2 was spray-coated on a mahogany plate, and irradiated with UV light (light amount about 800 mJ / cm 2 ) to obtain an intermediate coating film. At this time, the surface temperature of the mahogany plate rose to 62 ° C. due to the UV irradiation. The film thickness after curing was about 400 μm. With respect to such an intermediate coating film of Example 2, the color change ΔE before and after coating and the film hardness (curling hardness) after curing were measured. The color change ΔE is calculated by comparing the lightness and chromaticity before and after coating with a Microflash spectrophotometer (da
Tacolor). Table 1 shows the results.
（実施例３）
実施例１と同様の下塗りをした上に、紫外線硬化性樹脂としての光開始剤を含んだ中塗り用不飽和ポリエステルをスチレン等の反応性希釈剤に溶解させた溶液に対し、有機過酸化物系硬化剤として１時間半減期温度が１２１℃であるパーオキシケタール系硬化剤（商品名：トリゴノックスＤＴ−５０、化薬アクゾ社製）を１．０重量％添加したＵＶ塗料３を用意した。このＵＶ塗料３を実施例２と同様にマホガニー板にスプレー塗布し、これにＵＶ照射（光量約８００ｍＪ／ｃｍ２）を行うことで中塗り塗膜を得た。このような実施例３の中塗り塗膜について、塗装前後の色変化ΔＥと、硬化後の膜硬度（振稈硬度）とを測定した。なお、色変化ΔＥは、塗装前後の明度、色度をMicroflash分光測色機（data color社製）にて測定した値の差である。結果を表１に示す。
(Example 3)
A solution prepared by dissolving an unsaturated polyester for intermediate coating containing a photoinitiator as an ultraviolet-curable resin in a reactive diluent such as styrene was applied to the undercoating in the same manner as in Example 1, and an organic peroxide was used. A UV coating material 3 was added to which 1.0% by weight of a peroxyketal curing agent (trade name: Trigonox DT-50, manufactured by Kayaku Akzo Co.) having a one-hour half-life temperature of 121 ° C. was added as a system curing agent. This UV paint 3 was spray-coated on a mahogany plate in the same manner as in Example 2, and was irradiated with UV light (light amount about 800 mJ / cm 2 ) to obtain an intermediate coating film. With respect to such an intermediate coating film of Example 3, the color change ΔE before and after coating and the film hardness after curing (oscillation hardness) were measured. The color change ΔE is the difference between the values of the lightness and chromaticity before and after coating measured with a Microflash spectrophotometer (manufactured by Data Color). Table 1 shows the results.
（実施例４）
紫外線硬化性樹脂としての光開始剤を含んだ中塗り用不飽和ポリエステルをスチレン等の反応性希釈剤に溶解させた溶液に対し、有機過酸化物系硬化剤として１時間半減期温度が１３３℃であるケトンパーオキサイド系硬化剤（商品名：カヤメックＡ、化薬アクゾ社製）を１．０重量％添加したＵＶ塗料４を用意した。このＵＶ塗料４を、実施例２と同様にマホガニー板にスプレー塗布し、これにＵＶ照射（光量約８００ｍＪ／ｃｍ２）を行うことで中塗り塗膜を得た。このような実施例４の中塗り塗膜について、塗装前後の色変化ΔＥと、硬化後の膜硬度（振稈硬度）とを測定した。結果を表１に示す。
(Example 4)
A solution prepared by dissolving an unsaturated polyester for intermediate coating containing a photoinitiator as a UV-curable resin in a reactive diluent such as styrene has a one-hour half-life temperature of 133 ° C. as an organic peroxide-based curing agent. A UV paint 4 was added to which 1.0% by weight of a ketone peroxide-based curing agent (trade name: Kayamec A, manufactured by Kayaku Akzo) was added. This UV paint 4 was spray-coated on a mahogany plate in the same manner as in Example 2, and this was irradiated with UV (light amount about 800 mJ / cm 2 ) to obtain an intermediate coating film. With respect to such an intermediate coating film of Example 4, the color change ΔE before and after the coating and the film hardness (curling hardness) after curing were measured. Table 1 shows the results.
（実施例５）
紫外線硬化性樹脂としての光開始剤を含んだ中塗り用不飽和ポリエステルをスチレン等の反応性希釈剤に溶解させた溶液に対し、有機過酸化物系硬化剤として１時間半減期温度が１３３℃であるケトンパーオキサイド系硬化剤（商品名：カヤメックＡ、化薬アクゾ社製）を１．０重量％、コバルト系硬化促進剤を０．５重量％添加したＵＶ塗料５を用意した。このＵＶ塗料５を、実施例２と同様にマホガニー板にスプレー塗布し、これにＵＶ照射（光量約８００ｍＪ／ｃｍ２）を行うことで中塗り塗膜を得た。このような実施例５の中塗り塗膜について、塗装前後の色変化ΔＥと、硬化後の膜硬度（振稈硬度）とを測定した。結果を表１に示す。
(Example 5)
A solution prepared by dissolving an unsaturated polyester for intermediate coating containing a photoinitiator as a UV-curable resin in a reactive diluent such as styrene has a one-hour half-life temperature of 133 ° C. as an organic peroxide-based curing agent. A UV coating material 5 was prepared by adding 1.0% by weight of a ketone peroxide-based curing agent (trade name: Kayamec A, manufactured by Kayaku Akzo) and 0.5% by weight of a cobalt-based curing accelerator. This UV paint 5 was spray-coated on a mahogany plate in the same manner as in Example 2, and this was irradiated with UV (light amount about 800 mJ / cm 2 ) to obtain an intermediate coating film. With respect to such an intermediate coating film of Example 5, the color change ΔE before and after coating and the film hardness after curing (oscillation hardness) were measured. Table 1 shows the results.
（比較例２）
硬化剤及び促進剤を添加せず、紫外線硬化性樹脂としての光開始剤を含んだ中塗り用不飽和ポリエステルをスチレン等の反応性希釈剤に溶解させた溶液（比較塗料２）を、実施例２と同様にマホガニー板にスプレー塗布し、これにＵＶ照射（光量約８００ｍＪ／ｃｍ２）を行うことで中塗り塗膜を得た。このような比較例２の中塗り塗膜について、塗装前後の色変化ΔＥと、硬化後の膜硬度（振稈硬度）とを測定した。結果を表１に示す。
(Comparative Example 2)
A solution prepared by dissolving an unsaturated polyester for intermediate coating containing a photoinitiator as an ultraviolet curable resin in a reactive diluent such as styrene without adding a curing agent and an accelerator (Comparative Paint 2) was used in Example. In the same manner as in No. 2, a spray coating was performed on a mahogany plate, and this was irradiated with UV (light amount about 800 mJ / cm 2 ) to obtain an intermediate coating film. With respect to such an intermediate coating film of Comparative Example 2, the color change ΔE before and after the coating and the film hardness after curing (oscillation hardness) were measured. Table 1 shows the results.
このように、実施例２及び実施例３については、硬化前後の色変化も小さく、また得られた塗膜の硬度も十分高い値を示したが、実施例５では、コバルト系の硬化促進剤を添加したため、硬化前後において大きな色変化が見られた。また、比較例２では、硬化剤及び硬化促進剤を添加しなかったため、硬化反応が十分に進まず、塗膜の硬度が実施例２，３のものに比べて低いものとなった。また、実施例４，５では、１時間半減期温度が１３０℃を超えるため、硬化が遅く、実施例５で促進剤を入れることで硬度を上げた。 As described above, in Examples 2 and 3, the color change before and after curing was small, and the hardness of the obtained coating film was sufficiently high. However, in Example 5, a cobalt-based curing accelerator was used. , A large color change was observed before and after curing. In Comparative Example 2, since the curing agent and the curing accelerator were not added, the curing reaction did not proceed sufficiently, and the hardness of the coating film was lower than those of Examples 2 and 3. Further, in Examples 4 and 5, the one-hour half-life temperature exceeded 130 ° C., so that the curing was slow. In Example 5, the hardness was increased by adding an accelerator.
（実施例６）
紫外線硬化性樹脂としての光開始剤を含んだ穴埋め用不飽和ポリエステルをスチレン等の反応性希釈剤に溶解させた溶液に対し、有機過酸化物系硬化剤として１時間半減期温度が８８℃であるアルキルパーエステル系硬化剤（商品名：トリゴノックス１２１、化薬アクゾ社製）を１．０重量％添加したＵＶ塗料６を用意した。そして、実施例２〜実施例５の中塗り塗膜を研削して得られる塗膜上に残った小穴に対して、このＵＶ塗料６を筆にて埋め込み、ＵＶ照射（光量約８００ｍＪ／ｃｍ２）を行うことで穴埋めを行った。このとき、ＵＶ照射によりワークの表面温度は６０℃まで上昇した。ＵＶ照射後、Ｐ２４０ペーパーにて研削しても樹脂の染み出し等が発生せず、硬化ムラ、色付き等の問題も生じなかった。
(Example 6)
A solution in which an unsaturated polyester for filling holes containing a photoinitiator as a UV-curable resin is dissolved in a reactive diluent such as styrene is used as an organic peroxide-based curing agent at a one-hour half-life temperature of 88 ° C. A UV paint 6 to which 1.0% by weight of an alkyl perester-based curing agent (trade name: Trigonox 121, manufactured by Kayaku Akzo) was added was prepared. Then, the UV paint 6 was embedded in a small hole remaining on the coating film obtained by grinding the intermediate coating film of Examples 2 to 5 with a brush, and irradiated with UV light (light amount of about 800 mJ / cm 2). ) To fill in the gap. At this time, the surface temperature of the work rose to 60 ° C. due to the UV irradiation. After UV irradiation, no resin exudation or the like occurred even when ground with P240 paper, and there was no problem such as uneven curing and coloring.
（実施例７）
紫外線硬化性樹脂としての光開始剤を含んだ穴埋め用不飽和ポリエステルをスチレン等の反応性希釈剤に溶解させた溶液に対し、有機過酸化物系硬化剤として１時間半減期温度が５２℃であるジアシルパーオキサイド系硬化剤（商品名：カヤアシルＩＢ、化薬アクゾ社製）を１．０重量％添加したＵＶ塗料７を用意した。そして、実施例６と同様、塗膜上に残った小穴に対して、このＵＶ塗料７を筆にて埋め込み、ＵＶ照射（光量約８００ｍＪ／ｃｍ２）を行うことで穴埋めを行った。このとき、ＵＶ照射によりワークの表面温度は６０℃まで上昇した。ＵＶ照射後、Ｐ２４０ペーパーにて研削しても樹脂の染み出し等が発生せず、硬化ムラ、色付き等の問題も生じなかった。
(Example 7)
A solution of unsaturated polyester for filling holes containing a photoinitiator as a UV-curable resin dissolved in a reactive diluent such as styrene was used as an organic peroxide-based curing agent at a half-life temperature of 1 hour at 52 ° C. A UV coating material 7 was prepared by adding 1.0% by weight of a certain diacyl peroxide-based curing agent (trade name: Kayaacyl IB, manufactured by Kayaku Akzo). Then, in the same manner as in Example 6, the small holes remaining on the coating film were filled with this UV paint 7 with a brush, and the holes were filled by performing UV irradiation (light amount about 800 mJ / cm 2 ). At this time, the surface temperature of the work rose to 60 ° C. due to the UV irradiation. After UV irradiation, no resin exudation or the like occurred even when ground with P240 paper, and there was no problem such as uneven curing and coloring.
（比較例３）
硬化剤を添加せず、光開始剤を含んだ不飽和ポリエステルをスチレン等の反応性希釈剤に溶解させた溶液（比較塗料３）を、実施例６と同様に、塗膜上に残った小穴に対して筆にて埋め込み、ＵＶ照射（光量約８００ｍＪ／ｃｍ2）を行うことで穴埋めを行った。このとき、ＵＶ照射によりワークの表面温度は６０℃まで上昇した。ＵＶ照射後、Ｐ２４０ペーパーにて研削すると内部の未硬化部分が滲出した。
(Comparative Example 3)
A solution in which an unsaturated polyester containing a photoinitiator was dissolved in a reactive diluent such as styrene without adding a curing agent (Comparative Paint 3) was used in the same manner as in Example 6 to obtain small holes remaining on the coating film. Was filled with a brush, and the hole was filled by performing UV irradiation (light amount: about 800 mJ / cm 2). At this time, the surface temperature of the work rose to 60 ° C. due to the UV irradiation. After UV irradiation, the uncured portion inside was leached out when ground with P240 paper.
本発明の紫外線硬化性樹脂組成物は、木質材を始めとする各種被塗装物に対して紫外線硬化型塗料として使用できる。
The ultraviolet-curable resin composition of the present invention can be used as an ultraviolet-curable paint for various objects to be coated, such as wood materials.
Claims (5)
組成物を用いた塗膜形成方法であって、
塗膜形成対象物に前記紫外線硬化性樹脂組成物を塗布する工程と、
塗布した紫外線硬化性樹脂組成物に対して紫外線照射を行う工程を含み、
前記紫外線照射工程において、紫外線照射に伴う発熱により前記有機過酸化物
系硬化剤を分解し、該分解物により前記紫外線硬化性樹脂の硬化を促進させるこ
とを特徴とする塗膜形成方法。 A coating film forming method using the ultraviolet-curable resin composition according to any one of claims 1 to 4,
A step of applying the ultraviolet-curable resin composition to a coating film forming object,
Including a step of irradiating the applied ultraviolet curable resin composition with ultraviolet light,
The method of forming a coating film, wherein in the ultraviolet irradiation step, the organic peroxide-based curing agent is decomposed by heat generated by ultraviolet irradiation, and the decomposition product accelerates the curing of the ultraviolet-curable resin.
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