JPS5948007B2 - Manufacturing method for finely colored resin with excellent light resistance - Google Patents

Description

【発明の詳細な説明】 本発明は、耐光性に優れた微細着色樹脂の製法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a finely colored resin having excellent light resistance.

詳しくは、染料により着色された未硬化のベンゾグアナ
ミン系樹脂の乳化物にスルホン基を持つ水溶性の紫外線
吸収剤を添加し、必要に応じて他の硬化触媒の共存下で
乳化状態を保ちつつ樹脂を硬化させた後、硬化物を水媒
体より分離乾燥することから成る耐光性の飛躍的に改善
された微細着色樹脂の製法に関するものである。染料の
持つ鮮明な色彩を顔料に活かすべく、合成樹脂を染料で
着色した後微粉砕して顔料として用いる試みは、比較的
古くから行なわれている。In detail, a water-soluble ultraviolet absorber having a sulfonic group is added to an emulsion of uncured benzoguanamine resin colored with a dye, and if necessary, the resin is mixed while maintaining an emulsified state in the coexistence of other curing catalysts. The present invention relates to a method for producing a finely colored resin with dramatically improved light resistance, which comprises curing the resin and then separating and drying the cured product from an aqueous medium. In order to take advantage of the vivid colors of dyes in pigments, attempts have been made for a relatively long time to color synthetic resins with dyes, then pulverize them and use them as pigments.

しかし、このような方法では、用うべき合成樹脂として
は機械的微粉砕の容易なものに限られ、それゆえ、耐熱
性、耐溶剤性等の点で満足できるものは得られていない
。本発明者らは、耐水性、耐溶剤性、耐熱性に優れてい
るベンゾグアナミン系樹脂を微細着色樹脂として応用す
べく鋭意研究した結果、染料により着色された未硬化の
ベンゾグアナミン系樹脂の乳化物に硬化触媒を加え、乳
化状態に保ちながら硬化反応を進め、樹脂を不溶不融状
態に至らしめることにより、あるいは無着色未硬化のベ
ンゾグアナミン系樹脂の乳化物に特に水溶性染料を加え
、硬化触媒の共存下に乳化状態を保ちながら樹脂の硬化
反応を進め、不溶不融状態に至らしめることにより得ら
れる微細着色樹脂の懸濁物から樹脂固形分を分離乾燥す
ることからなる顔料として有効に用い得る微細着色樹脂
の製法を見い出している。However, in this method, the synthetic resins to be used are limited to those that can be easily mechanically pulverized, and therefore, it has not been possible to obtain a synthetic resin that is satisfactory in terms of heat resistance, solvent resistance, etc. As a result of intensive research into the application of benzoguanamine resin, which has excellent water resistance, solvent resistance, and heat resistance, as a finely colored resin, the present inventors found that an emulsion of uncured benzoguanamine resin colored with a dye By adding a curing catalyst and proceeding with the curing reaction while keeping it in an emulsified state, the resin becomes insoluble and infusible.Alternatively, by adding a water-soluble dye to an emulsion of uncolored, uncured benzoguanamine resin, the curing catalyst is It can be effectively used as a pigment by separating and drying the resin solid content from a suspension of fine colored resin obtained by proceeding with the curing reaction of the resin while maintaining an emulsified state in coexistence and reaching an insoluble and infusible state. We have discovered a method for producing finely colored resin.

この方法で得られる微細着色樹脂は、粒子径０．５〜１
０ミクロンの範囲の粒子で、耐熱性、耐溶剤性、耐色移
行性に優れた顔料として印刷インキ、プラスチツクの着
色、塗料および捺染等の種々の分野で有効に用いること
ができる。そして微細着色樹脂は、染料の持つ鮮明な色
彩を特徴としており、それら個有の特徴ある色彩ゆえに
他の顔料での代替は極めて困難な場合が多い。しかし、
惜しむらくは、これらの詳明な染料を使用して製造され
た微細着色樹脂の耐光性はいくらか劣つている場合があ
ることもあるということである。従来、樹脂顔料の耐光
性を改善すべく種々の努力がなされているが、その代表
的なものに紫外線吸収剤を用いる試みがある。The fine colored resin obtained by this method has a particle size of 0.5 to 1
With particles in the 0 micron range, it can be effectively used in various fields such as printing inks, plastic coloring, coatings, and textile printing as a pigment with excellent heat resistance, solvent resistance, and color transfer resistance. Fine colored resins are characterized by the vivid colors of dyes, and because of their unique, characteristic colors, it is often extremely difficult to replace them with other pigments. but,
Unfortunately, the lightfastness of micropigmented resins made using these specific dyes may be somewhat inferior. Conventionally, various efforts have been made to improve the light resistance of resin pigments, and a typical example is an attempt to use an ultraviolet absorber.

紫外線吸収剤は、特ノに劃旨顔料を構成する合成樹脂へ
の相溶性の大きなものが選択されて、合成樹脂中に染料
と共に添加されたり、あるいは樹脂顔料を各種分野へ使
用するに際し、被着色物である合成樹脂もしくは塗料、
インキのビヒクル中に添加されたりする。Ultraviolet absorbers are selected to have high compatibility with the synthetic resins that make up the pigments, and are added to the synthetic resins together with dyes, or when resin pigments are used in various fields. Synthetic resins or paints that are colored materials,
It is sometimes added to the ink vehicle.

より望ましくは、樹脂顔料を効果的に紫外線から保護す
べく、樹脂顔料を高濃度の紫外線吸収剤を含む層でコー
テイングする方法である。しかし、このようなコーテイ
ング方法は、一部塗料分野では紫外線吸収剤を含む透明
な保護被膜（クリアーオーバーレイ）として実用化され
ているが、作業性の点で問題を残しており、プラスチツ
クの着色、印刷インキ、捺染分野に至つては、その応用
は技術的に極めて困難な状況にある。本発明者らは、以
上の主旨に鑑み、かつ本発明者らの方法による染色され
た未硬化のベンゾグアミン系樹脂乳化物の特徴を応用し
、該乳化物にスルホン基を持つ水溶性の紫外線吸収剤を
添加して、あるいは該紫外線吸収剤とメラミン系初期縮
合物を添加して乳化状態を保ちつつ硬化させることによ
り、微細着色樹脂に優れた耐光性を付与できることを見
い出し、本発明を完成させたものである。More desirable is a method in which the resin pigment is coated with a layer containing a highly concentrated ultraviolet absorber in order to effectively protect the resin pigment from ultraviolet rays. However, although this coating method has been put into practical use as a transparent protective film (clear overlay) containing ultraviolet absorbers in some paint fields, it still has problems in terms of workability, such as coloring of plastics, In the field of printing ink and textile printing, its application is technically extremely difficult. In view of the above, the present inventors applied the characteristics of an uncured benzogamine resin emulsion dyed by the present inventors' method, and developed a water-soluble ultraviolet absorbing material having a sulfonic group in the emulsion. We have discovered that excellent light resistance can be imparted to finely colored resin by adding a UV absorber or a melamine-based initial condensate and curing it while maintaining an emulsified state, and have completed the present invention. It is something that

第１の発明は、染料で着色された未硬化のベンゾグアナ
ミン系樹脂の乳化物にスルホン基を持つ水溶性の紫外線
吸収剤を添加し、必要に応じて他の硬化触媒をさらに添
加し、乳化状態で樹脂の硬化反応を進め、硬化物を水媒
体から分離し乾燥することを特徴とすれものである。第
２の発明は、染料により着色された未硬化のベンゾグア
ナミン系樹脂の乳化物に、スルホン基を持つ水溶性の紫
外線吸収剤及びメラミンとホルムアルデヒドとの水溶性
初期縮合物、又はスルホン基を持つ水溶性の紫外線吸収
剤及びメラミン１００〜５０重量部とベンゾグアナミン
Ｏ〜５０重量部の割合で成る混合物とホルムアルデヒド
との水溶性初期縮合物を添加し、必要に応じて他の硬化
触媒をさらに添加し、乳化状態で樹脂の硬化反応を進め
、硬化物を水媒体から分離し乾燥することを特徴とする
ものである。The first invention involves adding a water-soluble ultraviolet absorber having a sulfonic group to an emulsion of uncured benzoguanamine resin colored with a dye, and further adding other curing catalysts as necessary to obtain an emulsified state. It is characterized by proceeding with the curing reaction of the resin, separating the cured product from the aqueous medium, and drying it. The second invention is to add a water-soluble ultraviolet absorber having a sulfonic group and a water-soluble initial condensate of melamine and formaldehyde to an emulsion of an uncured benzoguanamine resin colored with a dye, or a water-soluble initial condensate of melamine and formaldehyde. A water-soluble initial condensate of formaldehyde and a mixture of 100 to 50 parts by weight of melamine and 50 parts by weight of benzoguanamine is added, and if necessary, other curing catalysts are further added, It is characterized by proceeding with the curing reaction of the resin in an emulsified state, and separating the cured product from the aqueous medium and drying it.

本発明の方法によつて得られた微細着色樹脂は、従来法
である紫外線吸収剤を染料と共に微細着色樹脂を構成す
る合成樹脂に溶解させる方法や紫外線吸収剤を被着色物
である合成樹脂あるいは塗料、インキのビヒクル中に添
加する方法に比較して、紫外線吸収剤の作用がより効果
的に発揮せられる。The finely colored resin obtained by the method of the present invention can be obtained by a conventional method in which an ultraviolet absorber is dissolved together with a dye into a synthetic resin constituting the finely colored resin, or by a method in which an ultraviolet absorber is dissolved in a synthetic resin that is a material to be colored or The action of the ultraviolet absorber can be more effectively exerted compared to the method of adding it to the paint or ink vehicle.

また、微細着色樹脂自体に優れた耐光性が付与されてい
る点で、印刷インキ、プラスチツクの着色、塗料、捺染
等のすべての分野に極めて有効に適用できるものである
。本発明の優れた効果がいかなる作用によつて発現する
のかについて正確に説明することは困難であるが、恐ら
くつぎの理由に基づくものと思われる。Furthermore, since the finely colored resin itself has excellent light resistance, it can be extremely effectively applied to all fields such as printing inks, plastic coloring, paints, and textile printing. Although it is difficult to explain exactly how the excellent effects of the present invention are produced, it is probably based on the following reasons.

すなわち、染料によつて着色された未硬化の゛ ベンゾ
グアナミン系樹脂の乳化物に添加されたスルホン基を持
つ水溶性の紫外線吸収剤は、スルホン基に対して活性な
該乳化物粒子と該乳化物粒子の表面部分で反応する結果
、該乳化物粒子表面に紫外線吸収剤の高濃度に分布した
層が形成され、それゆえ、微細着色樹脂が極めて効果的
に紫外線より保護されることによつて、本発明の優れた
効果が発現されるものと思われる。しかし、このような
理由だけで本発明が制限されるものでなく、いずれにせ
よ、本発明の方法で得られた微細着色樹脂は、添加され
た紫外線吸収剤の作用が極めて効果的に発揮され、その
耐光性は非常に優れており、耐熱性、耐溶剤性等従来よ
り保有していた特色をそのまま保持している。本発明者
らは、本発明の処理を飾され、硬化反応を終えた後の懸
濁物の水相を分析した結果、水相の水溶性の紫外線吸収
剤による紫外線吸収能は極めて微弱であり、添加された
スルホン基を持つ水溶性の紫外線吸収剤は、ベンゾグア
ナミン系樹脂の乳化物粒子と反応し、水相よりベンゾグ
アナミン系樹脂相に移行したことを確認している。That is, the water-soluble ultraviolet absorber having a sulfone group added to the uncured benzoguanamine-based resin emulsion colored with a dye is capable of absorbing the emulsion particles and the emulsion that are active toward sulfone groups. As a result of the reaction at the surface part of the particles, a highly concentrated layer of ultraviolet absorber is formed on the surface of the emulsion particles, and the fine colored resin is therefore very effectively protected from ultraviolet rays. It is believed that the excellent effects of the present invention will be realized. However, the present invention is not limited solely by this reason, and in any case, the finely colored resin obtained by the method of the present invention exhibits the action of the added ultraviolet absorber extremely effectively. , its light resistance is very excellent, and it retains its conventional characteristics such as heat resistance and solvent resistance. The present inventors analyzed the aqueous phase of the suspension after the treatment of the present invention and completed the curing reaction, and found that the ultraviolet absorption ability of the water-soluble ultraviolet absorber in the aqueous phase was extremely weak. It has been confirmed that the added water-soluble ultraviolet absorber having a sulfone group reacts with the benzoguanamine-based resin emulsion particles and transfers from the aqueous phase to the benzoguanamine-based resin phase.

さらに、未硬化のベンゾグアナミン系樹脂の乳化物への
スルホン基を持つ水溶性の紫外線吸収剤の添加をメラミ
ンとホルムアルデヒドとの水溶性初期縮合物またはメラ
ミン１００〜５０重量部とベンゾグアナミン０〜５０重
量部の割合で成る混合物とホルムアルデ七ドとの水溶性
初期縮合物と共に行なうことによつて、耐光性について
はもちろんのこと、さらに、非常に優れた耐色移行性が
微細着色樹脂に付与されるものである。本発明における
染料により着色された未硬化のベンゾグアナミン系樹脂
の乳化物は種々の方法によつて容易に調製できるもので
ある。Furthermore, a water-soluble ultraviolet absorber having a sulfonic group is added to an emulsion of uncured benzoguanamine-based resin, or a water-soluble initial condensate of melamine and formaldehyde or 100 to 50 parts by weight of melamine and 0 to 50 parts by weight of benzoguanamine are added. By treating the mixture with a water-soluble initial condensate of formalde7de and a mixture consisting of a proportion of It is. The emulsion of uncured benzoguanamine resin colored with a dye in the present invention can be easily prepared by various methods.

例えば、ベンゾグアナミンもしくはベンゾグアナミン１
００〜５０重量部とメラミン０〜５０重量部とからなる
混合物とホルムアルデヒドとをベンゾグアナミンもしく
は該混合物１モルに対して１．２〜 ３．５モルの割合
で水媒体中で反応させ得られる反応生成物の水性液に染
料を加えて着色し、次いでそれを攪拌状態にある保護コ
ロイド水溶液に加えて乳化せしめる方法、またベンゾグ
アナミンもしくはベンゾグアナミン１００〜５０重量部
とメラミンｏ〜５０重量部とからなる混合物とホルムア
ルデヒドとをベンゾグアナミンもしくは該混合物ｌモル
に対して１．２ 〜 ３．５モルの割合で水媒体中で反
応させて得られる反応生成物を保護コロイドを用いて乳
化せしめた後、水溶性染料を加えて着色せしめる方法等
が挙げられる。しかし、このような方法だけで本発明に
おける染料で着色された未硬化のベンゾグアナミン系樹
脂の乳化物が制限されるものではない。本発明における
スルホン基を持つ水溶性の紫外線吸収剤としては、紫外
線吸収能に優れ、分子にスルホン基を有し、水溶性の化
合物であれば有効に使用できるものであり、下記の一般
式（式中、Ｒｌ，Ｒ２又はＲ３は−Ｈ，− ０Ｈ，−
０ＣＨ３，− ０ＣＨ心又は− ０Ｃ８Ｈ，７を表わし
、Ｍは− Ｈ，Ｎａ，−Ｋ又は−ＮＨ４を表わす。For example, benzoguanamine or benzoguanamine 1
A reaction product obtained by reacting a mixture of 0 to 50 parts by weight of melamine and formaldehyde in an aqueous medium at a ratio of 1.2 to 3.5 moles per mole of benzoguanamine or the mixture. A method in which a dye is added to an aqueous liquid of a product to color it, and then it is added to an aqueous solution of a protective colloid in a stirring state to emulsify it, or a method in which benzoguanamine or a mixture consisting of 100 to 50 parts by weight of benzoguanamine and 0 to 50 parts by weight of melamine is used. After emulsifying the reaction product obtained by reacting formaldehyde in an aqueous medium at a ratio of 1.2 to 3.5 moles per 1 mole of benzoguanamine or the mixture with a protective colloid, a water-soluble dye is added. In addition, a method of coloring may be mentioned. However, the emulsion of uncured benzoguanamine resin colored with a dye in the present invention is not limited only by such a method. The water-soluble ultraviolet absorber having a sulfone group in the present invention can be effectively used as long as it has excellent ultraviolet absorption ability, has a sulfone group in its molecule, and is water-soluble. In the formula, Rl, R2 or R3 is -H, - 0H, -
It represents 0CH3, -0CH core or -0C8H,7, and M represents -H, Na, -K or -NH4.

）で示されるベンゾフエノン系化合物が特に有効である
。し力化、スルホン基を持つ水溶性の紫外線吸収剤とし
ては、上記のものに限定されるものではなく、たとえば
下記の一般式（式中、Ｒ４又はＲ５は−Ｈ，−ＣＨ３，
− ｔ’− Ｃ４Ｈ９を表わし、Ｍは前記一般式のもの
と同じことを表わす。) are particularly effective. The water-soluble ultraviolet absorber having a sulfonic group is not limited to those mentioned above, and includes, for example, the following general formula (wherein R4 or R5 is -H, -CH3,
-t'- represents C4H9, and M represents the same as in the above general formula.

Ｘは、−Ｈ又は−Ｃｌを表わす。）で示されるベンゾト
リアゾール系化合物も本発明において有効に用い得る。X represents -H or -Cl. ) The benzotriazole compounds shown in ) can also be effectively used in the present invention.

そして、前記の如き両一般式において、Ｍが−Ｈで表わ
されるような化合物を用いると、該化合物自体が樹脂の
硬化触媒としても作用するので、他の硬化触媒を必ずし
も必要としないので、特に好ましいものである。スルホ
ン基を持つ水溶性の紫外線吸収剤の適正を使用量は、未
硬化のベンゾグアナミン系樹脂乳化物の樹脂固形分１０
０重量部に対して１〜５重量部の範囲の割合の量で十分
であり、使用量をこれより多くしてもさしつかえないが
、紫外線吸収剤の増量による効果はあまり期待できない
。染料によつて着色された未硬化のベンゾグアナミン系
樹脂の乳化物へのスルホン基を持つ水溶性の紫外線吸収
剤の添加方法としては、該紫外線吸収剤が水に極めて易
溶性のものである場合は粉末状のままで該乳化物へ直接
添加する方法を採用できるが、該紫外線吸収剤の該乳化
物の粒子への反応の円滑化という点で前もつて水に溶解
させて水溶液を作つておき、その水溶液を該乳化物へ添
加する方法の方が好ましい。スルホン基を持つ水溶性の
紫外線吸収剤の添加は、スルホン基に対し活性な樹脂よ
りなる染料で着色された未硬化のベンゾグアナミン系樹
脂の乳化物に対して行なうことが肝要で、他の硬化触媒
の共存下で樹脂の硬化反応を行なう場合においても、該
紫外線吸収剤は、該他の硬化触媒の添加前に添加してお
くのが好ましい。In both of the above general formulas, when a compound in which M is represented by -H is used, the compound itself also acts as a curing catalyst for the resin, so no other curing catalyst is necessarily required. This is preferable. The appropriate amount of a water-soluble ultraviolet absorber with a sulfone group to be used is 10% of the resin solid content of the uncured benzoguanamine resin emulsion.
An amount in the range of 1 to 5 parts by weight relative to 0 parts by weight is sufficient, and the amount used may be larger than this, but no significant effect can be expected from increasing the amount of the ultraviolet absorber. As a method for adding a water-soluble ultraviolet absorber having a sulfonic group to an emulsion of uncured benzoguanamine resin colored with a dye, if the ultraviolet absorber is extremely easily soluble in water, Although it is possible to directly add the ultraviolet absorber to the emulsion in powder form, in order to facilitate the reaction of the ultraviolet absorber to the particles of the emulsion, it is preferable to dissolve it in water in advance to create an aqueous solution. , a method in which an aqueous solution thereof is added to the emulsion is preferred. It is important to add a water-soluble ultraviolet absorber having a sulfone group to an emulsion of uncured benzoguanamine resin colored with a dye made of a resin that is active against sulfone groups. Even when the resin curing reaction is carried out in the coexistence of the UV absorber, it is preferable to add the ultraviolet absorber before adding the other curing catalyst.

染料で着色された未硬化のベンゾグアナミン系樹脂の乳
化物を該水溶性の紫外線吸収剤を添加することなく他の
硬化触媒の共存下に硬化せしめ、不溶不融状態の微細着
色樹脂よりなる懸濁物に該水溶性の紫外線吸収剤を添加
混合し、樹脂固形分を分離乾燥して得た微細着色樹脂で
は、耐光性の向上はほとんど認められない。また、乳化
に先立つて、ベンゾグアナミンもしくはベンゾグアナミ
ン１００〜５０重量部とメラミン０〜５０重量部とから
なる混合物をホルムアルデヒドと反応させ得られる反応
生成物あるいは保護コロイドを含む水溶液に、スルホン
基を持つ水溶性の紫外線吸収剤を溶解させておき、次い
で乳化物を作り、樹脂の硬化反応を進めることにより得
られる微細着色樹脂では、耐光性の向上は認められるが
、その効果は著しく小さく、また、該水溶性の紫外線吸
収剤はその多くが一方では酸性硬化触媒でもあるがゆえ
に反応の制御が著しく困難である。 ｊ本発
明で場合により使用さ肩るメラミンとホルムアルデヒド
との水溶性初期縮合物またはメラミン１００〜５０重量
部とベンゾグアナミンＯ〜５０重量部の割合でなる混合
物とホルムアルデヒドとの初期縮合物（以下、両縮合物
を併せてメラミン系初期縮合物と記す。An emulsion of uncured benzoguanamine-based resin colored with a dye is cured in the coexistence of other curing catalysts without adding the water-soluble ultraviolet absorber, resulting in a suspension of finely colored resin in an insoluble and infusible state. In the finely colored resin obtained by adding and mixing the water-soluble ultraviolet absorber to the product and separating and drying the resin solid content, almost no improvement in light resistance is observed. In addition, prior to emulsification, benzoguanamine or a mixture consisting of 100 to 50 parts by weight of benzoguanamine and 0 to 50 parts by weight of melamine is reacted with formaldehyde to produce a reaction product or an aqueous solution containing a protective colloid. Finely colored resin obtained by dissolving an ultraviolet absorber, then making an emulsion, and proceeding with the curing reaction of the resin has an improvement in light resistance, but the effect is extremely small, and the water-soluble Since most of the UV absorbers are also acidic curing catalysts, it is extremely difficult to control the reaction. j A water-soluble initial condensate of melamine and formaldehyde, which is optionally used in the present invention, or an initial condensate of formaldehyde and a mixture of 100 to 50 parts by weight of melamine and 50 parts by weight of benzoguanamine (hereinafter referred to as both) The condensates are collectively referred to as melamine-based initial condensates.

）は、従来公知方法に従つて、例えばメラミンもしくは
メラミン１００〜５０重量部とベンゾグアナミン０〜５
０重量部の割合でなる混合物１モルに対してホルムアル
デヒド２〜６モルを水媒体中でＰＨ６〜１１、反応温度
５０〜１００℃の条件で反応させることによつて容易に
得ることができる。メラミン系初期縮合物としては該初
期縮合物が水に対してよく混和する程度であれば良く、
その縮合度に特定の限定を加えるものではない。また、
メラミン系初期縮合物を噴霧乾燥して得られる粉状のも
のを再び水溶液とした該初期縮合物の水溶液も有効に使
用することができる。メラミン系初期縮合物の使用量は
広い範囲の量とすることができるが、未硬化のベンゾグ
アナミン系樹脂乳化物の樹脂固形分１００重量部に対し
て５〜３０重量部の割合の量である。), for example, melamine or 100 to 50 parts by weight of melamine and 0 to 5 parts by weight of benzoguanamine.
It can be easily obtained by reacting 2 to 6 moles of formaldehyde with respect to 1 mole of a mixture having a ratio of 0 parts by weight in an aqueous medium at a pH of 6 to 11 and a reaction temperature of 50 to 100°C. As the melamine-based initial condensate, it is sufficient that the initial condensate is well miscible with water;
No particular limitation is imposed on the degree of condensation. Also,
An aqueous solution of the melamine-based initial condensate obtained by spray-drying the powder and reconstituted into an aqueous solution can also be effectively used. The amount of the melamine-based initial condensate used can vary over a wide range, but is in the range of 5 to 30 parts by weight based on 100 parts by weight of the resin solid content of the uncured benzoguanamine-based resin emulsion.

メラミン系初期縮合物の水溶液の添加は、スルホン基を
持つ水溶性紫外線吸収剤と同様に染料で着色された未硬
化のベンゾグアナミン系樹脂の乳化物に対して行なう必
要がある。The aqueous solution of the melamine-based initial condensate must be added to an uncured benzoguanamine-based resin emulsion colored with a dye, similar to the water-soluble ultraviolet absorber having a sulfone group.

本発明で必要に応じて使用される他の硬化触媒としては
、アミノ系樹脂の縮合硬化触媒として用いられているも
の、例えば塩酸、硫酸、燐酸等の鉱酸類、安息香酸、フ
タール酸、酢酸等のカルボン酸類、ベンゼンスルホン酸
、パラトルエンスルホン酸、ドデシルベンゼンスルホン
酸等のスルホン酸類からなる群より適当に選んで使用す
ることができる。Other curing catalysts that may be used as necessary in the present invention include those used as condensation curing catalysts for amino resins, such as mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, benzoic acid, phthalic acid, and acetic acid. and sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, and dodecylbenzenesulfonic acid.

これらの硬化触媒は、スルホン基を持つ水溶性の紫外線
吸収剤がスルホン酸塩である場合には、その使用量はス
ルホン酸塩と当量あるいはそれ以上の量を添加する必要
がある。When the water-soluble ultraviolet absorber having a sulfonic group is a sulfonate, these curing catalysts need to be added in an amount equivalent to or more than the sulfonate.

また、スルホン基を持つ水溶性の紫外線吸収剤がスルホ
ン酸である場合にも、硬化反応の促進のため添加するこ
とができるが、これらの硬化触媒の添加量は染料で着色
された未硬化のベンゾグアナミン系樹脂の乳化ソ物の樹
脂固形分１００重量部に対し５重量部程度で十分である
。In addition, when the water-soluble ultraviolet absorber with a sulfonic group is a sulfonic acid, it can be added to promote the curing reaction, but the amount of these curing catalysts added should be It is sufficient to use about 5 parts by weight per 100 parts by weight of the resin solid content of the emulsified product of benzoguanamine resin.

染料で着色された未硬化のベンゾグアナミン決樹脂の乳
化物の硬化反応は、スルホン基を持つ水溶性の紫外線吸
収剤および必要に応じて他の硬化触媒の共存下に乳化状
態のままで４０〜１００℃の範囲の温度とすることによ
つて行ない、硬化物が不溶不融状態となつた時を硬化反
応の終点とする。The curing reaction of an emulsion of uncured benzoguanamine resin colored with a dye is carried out in an emulsified state in the presence of a water-soluble ultraviolet absorber having a sulfonic group and other curing catalysts as necessary. The curing reaction is carried out at a temperature in the range of °C, and the end point of the curing reaction is when the cured product becomes insoluble and infusible.

硬化反応時の染料で着色された未硬化のベンゾグアナミ
ン系着色樹脂の乳化物のＰＨは、２．０〜 ５．５の範
囲にある。硬化反応を終了した後、硬化物は水媒体から
分離し乾燥して微細着色樹脂とするものである。The pH of the uncured benzoguanamine-based colored resin emulsion colored with a dye during the curing reaction is in the range of 2.0 to 5.5. After the curing reaction is completed, the cured product is separated from the aqueous medium and dried to obtain a finely colored resin.

このようにして、スルホン基を持つ水溶性の紫外線吸収
剤を用いる本発明の方法によつて得られた微細着色樹脂
は、その耐光性が非常に優れており、従来より行なわれ
ている油溶性の紫外線吸収剤を微細着色樹脂を構成する
合成樹脂中に均一に溶解させて用いる方法、および微細
着色樹脂を各種分野に使用するに際し、紫外紫吸収剤を
被着色物である合成樹脂あるいは塗料、インキのビヒク
ル中に溶解させて用いる方法に比較して卓越した優位性
を発揮するものである。また、本発明の方法は、従来よ
りの方法と併用することによつても、その効果が相殺さ
れるものではない。そして、本発明の方法は、本発明者
らの染料により着色された未硬化のベンゾグアナミン系
樹脂乳化物を経て微細着色樹脂を得る方法に特に有効に
応用できるものである。以下、実施例により本発明をさ
らに詳しく説明する。In this way, the finely colored resin obtained by the method of the present invention using a water-soluble ultraviolet absorber having a sulfonic group has excellent light resistance, and it A method of uniformly dissolving an ultraviolet absorber into a synthetic resin constituting a finely colored resin, and a method of using a finely colored resin by dissolving it uniformly in a synthetic resin, and when using a finely colored resin in various fields, the ultraviolet violet absorber is used in a synthetic resin or paint that is a colored object, This method exhibits outstanding superiority compared to the method of dissolving it in an ink vehicle. Further, even when the method of the present invention is used in combination with conventional methods, the effects thereof are not canceled out. The method of the present invention can be particularly effectively applied to a method of obtaining a finely colored resin through an uncured benzoguanamine resin emulsion colored with the inventors' dye. Hereinafter, the present invention will be explained in more detail with reference to Examples.

実施例 １ 攪拌機、還流冷却器、温度計を備えた四つロフラスコに
ベンゾグアナミン１５０ｇ（０．８モル）、濃度３７％
のホルマリン１３０ｙ（ １．６モル）および濃度１０
％の炭酸ナトリウム水溶液０．５２ｙを仕込み、攪拌し
ながら９４〜９５゜Ｃの温度で５時間反応させてベンゾ
グアナミンとホルムアルデヒドの反応生成物を得た。Example 1 150 g (0.8 mol) of benzoguanamine, 37% concentration, was placed in a four-loaf flask equipped with a stirrer, reflux condenser, and thermometer.
formalin 130y (1.6 mol) and concentration 10
0.52 y of aqueous sodium carbonate solution was added, and the reaction was carried out at a temperature of 94 to 95° C. for 5 hours with stirring to obtain a reaction product of benzoguanamine and formaldehyde.

ポリビニルアルコール（クラレ株式会社製品゛“ＰＶＡ
２Ｏ５゛）６．０ｙを水６００ｇに溶解して得た水溶液
にホモミキサーを用いて激しく攪拌しながら上記の反応
生成物を含む溶液を加え乳化させた。Polyvinyl alcohol (PVA manufactured by Kuraray Co., Ltd.)
A solution containing the above reaction product was added to an aqueous solution obtained by dissolving 2O5')6.0y in 600 g of water with vigorous stirring using a homomixer and emulsified.

乳化物を３０’Ｃまで冷却した後、ローダミンυＢｌ．
５ｇとローダミン６ＧＣＰ１．５ｇを加えて３０分間室
温で攪拌し、染料で着色された未硬化のベンゾグアナミ
ン系樹脂の乳化物を得た。After cooling the emulsion to 30'C, rhodamine υBl.
5 g of rhodamine 6GCP and 1.5 g of rhodamine 6GCP were added and stirred for 30 minutes at room temperature to obtain an emulsion of uncured benzoguanamine resin colored with a dye.

２−ヒドロキシ−４−メトキシ− ５−スルフオ・ベン
ゾフエノン４．５ｙを水４０．５１に溶解して得られた
溶液を上記乳化物に加え、４０℃、５０℃、６０℃、７
０℃、８０℃、９０℃の各温度で順次２時間づつ加熱攪
拌し、乳化状態で硬化反応を進めさせて微細着色樹脂の
懸濁物を得た。A solution obtained by dissolving 4.5 y of 2-hydroxy-4-methoxy-5-sulfobenzophenone in 40.5 ml of water was added to the above emulsion, and the mixture was heated at 40°C, 50°C, 60°C, and 7°C.
The mixture was heated and stirred at 0° C., 80° C., and 90° C. for 2 hours in sequence to advance the curing reaction in an emulsified state to obtain a suspension of finely colored resin.

微細着色樹脂を濾別し、１００℃で乾燥し、１５０℃で
３時間加熱処理した後、乳鉢の中で軽く押しつぶすこと
により粉状の微細着色樹脂を得た。The finely colored resin was filtered off, dried at 100°C, heated at 150°C for 3 hours, and then lightly crushed in a mortar to obtain a powdered finely colored resin.

このようにして得た微細着色樹脂は、非常に優れた耐光
性を示した。The finely colored resin thus obtained exhibited very excellent light resistance.

実施例 ２ 実施例１で使用したのと同じフラスコにベンゾグアナミ
ン１５０９（ ０．８モル）、濃度３７％のホルマリン
１３０９（ １．６モル）および濃度１０％の炭酸ナト
リウム水溶液０．５２ｆＩを仕込み、攪拌しながら９４
〜９５℃の温度で５時間反応させた。Example 2 In the same flask as used in Example 1, benzoguanamine 1509 (0.8 mol), formalin 1309 (1.6 mol) with a concentration of 37%, and 0.52 fI of aqueous sodium carbonate solution with a concentration of 10% were charged and stirred. While 94
The reaction was carried out for 5 hours at a temperature of ~95°C.

その後カヤセツトエロ一 ・ Ｇ７．５ｌを加え、９４
〜９５℃に保ち３０分間攪拌し、染料をベンゾグアナミ
ンとホルムアルデヒドとの反応生成物に相溶させた。ポ
リビニルアルコール（クラレ株式会社製品““ＰＶＡ−
２０５゛）６．０θを水６００９に溶解して得た水溶液
にホモミキサーを用いて激しく攪拌しながら、上記着色
された反応生成物を含む溶液を加え、乳化させて染料で
着色された未硬化のベンゾグアナミン系樹脂の乳化物を
得た。After that, add 7.5l of Kayasetsutoeroichi・G7.5l, 94
The mixture was kept at ~95°C and stirred for 30 minutes to make the dye compatible with the reaction product of benzoguanamine and formaldehyde. Polyvinyl alcohol (PVA- manufactured by Kuraray Co., Ltd.)
205゛) To an aqueous solution obtained by dissolving 6.0θ in water 6009, while stirring vigorously using a homomixer, add the solution containing the above-mentioned colored reaction product and emulsify it to form an uncured dye-colored solution. An emulsion of benzoguanamine resin was obtained.

２−ヒドロキシ− ４−メトキシ− ５ −スルフオ・
ベンゾフエノン４．５９を水４０，５ｙに溶解して得ら
れた溶液を上記乳化物に加え、４０℃、５０℃、６０℃
、７０℃、８０℃、９０℃の各温度で順次２時間づつ加
熱攪拌し乳化状態で硬化反応を進めさせて微細着色樹脂
を得た。2-Hydroxy-4-methoxy-5-sulfo・
A solution obtained by dissolving 4.59 y of benzophenone in 40.5 y of water was added to the above emulsion, and the mixture was heated at 40°C, 50°C, and 60°C.
, 70° C., 80° C., and 90° C. for 2 hours with stirring to proceed with the curing reaction in an emulsified state to obtain a finely colored resin.

微細着色樹脂を濾別し、１００℃で乾燥し、１５０℃で
３時間加熱処理した後、乳鉢の中で軽く押しつぶすこと
により粉状の微細着色樹脂を得た。The finely colored resin was filtered off, dried at 100°C, heated at 150°C for 3 hours, and then lightly crushed in a mortar to obtain a powdered finely colored resin.

このようにして得た微細着色樹脂は、非常に優れた耐光
性を示した。The finely colored resin thus obtained exhibited very excellent light resistance.

実施例 ３ 実施例１で使用したのと同じフラスコにベンゾグアナミ
ン１５０９（０，８モル）、濃度３７％のホルマリン１
３０９（１．６モル）および濃度１０？の炭酸ナトリウ
ム水溶液０．５２９を仕込み撹拌しながら９４〜９５℃
の温度で５時間反応させた。Example 3 In the same flask as used in Example 1, benzoguanamine 1509 (0.8 mol) and formalin 1 at a concentration of 37% were added.
309 (1.6 mol) and concentration 10? Add 0.529% of sodium carbonate aqueous solution and heat to 94-95°C while stirring.
The reaction was carried out at a temperature of 5 hours.

その後カヤセツトエロ一・Ｇ７５９を加え９４〜９５℃
に保ち３０分間撹拌し染料をベンゾグアナミンとホルム
アルデヒドとの反応生成物に相溶させた。ポリビニルア
ルコール（クラレ株式会社製品″ＰＶＡ２Ｏ５″）６．
０９を水６００ｆ！に溶解して得た水溶液にホモミキサ
ーを用いて激しく攪拌しながら上記着色された反応生成
物を含む溶液を加え乳化させて染料で着色された未硬化
のベンゾグアナミン系樹脂の乳化物（以下、乳化物［Ａ
」と記す。Then add Kayasetsutoeroichi G759 to 94-95℃.
The dye was stirred for 30 minutes to dissolve the dye into the reaction product of benzoguanamine and formaldehyde. Polyvinyl alcohol (Kuraray Co., Ltd. product "PVA2O5") 6.
09 water 600f! A solution containing the above colored reaction product is added to the aqueous solution obtained by dissolving it in a homomixer while stirring vigorously, and the solution is emulsified to form an emulsion of uncured benzoguanamine resin colored with a dye (hereinafter referred to as an emulsion). thing [A
”.

）を得た。メラミン１５９（０，１１９モル）、濃度３
７％のホルマリン２９９（０，３５７モル）および２８
ｅのアンモニア水２．４９を還流冷却器を備えたフラス
コ中で８０℃、１０分間加熱撹拌してメラミン系初期縮
合物（以下、縮合物」と記す。) was obtained. Melamine 159 (0,119 mol), concentration 3
7% formalin 299 (0,357 mol) and 28
2.49 g of ammonia water was heated and stirred at 80° C. for 10 minutes in a flask equipped with a reflux condenser to obtain a melamine-based initial condensate (hereinafter referred to as “condensate”).

）の水溶液を調製した。４０℃に保たれた乳化物」に縮
合物」の水溶液および２−ヒドロキシ−４−メトキシ−
５ースルフオ・ベンゾフエノン４．５９を水４０，５９
に溶解して得られた溶液を加え、４０℃で２時間加熱攪
拌し、ついで１Ｎ一硫酸３０１を加えて５０℃、６０℃
、７０℃、８０℃、９０℃の各温度で順次２時間づつ加
熱攪拌し乳化状態で硬化反応を進めさせて微細着色樹脂
を得た。) was prepared. Aqueous solution of emulsion and condensate kept at 40°C and 2-hydroxy-4-methoxy-
5-Sulfobenzophenone 4.59 to water 40.59
Add the solution obtained by dissolving in and stir at 40°C for 2 hours, then add 1N monosulfuric acid 301 and heat at 50°C and 60°C.
, 70° C., 80° C., and 90° C. for 2 hours with stirring to proceed with the curing reaction in an emulsified state to obtain a finely colored resin.

微細着色樹脂をＦ別し、１００℃で乾燥し、１５０℃で
３時間加熱処理した後乳鉢の中で軽く押しつぶすことに
より粉状の微細着色樹脂を得た。The fine colored resin was separated by F, dried at 100°C, heat treated at 150°C for 3 hours, and then lightly crushed in a mortar to obtain a powdered fine colored resin.

このようにして得た微細着色樹脂は、非常に優れた耐光
性と共に卓越した耐色移行性を示した。実施例 ４実施
例１において、２−ヒドロキシ−４−メトキシ−５−ス
ルフオ・ベンゾフエノン４．５９を水４０，５９に溶解
させて得られた溶液の添加後、さらに１Ｎ一硫酸４０９
を添加する他は同じ手順に従つて粉状の微細着色樹脂を
得た。The finely colored resin thus obtained exhibited excellent light fastness and excellent color transferability. Example 4 In Example 1, after the addition of a solution obtained by dissolving 4.59 g of 2-hydroxy-4-methoxy-5-sulfobenzophenone in 40.59 g of water, 409 g of 1N monosulfuric acid was added.
A powdered finely colored resin was obtained by following the same procedure except that .

このようにして得た粉状の微細着色樹脂は、非常に優れ
た耐光性を示した。The powdered finely colored resin thus obtained exhibited very excellent light resistance.

実施例 ５ ノ 実施例４において、２−ヒドロキシ−４−メトキシ−５
−スルフオ・ベンゾフエノン４．５９を水４０．５９に
溶解させて得られた溶液の代わりに、ソデイウム２，ｊ
−ジヒドロキシ−４，４′−ジメトキシ−５−スルフオ
・ベンゾフエノン４．５９を水１０８９に溶解させて得
られた溶液を用いる他は同じ手順に従つて粉状の微細着
色樹脂を得た。Example 5 In Example 4, 2-hydroxy-4-methoxy-5
- instead of the solution obtained by dissolving 4.59 sulfobenzophenone in 40.59 ml of water, sodium 2,j
A fine colored resin in powder form was obtained by following the same procedure except that a solution obtained by dissolving 4.59 g of -dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone in 1089 g of water was used.

このようにして得た粉状の微細着色樹脂は、非常に優れ
た耐光性を示した。比較例 １ 実施例１において、２−ヒドロキシ−４−メトキシ−５
−スルフオ・ベンゾフエノンを乳化物に添加する代りに
ＩＮ硫酸４０９を添加する他は同じ手順に従つて粉状の
微細着色樹脂を得た。The powdered finely colored resin thus obtained exhibited very excellent light resistance. Comparative Example 1 In Example 1, 2-hydroxy-4-methoxy-5
A finely pigmented resin in powder form was obtained by following the same procedure except that instead of adding sulfobenzophenone to the emulsion, IN sulfuric acid 409 was added.

しかしながら、このようにして得た粉状の微細着色樹脂
は、実施例１のものに比較して耐光性が劣つていた。比
較例 ２ 実施例１で使用したのと同じフラスコにベンゾグアナミ
ン１５０９（０．８モル）、濃度３７％のホルマリン１
３０９（１．６モル）、濃度１０％の炭酸ナトリウム水
溶液０，５２９を仕込み、攪拌しながら９４〜９５℃の
温度で５時間反応させた。However, the powdery finely colored resin thus obtained was inferior in light resistance compared to that of Example 1. Comparative Example 2 In the same flask as used in Example 1, benzoguanamine 1509 (0.8 mol) and formalin 1 at a concentration of 37% were added.
309 (1.6 mol) and 0.529 mol of a 10% aqueous sodium carbonate solution were charged, and the mixture was reacted at a temperature of 94 to 95° C. for 5 hours with stirring.

その後、２−ヒドロキシ−４−メトキシーベンゾフエノ
ン４．５９を加え、９４〜９５℃に保ち３０分間攪拌し
、ベンゾグアナミンとホルムアルデヒドとの反応生成物
に相溶させた。ポリビニルアルコール（クラレ株式会社
製品″ＰＶＡ２Ｏ５８）６．０９を水６００９に溶解し
て得た水溶液にホモミキサーを用いて激しく撹拌しなが
ら上記の反応生成物を含む溶液を加え乳化させた。Thereafter, 4.59 g of 2-hydroxy-4-methoxybenzophenone was added and stirred for 30 minutes while maintaining the temperature at 94 to 95°C to dissolve the reaction product of benzoguanamine and formaldehyde. To an aqueous solution obtained by dissolving 6.09 g of polyvinyl alcohol (PVA2O58, a product of Kuraray Co., Ltd.) in 6009 g of water, a solution containing the above reaction product was added and emulsified while stirring vigorously using a homomixer.

乳化物を３０℃まで冷却した後、ローダミンＢｌ．５９
とローダミン６ＧＣＰ１．５ｆ！を加えて３０分間室温
で攪拌し染料で着色された未硬化のベンゾグアナミン系
樹脂の乳化物を得た。ついで、上記乳化物に１Ｎ一硫酸
４０９を加え、４０℃、５０℃、６０℃、７０℃、８０
℃、９０℃の各温度で順次２時間づつ加熱撹拌し、乳化
状態で硬化反応を進めさせて微細着色樹脂を得た。After cooling the emulsion to 30°C, rhodamine Bl. 59
And Rhodamine 6GCP1.5f! was added and stirred for 30 minutes at room temperature to obtain an emulsion of uncured benzoguanamine resin colored with a dye. Next, 1N monosulfuric acid 409 was added to the above emulsion, and the mixture was heated at 40°C, 50°C, 60°C, 70°C, and 80°C.
The mixture was heated and stirred for 2 hours at each temperature of .degree. C. and 90.degree. C. to advance the curing reaction in an emulsified state to obtain a finely colored resin.

微細着色樹脂を炉別し、１００℃で乾燥し、１５０℃で
３時間加熱処理した後、乳鉢の中で軽く押しつぶすこと
により粉状の微細着色樹脂を得た。しかしながら、この
ようにして得た微細着色樹脂は、実施例１のものに比較
して耐光性が劣つていた。The fine colored resin was separated in a furnace, dried at 100°C, heat treated at 150°C for 3 hours, and then lightly crushed in a mortar to obtain a powdered fine colored resin. However, the finely colored resin thus obtained was inferior in light resistance compared to that of Example 1.

比較例 ３ 比較例１で得られた微細着色樹脂に、さらに２−ヒドロ
キシ− ４ −メトキシーベンゾフエノン４．５９を乾
式混合して粉状の微細着色樹脂を得た。Comparative Example 3 The finely colored resin obtained in Comparative Example 1 was further dry mixed with 4.59 g of 2-hydroxy-4-methoxybenzophenone to obtain a powdery finely colored resin.

しかしながら、このようにして得た微細着色樹脂は、実
施例１のものに比較して耐光性が劣つていた。However, the finely colored resin thus obtained was inferior in light resistance compared to that of Example 1.

比較例 ４ 実施例１において、２−ヒドロキシ− ４ −メトキシ
一 ５−スルフオ・ベンゾフエノンの代わりにＩＮ一硫
酸４０ｆ１を用いる他は同じ手順に従つて硬化反応を終
えた。Comparative Example 4 The curing reaction was completed in accordance with the same procedure as in Example 1, except that IN monosulfuric acid 40f1 was used instead of 2-hydroxy-4-methoxy-5-sulfobenzophenone.

微細着色樹脂の涙別に先立つて、２−ヒドロキシ−４−
メトキシ− ５ −スルフオ・ベンゾフエノン４．５ｙ
を水４０．５ｙに溶解して得られた溶液を硬化反応を終
えた懸濁物に加え、９０′Ｃで１時間攪拌した後、実施
例１と同様に涙別、乾燥、加熱処理した後、乳鉢の中で
軽く押しつぶすことによつて粉状の微細着色樹脂を得た
。Prior to separation of the finely colored resin, 2-hydroxy-4-
Methoxy-5-sulfobenzophenone 4.5y
A solution obtained by dissolving 40.5 y of water was added to the suspension after the curing reaction, and after stirring at 90'C for 1 hour, the solution was separated, dried, and heat treated in the same manner as in Example 1. A powdery fine colored resin was obtained by light crushing in a mortar.

しかしながら、このようにして得た粉状の微細着色樹脂
は、実施例１のものに比較して耐光性が著しく劣つてい
た。However, the powdery finely colored resin thus obtained was significantly inferior in light resistance compared to that of Example 1.

比較飼 ５ 実施飼１において、２−ヒドロキシ− ４ −メトキシ
− ５ −スルフオ・ベンゾフエノンに替えて２ーヒド
ロキシ−４−メトキシ・ベンゾフエノンを同量用い、他
は実施例１と同じ手順に従つて粉状の微細着色樹脂を得
た。Comparative diet 5 In experimental diet 1, the same amount of 2-hydroxy-4-methoxy-benzophenone was used instead of 2-hydroxy-4-methoxy-5-sulfo-benzophenone, and the other procedures were the same as in Example 1, except that powdered A finely colored resin was obtained.

しかしながら、このようにして得た粉状の微細着色樹脂
は、実施例１のものに比較して耐光性が劣つていた。However, the powdery finely colored resin thus obtained was inferior in light resistance compared to that of Example 1.

実施例 ６ 実施例１および比較例１〜５で得られた微細着色樹脂の
耐光性を下記の方法で試験した。Example 6 The light resistance of the finely colored resins obtained in Example 1 and Comparative Examples 1 to 5 was tested by the following method.

粉状の微細着色樹脂をポリプロピレン（三井石油化学株
式会社製品”“Ｊ−６００“）へ１％混入し、射出成型
により厚さ３ｍｍの着色プレートを作成した。得られた
着色プレートをキセノンウエザーメータ一（スガ試験機
株式会社製品ＷＦ｝−６Ｘ−ＨＣ）中で２．５時間、５
時間、１０時間露光し、着色プレートの変色度を試験し
た。1% of powdered finely colored resin was mixed into polypropylene (Mitsui Petrochemical Co., Ltd. product "J-600") and a colored plate with a thickness of 3 mm was created by injection molding.The obtained colored plate was attached to a xenon weather meter. 1 (Suga Test Instruments Co., Ltd. product WF}-6X-HC) for 2.5 hours, 5
The color plate was exposed to light for 10 hours and the degree of discoloration of the colored plate was tested.

試験の結果は、第１表に示したとおりであつた。The results of the test were as shown in Table 1.

Claims (1)

【特許請求の範囲】 １ 染料により着色された未硬化のベンゾグアナミン系
樹脂の乳化物にスルホン基を持つ水溶性の紫外線吸収剤
を添加し、必要に応じて他の硬化触媒をさらに添加し、
乳化状態で樹脂の硬化反応を進め、硬化物を水媒体から
分離し乾燥することを特徴とする耐光性に優れた微細着
色樹脂の製法。 ２ 染料により着色された未硬化のベンゾグアナミン系
樹脂の乳化物に、スルホン基を持つ水溶性の紫外線吸収
剤及びメラミンとホルムアルデヒドとの水溶性初期縮合
物、又はスルホン基を持つ水溶性の紫外線吸収剤及びメ
ラミン１００〜５０重量部とベンゾグアナミン０〜５０
重量部の割合で成る混合物とホルムアルデヒドとの水溶
性初期縮合物を添加し、必要に応じて他の硬化触媒をさ
らに添加し、乳化状態で樹脂の硬化反応を進め、硬化物
を水媒体から分離し乾燥することを特徴とする耐光性に
優れた微細着色樹脂の製法。 ３ 紫外線吸収剤の使用量は乳化物の樹脂固形分１００
重量部に対して１〜５重量部の範囲の割合の量である特
許請求の範囲第１項又は第２項記載の製法。 ４ 紫外線吸収剤は一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿１、Ｒ＿２又はＲ＿３は−Ｈ、−ＯＨ、−
ＯＣＨ＿３、▲数式、化学式、表等があります▼又は−
ＯＣ＿８Ｈ＿１＿７を表わし、Ｍは−Ｈ、−Ｎａ、−Ｋ
又は−ＮＨ＿４を表わす。 ）で示されるスルホン基を持つ水溶性のベンゾフェノン
系化合物である特許請求の範囲第１項又は第２項記載の
製法。 ５ 紫外線吸収剤は一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿４又はＲ＿５は−Ｈ、−ＣＨ＿２又は−ｔ
−Ｃ＿４Ｈ＿９を表わし、Ｍは−Ｈ、−Ｎａ、−Ｋ又は
−ＮＨ＿４を表わす。 Ｘは−Ｈ又は−Ｃｌを表わす。）で示されるスルホン基
を持つ水溶性のベンゾトリアゾール系化合物である特許
請求の範囲第１項又は第２項記載の製法。[Claims] 1. A water-soluble ultraviolet absorber having a sulfonic group is added to an emulsion of uncured benzoguanamine resin colored with a dye, and if necessary, other curing catalysts are further added,
A method for producing finely colored resin with excellent light resistance, which is characterized by proceeding with the curing reaction of the resin in an emulsified state, separating the cured product from the aqueous medium, and drying it. 2. A water-soluble ultraviolet absorber with a sulfone group and a water-soluble initial condensate of melamine and formaldehyde, or a water-soluble ultraviolet absorber with a sulfone group in an emulsion of uncured benzoguanamine resin colored with a dye. and 100 to 50 parts by weight of melamine and 0 to 50 parts by weight of benzoguanamine.
A water-soluble initial condensate of a mixture of parts by weight and formaldehyde is added, other curing catalysts are further added as necessary, the curing reaction of the resin is proceeded in an emulsified state, and the cured product is separated from the aqueous medium. A manufacturing method for finely colored resin with excellent light resistance, which is characterized by drying. 3 The amount of ultraviolet absorber used is 100% of the resin solid content of the emulsion.
The method according to claim 1 or 2, wherein the amount is in the range of 1 to 5 parts by weight. 4 Ultraviolet absorbers have general formulas▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2 or R_3 are -H, -OH, -
OCH_3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼or-
OC_8H_1_7, M is -H, -Na, -K
Or it represents -NH_4. ) The method according to claim 1 or 2, which is a water-soluble benzophenone compound having a sulfone group. 5 Ultraviolet absorbers have general formulas▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_4 or R_5 is -H, -CH_2 or -t
-C_4H_9, and M represents -H, -Na, -K or -NH_4. X represents -H or -Cl. ) The method according to claim 1 or 2, which is a water-soluble benzotriazole compound having a sulfone group represented by: