JP2009242731A - Photopolymerizable japanese lacquer-containing copolymer and its production method - Google Patents
Photopolymerizable japanese lacquer-containing copolymer and its production method Download PDFInfo
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Description
本願発明は、光重合性含漆共重合体、及びその製造方法に関し、特に、漆の組成分であるゴム質、含窒素物、油中水系型（Ｗ／Ｏ型）エマルジョン粒子を微粒化してレベリング性と紫外線の透過性を向上させた光重合性含漆共重合体、及びその製造技術に関する。 The present invention relates to a photopolymerizable lacquer-containing copolymer and a method for producing the same, and in particular, by atomizing rubbery, nitrogen-containing, water-in-oil type (W / O type) emulsion particles that are lacquer components. The present invention relates to a photopolymerizable lacquer-containing copolymer having improved leveling properties and ultraviolet ray permeability, and a production technique thereof.
天然産漆（生漆）は、油中水系型のエマルジョン（乳濁液）を呈し、ウルシオール（二価フェノール誘導体）を主成分として、ゴム質（多糖質）、含窒素物（糖タンパク）、ラッカーゼ及び水分から構成されている。漆の乾燥硬化は、いわゆる水分の蒸発によるものではなく、適度な湿度と温度条件のもとで、油中水系中に含まれる酵素（ラッカーゼ）によるウルシオールの脱水素反応と自動酸化反応を経てゆっくりと自然硬化する。この酵素による反応は水を必要とするため７０〜７５％の高湿度環境が与えられる。この結果、漆塗膜はウルシオール重合体を骨格とするゴム質（多糖類）バリアの粒子が集積し、これが酸化劣化防止型の耐久性構造になることが知られている。 Naturally produced lacquer (raw lacquer) presents a water-in-oil type emulsion (emulsion), with urushiol (dihydric phenol derivative) as the main component, rubber (polysaccharides), nitrogenous substances (glycoprotein), Consists of laccase and moisture. Lacquer dry-curing is not due to the so-called evaporation of water, but through the dehydrogenation and auto-oxidation of urushiol by an enzyme (laccase) contained in a water-in-oil system under moderate humidity and temperature conditions. Naturally cures slowly. Since this enzyme reaction requires water, a high humidity environment of 70 to 75% is given. As a result, it is known that the lacquer coating film accumulates rubbery (polysaccharide) barrier particles having a urushiol polymer as a skeleton, which forms an oxidation-deterioration-proof durable structure.
この漆の自然硬化による乾燥法の他に、熱によって熱重合させる焼き付け乾燥法、及び光重合開始剤を添加して紫外線（ＵＶ）の照射によって重合体を形成させて行なう紫外線硬化乾燥法が開示されている（特許文献１、特許文献２）。いずれも自然硬化よりも短時間で硬化させことができ、紫外線硬化乾燥法に至っては数秒程度で硬化させることも可能である。 In addition to the drying method by natural curing of lacquer, a baking drying method in which heat polymerization is performed by heat, and an ultraviolet curing drying method in which a polymer is formed by irradiation with ultraviolet rays (UV) by adding a photopolymerization initiator are disclosed. (Patent Document 1, Patent Document 2). Both can be cured in a shorter time than natural curing, and can be cured in about several seconds until the ultraviolet curing drying method.
しかし、これらの特許文献で開示されている発明は、漆塗料の改質によるものではなく、従来組成の漆液に光重合開始剤を添加して塗布した塗膜に、紫外線を照射するものであるため、それ以前の従来技術に則った漆の乾燥時間が指触乾燥（指先で触れても跡が付かない程度の乾燥）５時間、硬化乾燥２４時間であったものを、指触乾燥２時間、硬化乾燥１０時間程度に短縮したに過ぎず、著しい生産性の向上を実現したものではなかった。 However, the inventions disclosed in these patent documents are not based on the modification of lacquer paint, but irradiate ultraviolet rays onto a coating film applied by adding a photopolymerization initiator to a lacquer liquid of a conventional composition. Therefore, the drying time of lacquer according to the prior art before that was 5 hours for finger touch drying (drying to the extent that no marks are made even if touched with the fingertips) and 24 hours for curing drying. The time was only shortened to about 10 hours for curing and drying, and no significant improvement in productivity was realized.
また、上記従来の紫外線硬化型の光重合性含漆塗料やインクは、厚を１０μｍ以下に薄膜化した被膜を形成すると、乾燥硬化後の漆の表面に柚子肌と呼ばれるザラによる凹凸が生じやかった。これは、漆の組成分であるゴム質や含窒素物又は添加した顔料などからなる粒径が数μｍ程度の粒子の残存によるものであり、これらの粒子がレベリング性（塗布面の滑らかさ）や塗膜の硬化障害の一因でもある紫外線の透過性を低下させて、漆独特の光沢や、感性的風合いである肉持ち感・しっとり感・ふっくら感を阻害していた。 In addition, when the conventional UV-curable photopolymerizable lacquer-containing paint or ink is formed into a thin film with a thickness of 10 μm or less, unevenness due to the texture called lion skin occurs on the surface of the lacquer after drying and curing. won. This is due to the residual particles with a particle size of several μm consisting of rubber, nitrogen-containing materials, added pigments, etc., which are components of lacquer, and these particles are leveling (smooth coated surface). UV transmittance, which is one of the causes of coating and coating failure, has been reduced to inhibit the unique luster and sensual texture of fleshiness, moistness, and plumpness.
そこで、これらゴム質や含窒素物の影響を少なくするため、これらの粒径をナノレベル（約５０〜約１５０ｎｍ）までに微粒化する技術が特許文献３、及び特許文献４において開示されている。
これは、生漆又は製造漆を、媒体攪拌ミルを使用して微粒化するもので、これにより油中水系型のエマルジョンの粒径を約５０〜約１５０ｎｍに微粒化するものである。ここでの微粒化工程においては、生漆又は製造漆の油性成分に対して水分が所定比率となるように含水率調節を行なうこと最良の形態としている。また、この微粒化処理後の生成物を塗料として、特に、噴射口の小さいインクジエットプリンターのインクとして使用する場合は、これに種々の公知の添加剤（油溶性の乾燥油、水溶性のポリオール類、並びに界面活性や分散安定剤、等）を添加して粘度を下げる処理と分散安定を図っている。
かかる上記特許文献３、４に開示している漆系塗料は、漆の油中水系型のエマルジョンの微粒化に主眼をおいており、かつこの微粒化した漆にエポキシ及びウレタン系樹脂を添加して塗装用の塗料として応用展開を図っている。また、微粒化については、特段に調整した独自の微粒化装置ではなく既存の剪断機器のみで行なっている。ただし、微粒化製造中熱重合を防ぐ意味で、冷却とさらには漆に添加剤を入れて製造している。
さらに、微小径（数〜数１０μｍ）な噴射口から射出させるインクジェットプリンター用インクの生成では、揮発性有機溶剤で希釈して粘度を下げる必要がある。しかし、この揮発性有機溶剤での希釈については、現在では環境保護などの目的・動向から問題があった。
In this method, raw lacquer or manufactured lacquer is atomized using a medium stirring mill, whereby the particle size of a water-in-oil emulsion is atomized to about 50 to about 150 nm. In the atomization step here, the best mode is to adjust the water content so that the water content becomes a predetermined ratio with respect to the oil component of raw lacquer or manufactured lacquer. In addition, when the product after the atomization treatment is used as a paint, particularly as an ink jet printer ink having a small ejection port, various known additives (oil-soluble drying oil, water-soluble polyol) As well as surfactants, dispersion stabilizers, etc.) to lower the viscosity and achieve dispersion stability.
The lacquer-based paints disclosed in Patent Documents 3 and 4 focus on atomization of lacquer water-in-oil emulsions, and epoxy and urethane resins are added to the atomized lacquer. As a paint for painting, the application is being developed. In addition, atomization is carried out only by existing shearing equipment, not by an original atomizer specially adjusted. However, in order to prevent thermal polymerization during atomization production, it is produced by adding an additive to cooling and further lacquer.
Furthermore, when producing ink for an ink jet printer to be ejected from a fine diameter (several to several tens of μm) ejection port, it is necessary to dilute with a volatile organic solvent to lower the viscosity. However, the dilution with the volatile organic solvent has a problem for the purpose and trend such as environmental protection.
そこで本願発明は、上記問題点に着目して成されたものであり、漆に光重合性のアクリレート化合物を添加して、漆を低粘度化して漆の成分であるゴム質や含窒素物を微粒化すると共に、逆ミセル構造を持つ漆特有の油中水系型エマルジョン粒子をも微粒化することよって、レベリング性と紫外線透過性を高めて、架橋密度の高い高品質の薄膜含漆被膜が形成できる光重合性含漆共重合体、及びその製造方法を提供するものである。 Therefore, the present invention has been made paying attention to the above-mentioned problems. A photopolymerizable acrylate compound is added to lacquer, and the viscosity of lacquer is reduced to make rubber and nitrogen-containing materials that are components of lacquer. In addition to atomization, the water-in-oil emulsion particles unique to lacquer with a reverse micelle structure are also atomized to improve leveling and UV transparency, and form a high-quality thin-film lacquer-coated film with a high crosslinking density The photopolymerizable lacquer-containing copolymer which can be produced, and its manufacturing method are provided.
上記課題を解決するため本願発明に係る光重合性含漆共重合体、及びこの製造方法は、以下のように構成している。 In order to solve the above problems, the photopolymerizable lacquer-containing copolymer according to the present invention and the production method thereof are configured as follows.
光重合性含漆共重合体は、製造漆又はクロメ返しを行った漆に、光重合性オリゴマー又はモノマーなどから成るアクリレート化合物を混合し、漆の構成物であるゴム質、及び含窒素物の粒子が平均粒径１μｍ以下の微粒子であることを特徴としている。また、これに顔料、又は顔料と分散剤とを添加し、さらに、光重合開始剤を添加して成ることを特徴としている。 A photopolymerizable lacquer-containing copolymer is a mixture of an acrylate compound composed of photopolymerizable oligomers or monomers, etc., into a lacquer that has been manufactured or chrome-turned, and is composed of rubber and nitrogen-containing lacquer. The particle is a fine particle having an average particle diameter of 1 μm or less. Further, it is characterized in that a pigment or a pigment and a dispersant are added to this, and a photopolymerization initiator is further added.
次に、この光重合性含漆共重合体は、以下の方法により製造している。
すなわち、製造漆又はクロメ返しを行った漆に、光重合性オリゴマー又はモノマーから成るアクリレート化合物を添加し、この混合物を微粒化工程により漆の構成物であるゴム質、及び含窒素物の粒子を微粒化し、次に、これらの粒子が平均粒径１μｍ以下となるように濾過製造したことを特徴とする。なお、この濾過精製には、減圧濾過、加圧濾過、等の公知の濾過手段が用いられる。
Next, this photopolymerizable lacquer copolymer is produced by the following method.
That is, an acrylate compound composed of a photopolymerizable oligomer or monomer is added to a manufactured lacquer or lacquered lacquer, and the mixture is made into particles of rubber and nitrogen-containing materials that are constituents of lacquer by a pulverization process. It is characterized by being atomized and then produced by filtration so that these particles have an average particle size of 1 μm or less. In this filtration purification, known filtration means such as vacuum filtration, pressure filtration, etc. are used.
また、製造漆又はクロメ返しを行った漆に、光重合性オリゴマー又はモノマーから成るアクリレート化合物を添加し、漆の構成物であるゴム質、及び含窒素物の粒子を微粒化して一次製造し、さらに上記アクリレート化合物、顔料、及び分散剤を添加して微粒化した後、前記粒子の平均粒径が１μｍ以下となるように濾過製造したことを特徴とする光重合性含漆共重合体の製造法。なお、上記微粒化は、超音波振動の付加、又は剪断処理装置であることが好ましい。超音波振動の付加は、超音波帯域の下限値（約１６ＫＨｚ）に近い周波数帯域がより好ましく、そしてその付加工程は１段階、又は数段階に分けて付加しても良い。また、回転剪断処理装置としては、弾性のあるゴムベラを回転させる方式の回転剪断処理装置がより好ましい。この弾性ゴムを用いることより微粒化工程時の加圧力を適宜に設定することができると共に、高加圧力による微粒化の効率化が図れる。 Moreover, to the lacquer which performed the production lacquer or the chrome back, the acrylate compound which consists of a photopolymerizable oligomer or a monomer is added, the rubber | gum which is a constituent of a lacquer, and the particle | grains of a nitrogen-containing material are primary-produced, Furthermore, after the above acrylate compound, pigment, and dispersant were added and atomized, the photopolymerizable lacquer-containing copolymer was produced by filtration so that the average particle diameter of the particles was 1 μm or less. Law. In addition, it is preferable that the said atomization is addition of an ultrasonic vibration, or a shear processing apparatus. The addition of ultrasonic vibration is more preferably a frequency band close to the lower limit of the ultrasonic band (about 16 KHz), and the addition process may be added in one step or in several steps. Further, as the rotational shearing processing device, a rotational shearing processing device of a method of rotating an elastic rubber spatula is more preferable. By using this elastic rubber, the pressure during the atomization step can be set appropriately, and the efficiency of atomization due to the high pressure can be increased.
さらにまた、光重合開始剤、及び界面活性剤等の助剤の添加は上記光重合性含漆共重合体製造工程の何れかの工程において行なっても良い。好ましくは、前記アクリレート化合物や顔料を添加して微粒化した後が良い。 Furthermore, you may perform addition of adjuvant, such as a photoinitiator and surfactant, in any process of the said photopolymerizable lacquer-containing copolymer manufacturing process. Preferably, after the acrylate compound or pigment is added and atomized.
本願発明は上記のような構成を採ることにより、以下に列挙する特徴的な効果を奏する。
１．漆の粘性を光重合性アクリレート化合物によって、低粘性の光重合性含漆共重合体となり、攪拌・剪断・粉砕機能を持つ機器による漆液の構成物であるゴム質や含窒素物の粒子の径を容易に１μｍ以下に微粒化させることができる。それと共に油中水系エマルジョンも微粒化されて、連鎖付加重合による架橋密度の高い、薄膜（１０μｍ以下）の光重合性含漆共重合体の被膜を得ることができる。
By adopting the above-described configuration, the present invention has the following characteristic effects.
1. The viscosity of lacquer is converted to a low-viscosity photopolymerizable lacquer-containing copolymer by photopolymerizable acrylate compounds, and rubber and nitrogen-containing particles that are constituents of lacquer liquids by equipment with stirring, shearing and grinding functions The diameter can be easily atomized to 1 μm or less. At the same time, the water-in-oil emulsion is also atomized, and a thin film (less than 10 μm) photopolymerizable lacquer-containing copolymer film having a high crosslinking density by chain addition polymerization can be obtained.
２．微粒化された光重合性含漆共重合体、及び必要により顔料を添加した有色（エナメル）の光重合性含漆共重合体は、光重合開始剤、助剤等を添加することにより、活性化エネルギーである紫外線を照射することによって秒単位で急速に硬化する。その硬化被膜は微粒化効果により連鎖付加重合による架橋密度が高く、厚さ５〜１０μｍ以下の薄膜形成時においてもゴム質や含漆窒素物が原因とされる凹凸の無い光沢に富んだ高品質の光重合性含漆共重合体の被膜が形成できる。 2. Atomized photopolymerizable lacquer-containing copolymer and colored (enamel) photopolymerizable lacquer-containing copolymer to which a pigment is added if necessary can be activated by adding photopolymerization initiators, auxiliaries, etc. It cures rapidly in seconds by irradiating it with UV energy. The cured film has a high cross-linking density due to chain addition polymerization due to the atomization effect, and is rich in gloss without the irregularities caused by rubber and lacquer-containing nitrogen even when forming a thin film with a thickness of 5 to 10 μm or less The photopolymerizable lacquer-containing copolymer film can be formed.
３．漆の感性的風合いである肉持ち感・しっとり感・ふっくら感を維持しつつ、仕様・用途・機能性を考慮しつつ、アクリレート化合物の選択・配合率によって高硬質から軟質までの被膜形成が可能である。 3. While maintaining the feeling of flesh, moistness, and plumpness, which is the sensibility of lacquer, it is possible to form coatings from high hardness to softness by selecting and blending acrylate compounds while considering specifications, applications, and functionality. It is.
４．漆液の油中水系エマルジョン構造及び漆液の構成物であるゴム質や含窒素物などの粒子が微粒化されたことで、ウレタン・エポキシ・ポリエステルアクリレート化合物との相溶性や光重合硬化の架橋密度が向上するとともに、熱変形度が減少し、熱可塑性樹脂を含めたプラスチック素地、金属素地、紙、布、皮、竹の他、木製素地や木質素地さらには、各種塗装塗膜へのコーティング剤として活用することができる。 4). The water-in-oil emulsion structure of lacquer liquid and the rubber and nitrogen-containing particles that are constituents of lacquer liquid have been atomized to achieve compatibility with urethane / epoxy / polyester acrylate compounds and crosslinking of photopolymerization and curing. As the density increases, the degree of thermal deformation decreases, and in addition to plastic substrates including thermoplastic resins, metal substrates, paper, cloth, leather, bamboo, wooden substrates and wooden substrates, and coatings to various paint films Can be used as an agent.
５．平均粒径が１μｍ以下の微粒子体となる光重合性含漆共重合体及び有色（エナメル）の含漆共重合体の生成物は、数〜数１０μｍの射出口径を持つインクジェットプリンターなどのデジタル印刷機用のインクとしても活用することができる他、シルクスクリーン用印刷インクとしても活用できる。また、従来の漆塗料の乾燥方式である酵素重合型硬化機能と比べ、光重合による秒速硬化をもたらす結果、作業性の向上の他に伝統的技法でもある蒔絵においても、金・銀粉・螺鈿などの蒔絵用材料を接着させるなど、多彩な技法表現に利用することができるため、今までにない嗜好の平蒔絵・高蒔絵・肉合蒔絵・漆絵の作成を可能にした。 5). The product of photopolymerizable lacquer copolymer and colored (enamel) lacquer copolymer that has an average particle size of 1 μm or less is digital printing such as inkjet printers with injection diameters of several to several tens of μm. In addition to being used as machine ink, it can also be used as silkscreen printing ink. Compared with the enzyme-curing type curing function, which is a conventional drying method for lacquer paints, it results in faster curing by photopolymerization. Because it can be used for various technique expressions, such as by adhering materials for lacquer painting, it has made it possible to create flat lacquer paintings, takatsuki paintings, meat paintings, and lacquer paintings that have never been seen before.
次に、本願発明に係る光重合性含漆共重合体、及びこの製造方法の最良な実施形態について、詳細に説明する。
１．基材となる漆は、ＪＩＳ５９５０に準じた製造漆、若しくはクロメ返しを行った漆を用い、これに光重合性オリゴマー・モノマーなどのアクリレート化合物を添加して混合物を製造する。ここで使用する光重合性アクレート化合物は、光重合性のオリゴマーであれば、ビスフェノールＡ型・ビスフェノールＦ型・ビスフェノールＳ型・エポキシ化油型・フェノールノボラック型・指環型など、多くの種類を持つエポキシアクリレート化合物の中から選択される。またウレタンアクリレートであれば、ジイソシアネート、ポリオール、ヒドロキシアクリレート及びその合成物から選択する。その他のオリゴマーとしては、不飽和ポリエステルアクリレートとその合成物などが使用できることから、同じ系に属する単官能基及び多官能基を持つモノマーと変性した溶液（１００部）に、クロメ返しを行った再製造漆（１０〜５０部）を配合・添加し、光重合性含漆共重合体とし、その溶液をボールミル（ボール径２〜１０ｍｍ）や回転攪拌・分散機器によって２〜３時間分散し、漆液中のゴム質、含窒素物を微粒化することが望ましい。
Next, the photopolymerizable lacquer-containing copolymer according to the present invention and the best embodiment of the production method will be described in detail.
1. The lacquer used as the base material is manufactured lacquer according to JIS5950 or lacquered lacquer, and an acrylate compound such as a photopolymerizable oligomer / monomer is added thereto to produce a mixture. If the photopolymerizable acrylate compound used here is a photopolymerizable oligomer, it has many types such as bisphenol A type, bisphenol F type, bisphenol S type, epoxidized oil type, phenol novolak type, and finger ring type. It is selected from epoxy acrylate compounds. In the case of urethane acrylate, it is selected from diisocyanates, polyols, hydroxy acrylates, and synthetic products thereof. As other oligomers, unsaturated polyester acrylates and synthetic products thereof can be used. Therefore, repolymerization was performed on a solution (100 parts) modified with monomers having monofunctional and polyfunctional groups belonging to the same system. Production lacquer (10-50 parts) is added and blended to make a photopolymerizable lacquer-containing copolymer, and the solution is dispersed for 2-3 hours with a ball mill (ball diameter 2-10 mm) or a rotating stirrer / dispersion device. It is desirable to atomize the rubber and nitrogen-containing substances in the liquid.
２．光重合性ウレタン及びエポキシ単官能基・多官能基モノマー（１００部）に、同じ系に属する光重合性オリゴマー（１０〜５０部）を添加し、製造漆あるいはクロメ返しを行った漆（１５〜７５部）を配合・添加し光重合性含漆共重合体とした後、１次微粒化工程として低い周波帯域（約１５〜２８ｋＨｚ）の超音波振動を付加して、その圧力波によって発生するキャビテーション（空洞現象）を利用した粉砕と攪拌によって微粒化したその後、さらに２次微粒化工程として上記周波数より高い周波数帯域（約２８〜４０ｋＨｚ）の超音波を照射する２段の微粒化工程によって、組成物中に含まれる漆成分のゴム質・含窒素物を微粒化することが望ましい。 2. Lacquer (15-) which is manufactured lacquer or chrome-turned by adding photopolymerizable oligomer (10-50 parts) belonging to the same system to photopolymerizable urethane and epoxy monofunctional group / polyfunctional group monomer (100 parts) 75 parts) is added and made into a photopolymerizable lacquer-containing copolymer, then ultrasonic vibration of a low frequency band (about 15 to 28 kHz) is added as a primary atomization process, and generated by the pressure wave After pulverization and agitation using cavitation (cavity phenomenon), and further by a two-stage atomization step of irradiating ultrasonic waves in a frequency band higher than the above frequency (about 28 to 40 kHz) as a secondary atomization step, It is desirable to atomize the rubbery and nitrogen-containing lacquer component contained in the composition.
３．有色（エナメル）の光重合性含漆共重合体の製造では、光重合性ウレタン及びエポキシ単官能基・多官能基モノマー（１００部）に、アゾ系・フタロシアニン系・キナクリドン系の有機系顔料あるいは、アナターゼ・ルチル（酸化チタン）、カーボンブラック、骨粉などの無機系顔料（２〜３０部）を添加し、回転式の剪断装置や下限値に近い周波帯域（約１６〜４０ｋＨｚ）の超音波などを用いた粉砕・剪断装置で微粒化し、有色（エナメル）の光重合性含漆共重合体を製造した後、さらに微粒化した光重合性含漆共重合体を添加し、有色（エナメル）の光重合性含漆共重合体を製造しても良い。 3. In the production of colored (enamel) photopolymerizable lacquer-containing copolymers, azo-, phthalocyanine-, quinacridone-based organic pigments or photopolymerizable urethane and epoxy monofunctional / polyfunctional monomers (100 parts) Addition of inorganic pigments (2-30 parts) such as anatase rutile (titanium oxide), carbon black, bone powder, etc., rotary shearing devices, ultrasonic waves in the frequency band (about 16-40 kHz) close to the lower limit, etc. After making a colored (enamel) photopolymerizable lacquered copolymer by adding a finely divided photopolymerizable lacquered copolymer, the colored (enamel) A photopolymerizable lacquer-containing copolymer may be produced.
４．または、光重合性ウレタン及びエポキシ単官能基・多官能基モノマー（１００部）に、製造漆あるいはクロメ返しを行った漆（１０〜３０部）を配合・添加し、アゾ系・フタロシアニン系・キナクリドン系の有機系顔料あるいは、アナターゼ・ルチル系の酸化チタン、カーボンブラック、骨粉などの無機系顔料（２〜３０部）を添加し、回転式の剪断装置や超音波（１５〜４０ｋＨｚ）などの粉砕・剪断装置で顔料及び漆液中のゴム質、含窒素物を微粒化した後、光重合性オリゴマー（５〜３０部）を添加しても良い。 4). Alternatively, lacquer (10-30 parts) that has been manufactured lacquer or chrome-backed is added to and added to photopolymerizable urethane and epoxy monofunctional group / polyfunctional group monomer (100 parts), and azo, phthalocyanine, quinacridone. Organic pigments or inorganic pigments (2-30 parts) such as anatase / rutile titanium oxide, carbon black, bone powder, etc., and grinding with a rotary shearing device or ultrasonic waves (15-40 kHz) -The photopolymerizable oligomer (5 to 30 parts) may be added after the rubber and nitrogen-containing material in the pigment and lacquer liquid are atomized with a shearing device.
５．これら光重合性含漆共重合体の硬化は、活性エネルギーとして紫外線を使用するが、その紫外線による硬化領域を２００〜４５０ｎｍとし、添加する光重合開始剤は、この領域で補うアルキルフェノン系光重合開始剤（α−ヒドロキシケトン・α−アミノケトン）の１−ヒドロキシーシクロヘキシルーフェニル−ケトン、２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オンまたは、アシルフォスフィンオキサイド系光重合開始剤（ビスアシルフォスフィンオキサイド）の２，４，６−トリメチルベンゾイルージフェニルーフォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイドなどを１０：９０〜９０：１０の割合で２種類以上を併用しても良い。 5). Curing of these photopolymerizable lacquer-containing copolymers uses ultraviolet rays as the active energy, but the curing region by the ultraviolet rays is set to 200 to 450 nm, and the added photopolymerization initiator is an alkylphenone-based photopolymerization supplemented in this region. 1-hydroxy-cyclohexyl ruphenyl-ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one or an acylphosphine as an initiator (α-hydroxyketone / α-aminoketone) Oxide-based photopolymerization initiator (bisacylphosphine oxide) such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc. 10: You may use 2 or more types together in the ratio of 90-90: 10.
（漆の製造）
［実施例１］
一般的に生漆は、油中水系型エマルジョン（逆ミセル）構造の中に通常１５〜３０％の水分を含み、さらにはウルシオール・水分・ゴム質・含窒素物などが含まれ、粒径は５〜１０μｍ程度と荒い。そのため、公知の特許発明（特許第３８３３２０号、特許第２８２１１１０号）では光重合性の含漆薄膜被膜を形成する際にゴム質が原因と推測されるザラによる凹凸が生じていたことから、ゴム質を微粒化する目的で公知の攪拌機器であるスリーワンモターＢＬ３００（新東化学株式会社製）の金属回転主軸に木篦を固定し、その木篦にゴム（ゴム硬度１０〜３０°）を装着し、セラミック容器とゴム篦の押圧、攪拌回転数１００〜１８０に高めたことで、剪断効果が向上した。その結果、通常の市販製造漆の硬化被膜の光沢値は６５〜７５％程度であったものが、本製造方式で製造された漆硬化被膜の光沢値は９５％以上の高い光沢値が得られた。光沢値が向上した要因としては、油中水系型エマルジョンやゴム質・含窒素物の粒子が微粒化されたことによる、ポリマー被膜の乱反射が無くなったことによる効果であることを確認した。
(Manufacture of lacquer)
[Example 1]
In general, raw lacquer usually contains 15-30% moisture in a water-in-oil emulsion (reverse micelle) structure, and further contains urushiol, moisture, rubber, nitrogen-containing materials, etc. As rough as 5-10 μm. Therefore, in the known patented invention (Patent No. 383320, Patent No. 2821110), when forming a photopolymerizable lacquer-containing thin film, irregularities due to the roughness, which is presumed to be caused by rubber, were generated. For the purpose of atomizing the quality, a wooden koji is fixed to the metal rotating main shaft of the three-one motor BL300 (manufactured by Shinto Chemical Co., Ltd.), which is a known stirring device, and rubber (rubber hardness 10-30 °) is attached to the wooden koji The shearing effect was improved by increasing the pressure between the ceramic container and the rubber bowl and increasing the stirring speed to 100 to 180. As a result, the gloss value of the cured film of ordinary commercially manufactured lacquer was about 65 to 75%, but the gloss value of the cured lacquer film manufactured by this production method was a high gloss value of 95% or more. It was. It was confirmed that the reason why the gloss value was improved was the effect of eliminating irregular reflection of the polymer film due to the atomization of water-in-oil type emulsions and rubber / nitrogen-containing particles.
［実施例２］
また、ＪＩＳ５９５０に準じた製造漆として生漆の他、なやし漆や素黒目漆をクロメ返しと称される再水分添加方式（含水率に対して２００〜３００％添加）で、含水率２〜３％台までのセラミック容器とゴム篦の押厚による剪断・脱水製造工程を経ることで、実施例１同様、ゴム質・含窒素物の他、油中水系型エマルジョン粒子が微粒化され、光沢値９０％以上の漆硬化被膜が得られた。
[Example 2]
In addition to raw lacquer as production lacquer in accordance with JIS 5950, Nayashi lacquer and plain black lacquer are re-moisture-added (200 to 300% added to the water content), and the water content is 2 to 2. By passing through a shear and dehydration manufacturing process by pressing up to 3% ceramic container and rubber punch, water-in-oil type emulsion particles are atomized and glossy in addition to rubbery and nitrogen-containing materials as in Example 1. A lacquer cured film having a value of 90% or more was obtained.
［表１］
●使用漆 なやし漆含水率６．３％
●含水率測定使用装置
（エー・アンド・ディ株式会社 加熱乾燥式水分計 ＭＸ−５０）
●実験前光沢 ７０％
（測定装置ＮＩＰＰＯＮ ＤＥＮＳＨＯＫＵ ＰＧ−１ 光沢度計６０°使用）
●製造条件 １００ｇなやし漆
（水分６．３％＝６．３ｇ×２００〜３００％水道水添加）
●アズワン真空デシケーターによる無酸素環境
●スリーワンモターＢＬ３００（新東化学株式会社）回転数（１００〜１１２）
●製造環境温度 ３０〜４０℃
●光沢測定塗布素地 ソーダーガラス平板
測定回数 測定量（ｇ） 時間（Ｈ） 含水率（％） 硬化被膜光沢値（％）
０ ７０
１ １．０７５ １ １６．６８
２ １．０９１ １ １２．８２
３ １．０７ ０．５ １０．２３
４ ０．９４７ ０．５ ８．６４
５ ０．９６８ １ ７．２３
６ ０．９６１８ ０．５ ６．４６
７ １．０７６ １ ４．９７
８ １．０１５ ０．５ ４．３６
９ １．０６０ ０．５ ３．３９ １０１．６
[Table 1]
● Used lacquer Nayashi lacquer water content 6.3%
● Moisture content measurement equipment (A & D Co., Ltd. Heating Drying Moisture Analyzer MX-50)
● 70% gloss before experiment
(Measurement device NIPPON DENSHOKU PG-1 Gloss meter 60 ° use)
● Production conditions 100g Nayashi Lacquer (moisture 6.3% = 6.3g x 200-300% tap water added)
● Anoxic environment with As One vacuum desiccator ● Three One Motor BL300 (Shinto Chemical Co., Ltd.) Speed (100-112)
● Manufacturing environment temperature 30-40 ℃
● Gloss measurement coating substrate Number of measurements of soda glass flat plate Measurement amount (g) Time (H) Moisture content (%) Hardened film gloss value (%)
0 70
1 1.075 1 16.68
2 1.091 1 12.82
3 1.07 0.5 10.23
4 0.947 0.5 8.64
5 0.968 1 7.23
6 0.9618 0.5 6.46
7 1.076 1 4.97
8 1.015 0.5 4.36
9 1.060 0.5 3.39 101.6
［実施例３］
他の微粒化製造方法としては、室内雰囲気において公知の回転篦式漆製造機を使用し、急激な水分揮発を防ぐ為に、なやし漆１００ｇの含水率に対して２００〜３００％の水道水若しくは蒸留水、さらには製造段階で松根油５〜１０ｇを添加し、実施例１同様にゴム篦の押圧と回転数を高めたことで光沢値８５％以上の漆硬化被膜が得られた。
[Example 3]
As another atomization manufacturing method, in order to prevent rapid water volatilization using a known rotary lacquer lacquer making machine in an indoor atmosphere, water supply of 200 to 300% with respect to the moisture content of 100 g of palm lacquer Water or distilled water and further 5 to 10 g of pine oil were added in the production stage, and a lacquer cured film having a gloss value of 85% or more was obtained by increasing the pressure and the number of rotations of the rubber jar as in Example 1.
（光重合性含漆共重合体の生成）
［実施例４］
実施例１〜３で製造された漆（１０〜５０部）と光重合性ウレタン及びエポキシ単官能基・多官能基モノマー（１００部）を混合しその後、公知の回転スクリュー機器において攪拌・分散した後、１次濾過精製を行った光重合性含漆共重合体に超音波振動子（例えば、本多電子社製プラスチックウェルダー）を用いて約２８ｋＨｚの超音波振動を付加して微粒化を行なった後、２次濾過精製として減圧濾過若しくは、自然落下方式による濾過を行なって１μｍ以下に微粒化された光重合性含漆共重合体を製造した。
(Generation of photopolymerizable lacquer-containing copolymer)
[Example 4]
The lacquer (10-50 parts) manufactured in Examples 1 to 3, photopolymerizable urethane, and epoxy monofunctional group / polyfunctional group monomer (100 parts) were mixed, and then stirred and dispersed in a known rotary screw device. After that, the photopolymerizable lacquer-containing copolymer subjected to the primary filtration purification is subjected to atomization by applying an ultrasonic vibration of about 28 kHz using an ultrasonic vibrator (for example, a plastic welder manufactured by Honda Electronics Co., Ltd.). After that, a photopolymerizable lacquer-containing copolymer that was atomized to 1 μm or less was manufactured by performing filtration under reduced pressure or filtration by a natural drop method as secondary filtration purification.
［実施例５］
実施例４以外の光重合性含漆共重合体の製造方法として、実施例１〜３でゴム質を微粒化した漆（１０〜５０部）と光重合性ウレタン及びエポキシ単官能基・多官能基モノマー（１００部）を混合し、公知の回転式ボールミル装置（セラミックボール粒径２〜１０ｍｍ球を使用）やゴムを装着した回転式剪断装置を使い 、攪拌・分散・剪断工程を行い、１次・２次濾過精製により１μｍ以下に微粒化された光重合性含漆共重合体が製造できた。
[Example 5]
As a method for producing a photopolymerizable lacquer-containing copolymer other than Example 4, lacquer (10-50 parts) obtained by atomizing rubber in Examples 1-3, photopolymerizable urethane, and epoxy monofunctional group / polyfunctional A basic monomer (100 parts) is mixed, and a known rotary ball mill device (using ceramic ball particle diameters of 2 to 10 mm) and a rotary shearing device equipped with rubber are used to perform stirring, dispersion, and shearing steps. A photopolymerizable lacquer-containing copolymer that was atomized to 1 μm or less by secondary / secondary filtration purification could be produced.
［実施例６］
実施例４．５で製造された光重合性含漆共重合体に、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイドを主成分とした２種類以上の光重合開始剤を６〜２０％配合し、再び超音波振動を照射する微粒化工程と濾過を経た後、アプリケーターで薄膜被膜（５〜１０μｍ程度）を形成し、硬化活性エネルギー線として紫外線（２００〜４５０ｎｍ）を照射し、光重合性含漆共重合体（生成物）による凹凸が生じない秒単位で硬化する漆被膜が得られた。膜厚計による測定結果は６〜８μｍ、光沢値９５％以上の硬質被膜を形成した。
[Example 6]
To the photopolymerizable lacquer-containing copolymer produced in Example 4.5, 6 or more kinds of photopolymerization initiators containing bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide as a main component are added. After blending ~ 20%, passing through the atomization process and irradiating ultrasonic vibration again and filtering, a thin film film (about 5 ~ 10μm) is formed with an applicator and irradiated with ultraviolet rays (200 ~ 450nm) as curing active energy rays As a result, a lacquer film that hardens in seconds with no unevenness caused by the photopolymerizable lacquer copolymer (product) was obtained. As a result of measurement by a film thickness meter, a hard film having a gloss value of 95% or more was formed.
［実施例７］
実施例４〜５で製造された光重合性含漆共重合体以外の配合比の異なる製造例としては単官能アクリレート（１００部）、漆（１０〜５０部）を添加し、実施例６で使用した光重合開始剤を６〜２０％添加し、紫外線（２００〜４５０ｎｍ）を照射した後、薄膜光重合型含漆被膜が得られたが、塗膜の鉛筆硬度（スガ鉛筆硬度試験器ＮＵＳ−ＩＳＯ−３）は２〜３Ｂであった。
[Example 7]
Monofunctional acrylate (100 parts) and lacquer (10 to 50 parts) were added as production examples with different compounding ratios other than the photopolymerizable lacquer-containing copolymer produced in Examples 4 to 5, and in Example 6 After adding 6 to 20% of the used photopolymerization initiator and irradiating with ultraviolet rays (200 to 450 nm), a thin film photopolymerization type lacquer-containing film was obtained, but the pencil hardness of the coating film (Suga pencil hardness tester NUS -ISO-3) was 2-3B.
［実施例８］
実施例７で使用した光重合性含漆共重合体に、多官能基モノマー（１０〜５０部）を添加し、再び紫外線を照射した結果、塗膜の鉛筆硬度（スガ鉛筆硬度試験器ＮＵＳ−ＩＳＯ−３）はＨＢ〜Ｆまでの塗膜硬度上昇が確認できた。このことから、多官能基モノマーの配合比は最大で１００部：１００部が望ましいことを確認した。
[Example 8]
As a result of adding a polyfunctional monomer (10 to 50 parts) to the photopolymerizable lacquer-containing copolymer used in Example 7 and irradiating ultraviolet rays again, the pencil hardness of the coating film (Suga pencil hardness tester NUS- ISO-3) was able to confirm an increase in coating film hardness from HB to F. From this, it was confirmed that the blending ratio of the polyfunctional monomer was desirably 100 parts: 100 parts at the maximum.
［実施例９］
実施例７で使用した光重合性含漆共重合体（１００部）に、光重合性オリゴマー（エポキシアクリレート）を１０ｇ添加し、実施例６同様ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイドを主成分とした２種類以上の光重合開始剤を添加しその後、紫外線（２００〜４５０ｎｍ）を照射した結果、塗膜硬度の上昇が確認できた。また、ここで使用した光重合性のオリゴマー（エポキシアクリレート）はノンソルタイプを使用したことから、揮発性有機溶剤を含まない環境配慮型及び無溶剤型の光重合性含漆共重合体となった。
[Example 9]
10 g of photopolymerizable oligomer (epoxy acrylate) was added to the photopolymerizable lacquer-containing copolymer (100 parts) used in Example 7, and bis (2,4,6-trimethylbenzoyl) -phenyl as in Example 6. As a result of adding two or more kinds of photopolymerization initiators mainly composed of phosphine oxide and then irradiating with ultraviolet rays (200 to 450 nm), an increase in coating film hardness was confirmed. In addition, since the photopolymerizable oligomer (epoxy acrylate) used here is a non-sol type, it becomes an environmentally friendly and solvent-free photopolymerizable lacquer-containing copolymer that does not contain volatile organic solvents. It was.
［実施例１０］
実施例４．５での漆配合比は単・多官能基アクリレートに対して（１０〜５０部）であったが、実施例７同様に単官能基アクリレートを使用した際、漆の配合比は５０部以上の添加が可能であり、その後実施例８．９に準じて多官能基アクリレートと光重合性オリゴマーを添加し、漆の添加率の上昇とともに光重合開始剤の添加率を上昇させることで秒速硬化し、漆の肉持ち感、ふっくら感と潜在的機能性を兼ね備えた光重合型含漆共重合体となった。
[Example 10]
The lacquer blending ratio in Example 4.5 was (10 to 50 parts) with respect to the mono- and polyfunctional acrylate, but when using the monofunctional acrylate as in Example 7, the lacquer blending ratio was Addition of 50 parts or more is possible, and then add a polyfunctional acrylate and a photopolymerizable oligomer according to Example 8.9, and increase the addition rate of the photopolymerization initiator as the lacquer addition rate increases. The photo-curing type lacquer-containing copolymer that combines the lacquer fleshiness, plumpness and potential functionality.
［実施例１１］
実施例４．５で製造された光重合性含漆共重合体に、アゾ系・フタロシアニン系・キナクリドン系の有機系顔料あるいは、アナターゼ・ルチル（酸化チタン）、カーボンブラック、骨粉などの無機系顔料（２〜３０部）を添加し次に、分散剤などの添加剤を顔料比に対して０．５〜６０％添加し、約２８ｋＨｚの超音波振動を６〜１２時間付加して、攪拌・分散・粉砕工程を経ることにより顔料が微粒化され、濾過精製工程を経て粒径１μｍ以下の有色（エナメル）の光重合性含漆共重合体を製造した。次に、実施例６同様にビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイドを主成分とした２種類以上の光重合開始剤を添加、その後、組成物被膜に硬化活性エネルギー線として紫外線（２００〜４５０ｎｍ）を照射することで秒速硬化の薄膜光重合性含漆共重合体の被膜が形成された。
[Example 11]
To the photopolymerizable lacquer-containing copolymer produced in Example 4.5, an inorganic pigment such as an azo-based, phthalocyanine-based, or quinacridone-based organic pigment, or anatase-rutile (titanium oxide), carbon black, bone powder, etc. (2-30 parts) is added, and then an additive such as a dispersant is added in an amount of 0.5-60% with respect to the pigment ratio, and an ultrasonic vibration of about 28 kHz is added for 6-12 hours. The pigment was atomized by passing through a dispersion / pulverization step, and a colored (enamel) photopolymerizable lacquer-containing copolymer having a particle size of 1 μm or less was produced through a filtration purification step. Next, in the same manner as in Example 6, two or more kinds of photopolymerization initiators mainly composed of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide were added, and then a curing active energy ray was applied to the composition film. As a result of irradiating with ultraviolet rays (200 to 450 nm), a coating film of a thin film photopolymerizable lacquer-containing copolymer that was cured in seconds was formed.
［実施例１２］
実施例１１における顔料の微粒化には分散剤、界面活性剤を顔料比に対して０．５〜６０％添加後、ゴムを装着した回転式剪断装置のセラミック容器の中にセラミックボール２．５．８．１０ｍｍ球を混合させ約７２〜９６時間の攪拌・分散・剪断工程を経ることにより、１μｍ以下の光重合性含漆共重合体となった。その後、実施例６同様に光重合開始剤を添加、硬化活性エネルギー線として紫外線を照射することで秒速硬化の光重合性含漆共重合体（生成物）の被膜が得られたが微粒化製造時間としては、超音波照射による微粒化の方法が短時間で製造できることを確認した。
[Example 12]
In Example 11, the pigment is atomized by adding 0.5 to 60% of a dispersant and a surfactant to the pigment ratio, and then adding ceramic balls 2.5 in a ceramic container of a rotary shearing device equipped with rubber. 8. A 10-mm sphere was mixed and subjected to a stirring, dispersion, and shearing process for about 72 to 96 hours to obtain a photopolymerizable lacquer-containing copolymer of 1 μm or less. Thereafter, a photopolymerization initiator was added in the same manner as in Example 6, and a film of photopolymerizable lacquer-containing copolymer (product) that was cured in seconds was obtained by irradiating ultraviolet rays as a curing active energy ray. As for time, it was confirmed that the atomization method by ultrasonic irradiation can be manufactured in a short time.
［実施例１３］
単官能基モノマー１００ｇ、多官能基モノマー３０ｇに、実施例１１．１２同様、分散剤、界面活性剤を顔料比に対して０．５〜６０％添加し攪拌・分散後、有機・無機系顔料を２〜３０部添加し、約２８ｋＨｚの超音波振動を付加した。その際、マグネットスターラーを使用して有色の光重合性含漆共重合体を攪拌すると共に、超音波の圧力波の液中伝搬による攪拌・粉砕、加えて超音波振動によって生じたキャビテーションの空泡の破裂による分散と粉砕機能により微粒化する。液温は６０℃を保持しつつ、約６〜１２時間の微粒化作業を行った。その後、微粒化した光重合性含漆共重合体に実施例４．５で製造した生成物（光重合性含漆共重合体）を配合し、さらに実施例６と同様に光重合開始剤を添加して塗布した後に硬化活性エネルギー線として紫外線（２００〜４５０ｎｍ）を照射して、秒速硬化型の有色（赤・青・黄・白・黒）の光重合性含漆共重合体の被膜が得られた。
[Example 13]
As in Example 11.12, 100% monofunctional group monomer and 30 g polyfunctional group monomer were added with a dispersant and a surfactant in an amount of 0.5 to 60% based on the pigment ratio, stirred and dispersed, and then an organic / inorganic pigment. Was added, and ultrasonic vibration of about 28 kHz was added. At that time, the colored photopolymerizable lacquer-containing copolymer is stirred using a magnetic stirrer, stirring and pulverization by propagation of ultrasonic pressure waves in the liquid, and cavitation bubbles generated by ultrasonic vibration. It is atomized by the dispersion and pulverization function by bursting. While maintaining the liquid temperature at 60 ° C., the atomization work was performed for about 6 to 12 hours. Thereafter, the product (photopolymerizable lacquer-containing copolymer) produced in Example 4.5 was blended into the atomized photopolymerizable lacquer-containing copolymer, and a photopolymerization initiator was added in the same manner as in Example 6. After applying and applying ultraviolet rays (200 to 450 nm) as a curing active energy ray, a coating film of a photopolymerizable lacquer copolymer of colored (red / blue / yellow / white / black) with a fast-curing type is applied. Obtained.
（物性の検証と実用化の検討）
［実施例１４］
次に、これらの光重合性含漆共重合体を実際のインクジェットプリター用インキまたは、コーティング剤としての機能性を検討する目的で粘度３０ｍＰａ．ｓに調整し、温度依存性を測定した。その結果、２５℃では白２３．４ｍＰａ．ｓ、赤２３．９ｍＰａ．ｓ、黄２７ｍＰａ．ｓ、青２９．６ｍＰａ．ｓの粘性となり、５０℃では白８．９２ｍＰａ．ｓ、赤１０．１ｍＰａ．ｓ、黄１０．９ｍＰａ．ｓ、青１３．５ｍＰａ．ｓの低粘性の有色光重合性含漆共重合体（図・表２）が生成された。
(Verification of physical properties and examination of practical application)
[Example 14]
Next, these photopolymerizable lacquer-containing copolymers were used with a viscosity of 30 mPa.s for the purpose of examining the functionality as an actual ink for ink jet printer or a coating agent. The temperature dependence was measured after adjusting to s. As a result, at 25 ° C., white 23.4 mPa.s. s, red 23.9 mPa.s s, yellow 27 mPa.s. s, blue 29.6 mPa.s. s, and at 50 ° C., white 8.92 mPa.s. s, red 10.1 mPa.s. s, yellow 10.9 mPa.s s, blue 13.5 mPa.s A low-viscosity colored photopolymerizable lacquer-containing copolymer (Figure / Table 2) was produced.
［表２］ 光重合含漆共重合体の温度依存性数値
粘度（ｍＰａ・ｓ）
温度（℃） ＵＶ白 ＵＶ赤 ＵＶ黄 ＵＶ青
２５ ２３．４ ２３．９ ２７ ２９．６
３０ １８．２ １９ ２１．３ ２４．１
３５ １４．６ １５．７ １７．４ ２０．１
４０ １２ １３．２ １４．５ １７．１
４５ １０．２ １１．３ １２．４ １５
５０ ８．９２ １０．１ １０．９ １３．５
[Table 2] Temperature-dependent numerical values of photopolymerized lacquer copolymer
Viscosity (mPa · s)
Temperature (° C.) UV White UV Red UV Yellow UV Blue 25 23.4 23.9 27 29.6
30 18.2 19 21.3 24.1
35 14.6 15.7 17.4 20.1
40 12 13.2 14.5 17.1
45 10.2 11.3 12.4 15
50 8.92 10.1 10.9 13.5
［実施例１５］
実施例６〜１３で生成された光重合性含漆共重合体は、光重合オリゴマーや多官能基モノマー・アクリレートの配合比により薄膜の軟質から硬質の硬化被膜が得られる。そのため、熱可塑性樹脂であればポリプロピレン樹脂・ポリアミド樹脂・ポリエーテルケトン・ポリカーボネイト樹脂等の柔軟性のある素材や熱硬化性樹脂ではエポキシ樹脂・フェノール樹脂・メラミン樹脂等などのプラスチック工業用製品素材などへの装飾用インキまたはコーティング剤として使用できる。また、無垢の木材を含む木質系有機質素材、ガラスや金属系の無機質素材などへの装飾インキ及びコーティング剤としても塗布及び射出できる機能性を持つ。
[Example 15]
The photopolymerizable lacquer-containing copolymer produced in Examples 6 to 13 can be obtained from a soft thin film to a hard cured film depending on the blending ratio of the photopolymerization oligomer and the polyfunctional monomer / acrylate. Therefore, flexible materials such as polypropylene resin, polyamide resin, polyetherketone, and polycarbonate resin for thermoplastic resins, and plastic industrial product materials such as epoxy resin, phenolic resin, and melamine resin for thermosetting resins, etc. Can be used as decorative ink or coating agent. It also has the functionality that can be applied and injected as a decorative ink and coating agent for woody organic materials including solid wood, glass and metal inorganic materials.
［実施例１６］
実施例６〜１３で生成された光重合性含漆共重合体は、１ｐｌ以上のインクジェットプリンターノズルからの射出が可能である。特に、工業用インクジェットプリンターノズルのようにピエゾ加温方式（オンデマンドピエゾを含む。）のものであれば４〜４２ｐｌからの射出が可能である。そのため、光重合性含漆共重合体の生成物は、顔料が含まれない透きインキとして使用した、顔料を添加した光重合性含漆共重合体の生成物はカラーインキであることから様々な彩色が可能となった。その応用素地としては、実施例１５に記載したとおりである。特にその中でも、ウレタン・油性・漆塗装塗膜へ日本固有の伝統技法である蒔絵が再現できる。
[Example 16]
The photopolymerizable lacquer-containing copolymer produced in Examples 6 to 13 can be ejected from an inkjet printer nozzle of 1 pl or more. In particular, injection from 4 to 42 pl is possible with a piezo heating method (including on-demand piezo) such as an industrial inkjet printer nozzle. For this reason, the photopolymerizable lacquer-containing copolymer product used as a transparent ink that does not contain a pigment, and the photopolymerizable lacquer-containing copolymer product added with a pigment is a color ink. Coloring is now possible. The application base is as described in the fifteenth embodiment. In particular, it is possible to reproduce the traditional Japanese traditional technique of maki-e on urethane, oily, and lacquered paint films.
［実施例１７］
インクジェットプリンターピエゾ加温方式による蒔絵技法の再現では、本発明の特徴であるところの、薄膜でしかも平滑さが求められる平蒔絵のインキとして最適な活用である。光重合性含漆共重合体の生成物を４〜４２ｐｌのノズルから射出した後、紫外線（２００〜４５０ｎｍ）を照射し、インキ中に含まれる微粒化オリゴマー成分の作用によって消金粉などの金属粉が蒔き付けられ固着することで完成する。また、紫外線を照射する前に本金・本銀丸粉・平目粉などを蒔き付けることで、漆加飾技法の中でも高度で且つ高級感のある平研蒔絵、丘研蒔絵、梨地蒔絵や厚膜を形成する肉合蒔絵、高上げ蒔絵などの伝統的技法を再現できることから、光重合性含漆蒔絵工法が構築できた。そのほか、有色の光重合性含漆共重合体からなる生成物を同じくインクジェットノズルから赤・青・黄色の３原色を射出することで、シルクスクリーン印刷の際に必要なポジフィルムを作らずに、コンピューターのデジタル画像をダイレクトにしかも短時間でフルカラー印刷ができたことから、漆絵の様な極彩色の漆絵技法が構築できた。
[Example 17]
The reproduction of the maki-e technique by the inkjet printer piezo heating method is the best use as a flat maki-e ink that is a thin film and requires smoothness, which is a feature of the present invention. After injecting the photopolymerizable lacquer-containing copolymer product from a nozzle of 4 to 42 pl, irradiating with ultraviolet rays (200 to 450 nm), metal powder such as metal powder by the action of atomized oligomer components contained in the ink Is completed by sticking and sticking. In addition, by applying gold, genuine silver round powder, and flat-meal powder before irradiating with ultraviolet rays, the lacquer decoration technique has a high-class and high-class impression of Hiraken Maki, Oka Maki, Nashiji Maki and Thick Traditional techniques such as Mikugoe and Takarae paintings that form films can be reproduced, so a photopolymerizable lacquer lacquer painting method has been established. In addition, by injecting the three primary colors of red, blue, and yellow from the inkjet nozzle, the product made of colored photopolymerizable lacquer-containing copolymer, without making the positive film necessary for silk screen printing, Because it was possible to print digital images directly from a computer directly in a short time, a lacquer painting technique with a brilliant color like a lacquer painting could be constructed.
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| JP2013189001A (en) * | 2012-03-13 | 2013-09-26 | Sugishima Toryo Kk | Container-like shaped body and method for coating the same |
| JP2015048473A (en) * | 2013-09-04 | 2015-03-16 | ハンコック ナショナル コープＨａｎｋｏｏｋ Ｎａｔｉｏｎａｌ Ｃｏｒｐ． | Non-allergic urushiol polymer |
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| EP2527410A2 (en) * | 2009-12-30 | 2012-11-28 | Posco | Surface treatment method for a substrate denatured urushiol derived from toxicodendron vernicifluum |
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| JP2013189001A (en) * | 2012-03-13 | 2013-09-26 | Sugishima Toryo Kk | Container-like shaped body and method for coating the same |
| JP2015048473A (en) * | 2013-09-04 | 2015-03-16 | ハンコック ナショナル コープＨａｎｋｏｏｋ Ｎａｔｉｏｎａｌ Ｃｏｒｐ． | Non-allergic urushiol polymer |
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