JPWO2013115165A1 - Composite aggregated resin particles and composition containing the particles - Google Patents

Composite aggregated resin particles and composition containing the particles Download PDF

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JPWO2013115165A1
JPWO2013115165A1 JP2013556401A JP2013556401A JPWO2013115165A1 JP WO2013115165 A1 JPWO2013115165 A1 JP WO2013115165A1 JP 2013556401 A JP2013556401 A JP 2013556401A JP 2013556401 A JP2013556401 A JP 2013556401A JP WO2013115165 A1 JPWO2013115165 A1 JP WO2013115165A1
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西村修平
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Abstract

【課題】従来の再分散性の良好な粒子は界面活性剤等の分散安定剤を含んでおり、各種成型体や塗料に添加した際に、物性を低下させたり、着色を起こしたりするなどの問題点があった。本発明は、これらの問題を解決し、インキ、塗料や樹脂成型品をはじめとする種々の用途に幅広く用いることができ、ハンドリング性に優れ、有機溶剤に添加、または各種樹脂に練りこんだ際に容易に１次粒子まで再分散する凝集状微粒子を提供することを目的とする。【解決手段】微小樹脂粒子が凝集してなる原料凝集粒子に油溶性ビニル系重合体が複合された凝集樹脂粒子であって、全体としては不定形の形状を有しており、かつ含有されている前記微小樹脂粒子は凝集前の形状を維持している複合凝集樹脂粒子。【選択図】図１The conventional particles having good redispersibility contain a dispersion stabilizer such as a surfactant, and when added to various moldings and paints, the physical properties are lowered or coloring is caused. There was a problem. The present invention solves these problems and can be widely used for various applications including inks, paints, and resin molded products, has excellent handling properties, and is added to an organic solvent or kneaded into various resins. Another object of the present invention is to provide agglomerated fine particles that easily re-disperse to primary particles. Agglomerated resin particles in which oil-soluble vinyl polymers are combined with raw material agglomerated particles obtained by agglomerating fine resin particles, and have an indefinite shape as a whole and are contained therein. The fine resin particles are composite agglomerated resin particles that maintain the shape before agglomeration. [Selection] Figure 1

Description

本発明は複合凝集樹脂粒子に関する。具体的には、本発明は有機溶剤中において容易にサブミクロンサイズの微粒子に再分散可能であるとともに、ハンドリング性に優れる凝集粒子に関する。   The present invention relates to composite aggregated resin particles. Specifically, the present invention relates to agglomerated particles that can be easily redispersed into submicron-sized fine particles in an organic solvent and have excellent handling properties.

従来から、サブミクロンサイズの微粒子は各種フィラー、トナー、プラスチック、塗料、インキ等において利用されている。これらの用途においては、微粒子の良好な分散性が求められるが、サブミクロンサイズの微粒子は凝集しやすく、再分散するには一般的に極めて複雑で、かつ高コストとなるような分散工程を必要とする。そこで、かかるサブミクロンサイズの微粒子を容易に再分散するために各種界面活性剤による表面処理による手法が提案されている。   Conventionally, submicron-sized fine particles have been used in various fillers, toners, plastics, paints, inks and the like. In these applications, good dispersibility of fine particles is required, but submicron-sized fine particles tend to aggregate, and redispersion generally requires a dispersion process that is extremely complicated and expensive. And Therefore, a method by surface treatment with various surfactants has been proposed in order to easily redisperse such submicron-sized fine particles.

例えば、特許文献１には、水性媒体中に界面活性剤を用いてポリウレタンプレポリマーを強制乳化させ、乳化重合させることによって、粒子径が１００ｎｍ〜１００μｍの範囲にある再分散性に優れたポリウレタン系エマルジョンを製造する方法が提案されている。その界面活性剤として、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンラウリルエーテル、等のノニオン性界面活性剤が挙げられ、その中でもＨＬＢ値が６〜２０のノニオン性界面活性剤が好適に用いられると記載されている。   For example, Patent Document 1 discloses a polyurethane system excellent in redispersibility in which a particle diameter is in a range of 100 nm to 100 μm by forcibly emulsifying a polyurethane prepolymer using a surfactant in an aqueous medium and emulsion polymerization. Methods for producing emulsions have been proposed. Examples of the surfactant include nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, and polyoxyethylene lauryl ether. Among them, nonionic surfactants having an HLB value of 6 to 20 are included. It is described that the agent is preferably used.

また、特許文献２には、エチレン性不飽和カルボン酸単位を含有する水分散性共重合体を水分散媒体中に分散させて、それを保護コロイドとして、（メタ）アクリル酸の炭素数１〜１８のアルキルエステル、スチレン、グリシジルメタクリレート、アクリル酸アミド、酢酸ビニル、アクリロニトリル等の不飽和モノマーを乳化重合させて、平均粒子径が３０〜８０ｎｍの範囲にある超微細粒子の水性樹脂エマルジョンを製造する方法が提案されている。   Patent Document 2 discloses that a water-dispersible copolymer containing an ethylenically unsaturated carboxylic acid unit is dispersed in an aqueous dispersion medium and used as a protective colloid, and (meth) acrylic acid having 1 to 1 carbon atoms. Emulsion polymerization of unsaturated monomers such as 18 alkyl esters, styrene, glycidyl methacrylate, acrylic acid amide, vinyl acetate, acrylonitrile, etc. to produce an ultrafine particle aqueous resin emulsion having an average particle size in the range of 30 to 80 nm. A method has been proposed.

特許文献３には、アニオン系、カチオン系、ノニオン系の重合性乳化剤の重合物の存在下でアクリル系単量体を乳化重合させて得られたエマルジョンを噴霧乾燥させてなる再分散性に優れた樹脂粉末が記載されている。   Patent Document 3 discloses excellent redispersibility obtained by spray-drying an emulsion obtained by emulsion polymerization of an acrylic monomer in the presence of a polymer of an anionic, cationic or nonionic polymerizable emulsifier. Resin powder is described.

しかしながら界面活性剤等の乳化剤は各種成型体や塗料の物性低下、耐水性悪化、着色問題など悪影響を及ぼすことから一般的には低添加量となるほど望ましい。   However, emulsifiers such as surfactants are generally desired to be added in a lower amount because they have adverse effects such as deterioration of physical properties, deterioration of water resistance, and coloring problems of various molded products and paints.

特開２０００−１３６２２７JP 2000-136227 A 特開平１１−２９６０８JP-A-11-29608 特開平７−５３７３０JP-A-7-53730

本発明は、かかる現状に基づきなされたものであり、インキ、塗料や樹脂成型品をはじめとする種々の用途に幅広く用いることができ、不純物が少なく、ハンドリング性に優れ、有機溶剤に添加、または各種樹脂に練りこんだ際に容易に１次粒子まで再分散する凝集状微粒子を提供することを目的とする。   The present invention has been made based on the present situation, can be widely used in various applications including ink, paint and resin molded products, has few impurities, has excellent handling properties, is added to an organic solvent, or An object of the present invention is to provide aggregated fine particles that are easily redispersed to primary particles when kneaded into various resins.

本発明者らは上記目的について検討を重ねた結果、微小樹脂粒子が凝集してなる原料凝集粒子に油溶性ビニル系重合体が複合することにより、上記目的が達成されることを見出し、本発明に到達した。すなわち、本発明の目的は、以下の手段により達成される。   As a result of repeated studies on the above object, the present inventors have found that the above object can be achieved by combining an oil-soluble vinyl polymer with raw material aggregated particles obtained by agglomerating fine resin particles. Reached. That is, the object of the present invention is achieved by the following means.

［１］ 微小樹脂粒子が凝集してなる原料凝集粒子に油溶性ビニル系重合体が複合された凝集樹脂粒子であって、全体としては不定形の形状を有しており、かつ含有されている前記微小樹脂粒子は凝集前の形状を維持している複合凝集樹脂粒子。
［２］ 嵩密度が０．２０〜０．５０ｇ／ｃｍ３であることを特徴とする［１］に記載の複合凝集樹脂粒子。
［３］ 含有されている微小樹脂粒子のＳＥＭ画像によって測定した平均粒子径が１００〜６００ｎｍであることを特徴とする［１］または［２］に記載の複合凝集樹脂粒子。
［４］ 粒度分布測定結果を体積基準で微粒側から積算した場合の１０％粒子径が１μｍ以上であることを特徴とする［１］〜［３］のいずれかに記載の複合凝集樹脂粒子。[1] Agglomerated resin particles in which oil-soluble vinyl-based polymers are combined with raw material agglomerated particles obtained by agglomerating fine resin particles, and have an irregular shape as a whole and are contained. The fine resin particles are composite agglomerated resin particles maintaining a shape before agglomeration.
[2] The composite aggregated resin particle according to [1], wherein the bulk density is 0.20 to 0.50 g / cm 3 .
[3] The composite agglomerated resin particles according to [1] or [2], wherein an average particle diameter measured by an SEM image of the contained fine resin particles is 100 to 600 nm.
[4] The composite agglomerated resin particles according to any one of [1] to [3], wherein the 10% particle diameter when the particle size distribution measurement results are integrated from the fine particle side on a volume basis is 1 μm or more.

［５］ 凝集剤を含有しないことを特徴とする［１］〜［４］のいずれかに記載の複合凝集樹脂粒子。
［６］ 乳化剤を含有しないことを特徴とする［１］〜［５］のいずれかに記載の複合凝集樹脂粒子。
［７］油溶性ビニル系重合体の含有量が原料凝集粒子の１５重量％未満であることを特徴とする［１］〜［６］のいずれかに記載の複合凝集樹脂粒子。[5] The composite agglomerated resin particle according to any one of [1] to [4], which does not contain a flocculant.
[6] The composite agglomerated resin particle according to any one of [1] to [5], which does not contain an emulsifier.
[7] The composite agglomerated resin particles according to any one of [1] to [6], wherein the content of the oil-soluble vinyl polymer is less than 15% by weight of the raw material agglomerated particles.

［８］ 原料凝集粒子が、全単量体重量に対して、水に対する溶解性が３重量％未満であるビニル系単量体９０〜１００重量％と、水溶性重合開始剤０．２５〜３重量％を用いて、水中で重合することにより形成されたものであることを特徴とする［１］〜［７］のいずれかに記載の複合凝集樹脂粒子。
［９］ 微小樹脂粒子が凝集してなる原料凝集粒子を含有する水分散液中において、油溶性重合開始剤を用いてビニル系単量体を重合させることによって、前記原料凝集粒子に油溶性ビニル系重合体を複合させたものであることを特徴とする［１］〜［８］のいずれかに記載の複合凝集樹脂粒子。[8] The raw material aggregated particles are 90 to 100% by weight of a vinyl monomer having a solubility in water of less than 3% by weight based on the total weight of the monomer, and a water-soluble polymerization initiator 0.25 to 3 The composite agglomerated resin particles according to any one of [1] to [7], wherein the composite agglomerated resin particles are formed by polymerization in water using a weight percent.
[9] In a water dispersion containing raw material aggregated particles obtained by agglomerating fine resin particles, a vinyl monomer is polymerized using an oil-soluble polymerization initiator, whereby oil-soluble vinyl is added to the raw material aggregated particles. The composite agglomerated resin particles according to any one of [1] to [8], wherein the composite polymer is combined.

［１０］ ［１］〜［９］のいずれかに記載の複合凝集樹脂粒子を含有する塗料組成物。
［１１］ ［１］〜［９］のいずれかに記載の複合凝集樹脂粒子を含有するインキ組成物。
［１２］ ［１］〜［９］のいずれかに記載の複合凝集樹脂粒子を含有する樹脂成型品。[10] A coating composition containing the composite agglomerated resin particles according to any one of [1] to [9].
[11] An ink composition containing the composite agglomerated resin particles according to any one of [1] to [9].
[12] A resin molded product containing the composite agglomerated resin particles according to any one of [1] to [9].

本発明の複合凝集樹脂粒子は有機溶剤に対する再分散性に優れ、凝集剤や乳化剤の含有量が少なく、取扱時においては適度な凝集状態を維持するため、不純物の少ないナノ樹脂粒子の分散体を特別な設備を用いることなく簡易に得ることが出来る。また、本発明の複合凝集樹脂粒子は水系溶剤中では、再分散せず凝集状態を維持するので、水系塗料などに添加した場合には、見る角度に関わらず優れたつや消し効果を発現させる塗膜を得ることができる。   The composite agglomerated resin particles of the present invention are excellent in redispersibility in organic solvents, have a low content of aggregating agents and emulsifiers, and maintain an appropriate agglomerated state during handling. It can be easily obtained without using special equipment. In addition, since the composite agglomerated resin particles of the present invention maintain an agglomerated state without being redispersed in an aqueous solvent, a coating film that exhibits an excellent matting effect regardless of the viewing angle when added to an aqueous paint or the like. Can be obtained.

実施例１で得られた複合凝集樹脂粒子のＳＥＭ画像を示す。The SEM image of the composite aggregation resin particle obtained in Example 1 is shown. 実施例１で得られた複合凝集樹脂粒子中の微小樹脂粒子のＳＥＭ画像を示す。The SEM image of the fine resin particle in the composite aggregation resin particle obtained in Example 1 is shown.

以下、本発明を詳述する。本発明の複合凝集樹脂粒子は、微小樹脂粒子が凝集してなる原料凝集粒子に油溶性ビニル系重合体が複合された不定形状の凝集樹脂粒子である。かかる微小樹脂粒子は複合凝集樹脂粒子を形成している状態において、凝集前の形状を維持している。ここで「凝集前の形状を維持している」とは、複合凝集樹脂粒子をＳＥＭで観察した場合に、微小樹脂粒子同士が融着して凝集前の微小樹脂粒子の輪郭がはっきりしないような状態ではなく、一つ一つの微小樹脂粒子が区別できる程度に輪郭が維持されていることを言う。従って、例えば一部融着していているような状態でも、ＳＥＭ画像上で一つ一つの微小樹脂粒子を区別して見ることができる限り「凝集前の形状を維持している」状態である。   The present invention is described in detail below. The composite agglomerated resin particles of the present invention are irregularly shaped agglomerated resin particles in which an oil-soluble vinyl polymer is compounded with raw material agglomerated particles obtained by agglomerating fine resin particles. Such fine resin particles maintain the shape before aggregation in a state where composite aggregated resin particles are formed. Here, “maintaining the shape before agglomeration” means that when the composite agglomerated resin particles are observed with an SEM, the fine resin particles are fused together and the outline of the fine resin particles before agglomeration is not clear. It means that the contour is maintained to such an extent that each fine resin particle can be distinguished, not the state. Therefore, for example, even in a partially fused state, as long as each fine resin particle can be distinguished and seen on the SEM image, it is in a state of “maintaining the shape before aggregation”.

また、本発明の複合凝集樹脂粒子においては、原料凝集粒子に油溶性ビニル系重合体が複合されている。ここで、複合された状態とは、原料凝集粒子を油溶性ビニル系重合体の溶液に浸漬することで油溶性ビニル系重合体を原料凝集粒子に付着させた状態や、原料凝集粒子の水分散液中において油溶性ビニル系重合体の原料となるビニル系単量体を重合させて得られる状態などが挙げられる。このようにして得られる状態においては、油溶性ビニル系重合体は原料凝集粒子の表面を覆うように付着しており、一部は凝集している微小樹脂粒子間の隙間に入り込んでいるが原料凝集粒子の中心部には達していないと思われる。また、微視的に見るとビニル系重合体の一部は微小樹脂粒子の表層部内に含まれていると思われる。   In the composite agglomerated resin particles of the present invention, the oil-soluble vinyl polymer is composited with the raw material agglomerated particles. Here, the composite state refers to a state where the oil-soluble vinyl polymer is adhered to the raw material aggregated particles by immersing the raw material aggregated particles in the solution of the oil-soluble vinyl polymer, or water dispersion of the raw material aggregated particles. Examples include a state obtained by polymerizing a vinyl monomer that is a raw material for an oil-soluble vinyl polymer in the liquid. In the state obtained in this way, the oil-soluble vinyl polymer is adhered so as to cover the surface of the raw material aggregated particles, and some of the raw materials are contained in the gaps between the aggregated fine resin particles, but the raw material It seems that it did not reach the center of the aggregated particles. Further, when viewed microscopically, it seems that a part of the vinyl polymer is contained in the surface layer portion of the fine resin particles.

また、本発明の複合凝集樹脂粒子の形状は不定形である。ここで、複合凝集樹脂粒子の形状とは複合凝集樹脂粒子の細部の形状ではなく、全体的な形状を対象とするものである。また、「不定形」とは、一つ一つの複合凝集樹脂粒子の形状がまちまちである状態のことである。かかる状態においては、大部分の粒子が球状とは言い難い形状を有しており、粒子を一方向から見た像、すなわち粒子投影像の周囲に凹凸を有している。   Moreover, the shape of the composite aggregation resin particle of this invention is an indeterminate form. Here, the shape of the composite agglomerated resin particles is intended not for the shape of the details of the composite agglomerated resin particles but for the overall shape. Further, “indefinite shape” means a state in which the shape of each composite aggregated resin particle varies. In such a state, most of the particles have a shape that is difficult to say spherical, and has an unevenness around the image of the particles viewed from one direction, that is, the particle projection image.

この不定形の度合いを表す尺度として、下記式によって定義される円形度を用いることができる。
粒子投影像の円形度＝（粒子投影面積と同じ面積の円の周長）／（粒子投影像の周長）
粒子投影像の円形度の平均値＝粒子の円形度
すなわち、円形度は真円の場合に１となり、不定形の度合いが増すにつれ、より小さい値となる。本発明の複合凝集樹脂粒子においては、上記の粒子の円形度として０．５０〜０．９４の範囲が好ましく、０．７０〜０．９０の範囲がより好ましい。なお、かかる円形度は、例えば、シスメックス株式会社製フロー式粒子像分析装置「ＦＰＩＡ−３０００Ｓ」を用いて測定することができる。As a scale representing the degree of this irregular shape, the circularity defined by the following formula can be used.
Circularity of particle projection image = (circumference of a circle having the same area as the particle projection area) / (perimeter of particle projection image)
Average value of circularity of particle projection image = circularity of particle In other words, the circularity is 1 in the case of a perfect circle, and becomes a smaller value as the degree of irregularity increases. In the composite aggregated resin particles of the present invention, the circularity of the above particles is preferably in the range of 0.50 to 0.94, more preferably in the range of 0.70 to 0.90. The circularity can be measured using, for example, a flow type particle image analyzer “FPIA-3000S” manufactured by Sysmex Corporation.

本発明の複合凝集樹脂粒子は、上述のように微小樹脂粒子が凝集前の形状を維持しており、かつ、油溶性ビニル系重合体が複合されていることにより、取り扱いが容易で有機溶剤中で容易に微小樹脂粒子の単位まで再分散することが出来るという特徴を発現する。すなわち、本発明の複合凝集樹脂粒子は、乾燥状態においては油溶性ビニル系重合体により凝集状態を維持できるので、微粉が発生しにくく取り扱いやすい。一方、有機溶剤中においては、油溶性ビニル系重合体が溶解除去され、凝集状態の微小樹脂粒子は互いの融着がない、あるいは、融着している部分が少ないので、撹拌等で外部からの力を加えることにより微小樹脂粒子の単位にまで容易にほぐすことができる。   The composite agglomerated resin particles of the present invention maintain the shape before the agglomeration of the fine resin particles as described above, and are easy to handle in an organic solvent because the oil-soluble vinyl polymer is composited. It is easy to re-disperse to the unit of fine resin particles. That is, the composite agglomerated resin particles of the present invention can be maintained in an agglomerated state by an oil-soluble vinyl polymer in a dry state, and therefore fine powder is not easily generated and is easy to handle. On the other hand, in the organic solvent, the oil-soluble vinyl polymer is dissolved and removed, and the fine resin particles in an agglomerated state are not fused to each other, or there are few fused parts. By applying the force, it can be easily loosened to the unit of fine resin particles.

さらに、本発明の複合凝集樹脂粒子は、水中においてはほぐれにくく凝集状態を維持するので、水系塗料などに添加して塗膜とした場合、複合凝集樹脂粒子の表面上にさまざまな角度の面が密に偏りなく存在することになり、任意の方向からの入射光を斑なく散乱する効果を得ることができる。加えて、本発明の複合凝集樹脂粒子は不定形を有しているため、入射光を様々な方向に散乱する効果を得ることもできる。すなわち、通常の球状粒子による塗膜のつや消し効果は、塗膜を見る角度によって大きく変化するのに対して、上記効果を有する本発明の複合凝集樹脂粒子を用いれば、見る角度に依存せず、広範囲の角度にわたって高い艶消し効果を発現することが期待できる。具体的には、２０°、６０°、８５°グロス値の全てを０〜３０％という低いレベルにすることも可能である。   Furthermore, since the composite agglomerated resin particles of the present invention are not easily loosened in water and maintain an agglomerated state, when added to a water-based paint or the like to form a coating film, surfaces of various angles are formed on the surface of the composite agglomerated resin particles. It will exist densely, and the effect of scattering incident light from an arbitrary direction can be obtained. In addition, since the composite agglomerated resin particles of the present invention have an irregular shape, it is possible to obtain an effect of scattering incident light in various directions. That is, the matte effect of the coating film by the normal spherical particles greatly changes depending on the angle at which the coating film is viewed, whereas if the composite aggregated resin particles of the present invention having the above effects are used, it does not depend on the viewing angle, A high matting effect can be expected over a wide range of angles. Specifically, all of the 20 °, 60 °, and 85 ° gloss values can be set to a low level of 0 to 30%.

かかる本発明の複合凝集樹脂粒子においては、嵩密度が０．２０〜０．５０ｇ／ｃｍ３であることが好ましく、０．２５〜０．４０ｇ／ｃｍ３であることがより好ましい。かかる嵩密度は微小樹脂粒子の凝集状態を確認する尺度として捉えることができ、嵩密度が高すぎる場合、微小樹脂粒子が融着、あるいは強固に凝集しており、このような場合には微小樹脂粒子が再分散しない恐れがある。In the composite aggregated resin particles according the present invention, it is preferable that the bulk density is 0.20~0.50g / cm 3, more preferably 0.25~0.40g / cm 3. Such bulk density can be taken as a measure for confirming the aggregation state of the fine resin particles. When the bulk density is too high, the fine resin particles are fused or strongly aggregated. The particles may not redisperse.

また、本発明の複合凝集樹脂粒子においては、粒度分布測定結果を体積基準で微粒側から積算した場合の１０％粒子径が１μｍ以上であることが好ましく、より好ましくは３μｍ以上、さらに好ましくは５μｍ以上である。１０％粒子径が１μｍ未満であると、微小な粒子が多く、これらの飛散が多くなったり、脱水時に濾布が目詰まりしやすくなったりするなどして取り扱い性が低下する恐れがある。   In the composite agglomerated resin particles of the present invention, the 10% particle diameter when the particle size distribution measurement results are integrated from the fine particle side on a volume basis is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm. That's it. If the 10% particle diameter is less than 1 μm, there are many fine particles, and these scatters increase, and the filter cloth is likely to be clogged during dehydration, which may reduce the handling property.

また、本発明の複合凝集樹脂粒子の体積平均粒子径としては、５〜５０μｍであることが好ましく、より好ましくは５〜３０μｍである。平均粒子径が５μｍ未満であると、塗膜の表面に凹凸が付き難くなって低角度から見た場合に十分な艶消し効果を発現できない恐れがある。一方、平均粒子径が５０μｍを越えると、塗膜への添加重量が同じであっても粒子数が減るため塗膜表面の凹凸数が減り、低角度から見た際の艶消し効果が不十分となる恐れがある。また、塗工時に斑が発生しやすくなり、塗膜表面にざらつきを与えるほか塗膜物性の低下を引き起こす可能性が高くなる。   Moreover, as a volume average particle diameter of the composite aggregation resin particle of this invention, it is preferable that it is 5-50 micrometers, More preferably, it is 5-30 micrometers. If the average particle size is less than 5 μm, the surface of the coating film becomes difficult to be uneven, and there is a possibility that a sufficient matting effect cannot be exhibited when viewed from a low angle. On the other hand, if the average particle diameter exceeds 50 μm, the number of particles will decrease even if the weight added to the coating is the same, so the number of irregularities on the surface of the coating will decrease, and the matte effect when viewed from a low angle will be insufficient. There is a risk of becoming. Moreover, it becomes easy to generate | occur | produce a spot at the time of coating, and the possibility of causing the fall of a coating-film physical property besides giving a rough surface to a coating-film surface becomes high.

また、本発明の複合凝集樹脂粒子は凝集剤を含有しないことが望ましい。ここで、凝集剤とは一次粒子を凝集させるために添加される添加物であって、例えば、高分子凝集剤や無機塩類が挙げられる。凝集粒子中には凝集剤が含有されている場合が多いが、凝集剤を多く含む凝集粒子を塗料に添加すると、塗料や塗膜の特性を低下させる場合がある。また、有機溶剤に対する再分散性を低下させる場合がある。   Moreover, it is desirable that the composite agglomerated resin particles of the present invention do not contain a flocculant. Here, the flocculant is an additive added to agglomerate the primary particles, and examples thereof include a polymer flocculant and inorganic salts. Aggregating particles often contain an aggregating agent, but adding aggregated particles containing a large amount of the aggregating agent to the paint may deteriorate the properties of the paint or coating film. Moreover, the redispersibility with respect to an organic solvent may be reduced.

また、乳化剤についても含有しないことが望ましい。ここで、乳化剤とは界面活性剤を指し、重合工程等で添加される。乳化剤を多く含む凝集粒子を塗料に添加すると、塗料や塗膜の特性を低下させる場合がある。また、水系溶剤中で凝集状態を維持する特性を低下させる場合がある。   Moreover, it is desirable not to contain an emulsifier. Here, an emulsifier refers to a surfactant and is added in a polymerization step or the like. If aggregated particles containing a large amount of emulsifier are added to the paint, the properties of the paint or the coating film may be deteriorated. Moreover, the characteristic which maintains an aggregation state in an aqueous medium may be reduced.

本発明の複合凝集樹脂粒子に含まれる微小樹脂粒子の平均粒子径としては１００〜６００ｎｍとするのが好ましく、１５０〜５００ｎｍであることがより好ましい。この平均粒子径が小さすぎると凝集力が強固となり、目的の再分散性が得られなくなる。逆に大きすぎると微小樹脂粒子同士の凝集状態を維持できなくなる場合がある。また、光散乱の効果の観点からも、かかる平均粒子径とすることが好ましい。   The average particle size of the fine resin particles contained in the composite agglomerated resin particles of the present invention is preferably 100 to 600 nm, and more preferably 150 to 500 nm. If this average particle size is too small, the cohesive force becomes strong and the desired redispersibility cannot be obtained. Conversely, if it is too large, the aggregated state of the fine resin particles may not be maintained. Moreover, it is preferable to set it as this average particle diameter also from a viewpoint of the effect of light scattering.

また、微小樹脂粒子の樹脂の種類としては特に限定されないが、例えば、複合凝集樹脂粒子が添加される塗料樹脂との屈折率差ができるだけ小さくなる樹脂を微小樹脂粒子の樹脂として選択することにより、得られる塗膜の内部ヘイズ値が低下し、透明性が向上する。逆に、屈折率差が大きくなる樹脂を微小樹脂粒子の樹脂として選択することにより、得られる塗膜の内部ヘイズ値が上昇し、防眩や紫外線散乱等の各種光学特性を得ることが出来、目的に応じて任意に選択してよい。また、有機溶剤に再分散させる場合などには、かかる有機溶剤への溶解性や膨潤性が微小樹脂粒子の樹脂の種類を選択する上での考慮事項となりうる。   In addition, the type of resin of the fine resin particles is not particularly limited, but for example, by selecting a resin with a refractive index difference as small as possible with the coating resin to which the composite aggregated resin particles are added, as the resin of the fine resin particles, The internal haze value of the resulting coating film is lowered and the transparency is improved. Conversely, by selecting a resin with a large refractive index difference as the resin of the fine resin particles, the internal haze value of the resulting coating film is increased, and various optical characteristics such as anti-glare and ultraviolet scattering can be obtained. You may select arbitrarily according to the objective. In addition, when redispersed in an organic solvent, the solubility and swelling property in the organic solvent can be a consideration in selecting the resin type of the fine resin particles.

用途により要求特性が様々であるという観点から、微小樹脂粒子の樹脂としては、利用できる単量体の種類が豊富なビニル系樹脂が好ましい。かかるビニル系樹脂を採用する場合に利用できるビニル系単量体としては、アクリル酸メチル、アクリル酸エチル、アクリル酸２−エチルヘキシル、アクリル酸ラウリル、ジメチルアミノエチルアクリレート、ジエチルアミノエチルアクリレート等のアクリル酸エステル系単量体、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ラウリル、ジメチルアミノエチルメタクリレート等のメタクリル酸エステル系単量体、スチレン、ｐ−メチルスチレン等のスチレン系単量体、メチルビニルエーテル、エチルビニルエーテル等のアルキルビニルエーテル、酢酸ビニル、酪酸ビニル等のビニルエステル系単量体、Ｎ−メチルアクリルアミド、Ｎ−エチルアクリルアミド等のＮ−アルキル置換（メタ）アクリルアミド、アクリロニトリル、メタクリロニトリル等のニトリル系単量体、ジビニルベンゼン、エチレングリコールジ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート等の多官能単量体等が挙げられる。このような単量体は、単独で、または２種類以上を組合せて用いてもよい。   From the viewpoint that the required characteristics vary depending on the application, the resin of the fine resin particles is preferably a vinyl resin rich in the types of monomers that can be used. Examples of vinyl monomers that can be used when adopting such vinyl resins include acrylic acid esters such as methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, dimethylaminoethyl acrylate, and diethylaminoethyl acrylate. Monomers, methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, lauryl methacrylate, dimethylaminoethyl methacrylate, styrene monomers such as styrene and p-methylstyrene, methyl vinyl ether, ethyl vinyl ether Vinyl ester monomers such as alkyl vinyl ethers such as vinyl acetate and vinyl butyrate, N-alkyl substituted (meth) acrylamides such as N-methyl acrylamide and N-ethyl acrylamide, acrylonitrile, Polyfunctional monomers such as nitrile monomers such as acrylonitrile, divinylbenzene, ethylene glycol di (meth) acrylate, polyethylene glycol mono (meth) acrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Examples include the body. Such monomers may be used alone or in combination of two or more.

本発明に採用する原料凝集粒子は、上述した微小樹脂粒子が凝集してなるものであり、例えば、乳化重合して得られた微小樹脂粒子の分散体に凝集剤を加えて凝集させることにより得ることができる。しかしながら、メタクリル酸メチルやエチレングリコールジメタクリレートなどの水に対する溶解性が３重量％未満であるビニル系単量体を用いて、後述する製造方法により得られる原料凝集粒子であれば、乳化剤および凝集剤のいずれも含有しておらず、より好ましく採用できる。   The raw material agglomerated particles employed in the present invention are obtained by agglomerating the above-mentioned fine resin particles. For example, the raw material agglomerated particles are obtained by adding a flocculant to a dispersion of fine resin particles obtained by emulsion polymerization and aggregating them. be able to. However, emulsifiers and aggregating agents can be used as long as they are raw material agglomerated particles obtained by a production method described later using a vinyl monomer having a solubility in water of less than 3% by weight, such as methyl methacrylate and ethylene glycol dimethacrylate. None of these are contained and can be more preferably employed.

また、本発明における微小樹脂粒子の粒子径については、重合条件や、乳化剤を用いる場合であればその量などによって調節することができる。同様に、本発明における原料凝集粒子の粒子径としても、原料凝集粒子を製造する際の重合条件や、凝集剤を用いる場合であればその量などによって調節することができる。また、後述する原料凝集粒子の製造方法においては、ポリビニルアルコールの添加によって、原料凝集粒子の粒子径を調節することが可能である。具体的には、ビニル系単量体の重合系中に、該単量体１００重量部に対して、ポリビニルアルコールを好ましくは０．００１〜１重量部、より好ましくは０．０１〜０．１重量部添加して重合する。かかる範囲においてポリビニルアルコールを添加すると、添加しない場合に比べて原料凝集粒子の粒子径が小さくなる傾向が見られる。これは、重合によって生成される微小樹脂粒子の凝集が若干抑制されるためではないかと考えられる。   In addition, the particle size of the fine resin particles in the present invention can be adjusted by polymerization conditions or the amount of emulsifier if used. Similarly, the particle diameter of the raw material agglomerated particles in the present invention can also be adjusted by the polymerization conditions when producing the raw material agglomerated particles, the amount of the aggregating agent, and the like. Moreover, in the manufacturing method of the raw material aggregated particle mentioned later, it is possible to adjust the particle diameter of raw material aggregated particle by addition of polyvinyl alcohol. Specifically, in the polymerization system of the vinyl monomer, the polyvinyl alcohol is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.1 part with respect to 100 parts by weight of the monomer. Polymerization is carried out by adding parts by weight. When polyvinyl alcohol is added in such a range, the particle diameter of the raw material aggregated particles tends to be smaller than when the polyvinyl alcohol is not added. This is thought to be because the aggregation of the fine resin particles produced by polymerization is somewhat suppressed.

本発明に採用する油溶性ビニル系重合体は、上述したように、乾燥状態あるいは水中においては本発明の複合凝集樹脂粒子の凝集状態を維持させるものである。さらに、油溶性ビニル系重合体が有機溶剤中において溶解除去されることにより、本発明の複合凝集樹脂粒子を微小樹脂粒子の単位に容易に再分散させることも可能である。かかる油溶性ビニル系重合体は、水溶性でないものであり、さらに、有機溶剤中で再分散させる場合には、架橋構造を有さないなど、使用する有機溶剤に対して溶解しやすいものであることが望ましい。従って、油溶性ビニル系重合体の選択にあたっては、例えば、再分散に使用する有機溶剤の溶解性パラメータを参考とすることができる。   As described above, the oil-soluble vinyl polymer employed in the present invention maintains the aggregated state of the composite aggregated resin particles of the present invention in a dry state or in water. Furthermore, by dissolving and removing the oil-soluble vinyl polymer in an organic solvent, the composite aggregated resin particles of the present invention can be easily redispersed in units of fine resin particles. Such an oil-soluble vinyl polymer is not water-soluble and, when redispersed in an organic solvent, does not have a cross-linked structure and is easily soluble in the organic solvent to be used. It is desirable. Therefore, in selecting the oil-soluble vinyl polymer, for example, the solubility parameter of the organic solvent used for redispersion can be referred to.

また、後述するように本発明に採用する油溶性ビニル系重合体は、原料凝集粒子を含有する水分散液中において、油溶性重合開始剤を用いてビニル系単量体を重合させることによって、原料凝集粒子に複合させることができる。この場合、使用するビニル系単量体としては、複合させたい油溶性ビニル系重合体が得られるように選択することは当然であるが、ビニル系単量体と微小樹脂粒子の親和性についても考慮すべきである。すなわち、ビニル系単量体を添加した際に微小樹脂粒子が溶解したり、激しく膨潤したりする場合には、微小樹脂粒子が凝集前の形状を維持できず、微小樹脂粒子同士が結着したり合一したりして微小樹脂粒子の単位に再分散出来なくなったり、艶消し性能などの光学特性が低下したりする恐れがある。   Further, as will be described later, the oil-soluble vinyl polymer employed in the present invention is obtained by polymerizing a vinyl monomer using an oil-soluble polymerization initiator in an aqueous dispersion containing raw material aggregated particles. The raw material aggregated particles can be combined. In this case, it is natural to select the vinyl monomer to be used so as to obtain an oil-soluble vinyl polymer to be combined, but the affinity between the vinyl monomer and the fine resin particles is also selected. Should be considered. In other words, when the fine resin particles dissolve or vigorously swell when the vinyl monomer is added, the fine resin particles cannot maintain the shape before aggregation, and the fine resin particles are bound together. Or united with each other, and may not be redispersed into fine resin particle units, or optical properties such as matting performance may be deteriorated.

このように、微小樹脂粒子の形状を維持するという観点からも、本発明に採用する油溶性ビニル系重合体におけるビニル系単量体の種類、及び使用量を考慮する必要があるが、微小樹脂粒子に予め架橋構造を導入し、溶解や膨潤を抑制することにより、ビニル系単量体の選択の幅を広げることが出来る。   Thus, from the viewpoint of maintaining the shape of the fine resin particles, it is necessary to consider the type and amount of vinyl monomer used in the oil-soluble vinyl polymer employed in the present invention. By introducing a crosslinked structure into the particles in advance and suppressing dissolution and swelling, the range of selection of vinyl monomers can be expanded.

以上に述べた本発明に採用する油溶性ビニル系重合体としては、例えば、上述した微小樹脂粒子の樹脂において採用可能なビニル系単量体などの単独重合体や共重合体を挙げることができる。このうち二重結合を複数有する単量体は重合すると架橋構造を形成して油溶性ビニル系重合体の溶解性を低下させるので、有機溶剤への再分散性が求められる場合には全く使用しないか、使用しても少量にとどめることが望ましい。具体的には、ポリ（メタ）アクリル酸エステル、ポリスチレン、ポリ酢酸ビニル、複数種の（メタ）アクリル酸エステルの共重合体などが例示される。なお、「（メタ）アクリル酸」との表記は、「メタアクリル酸」と「アクリル酸」の両者を指し示すものである。   Examples of the oil-soluble vinyl polymer employed in the present invention described above include homopolymers and copolymers such as vinyl monomers that can be employed in the resin of the fine resin particles described above. . Among these, monomers having a plurality of double bonds form a cross-linked structure when polymerized and lower the solubility of the oil-soluble vinyl polymer, so they are not used at all when redispersibility in an organic solvent is required. Or even if it is used, it is desirable to keep it small. Specific examples include poly (meth) acrylic acid esters, polystyrene, polyvinyl acetate, and copolymers of plural types of (meth) acrylic acid esters. The expression “(meth) acrylic acid” indicates both “methacrylic acid” and “acrylic acid”.

また、本発明に採用する油溶性ビニル系重合体を原料凝集粒子に複合する量の上限としては、原料凝集粒子の１５重量％未満であることが好ましく、５重量％未満であることがより好ましく、３重量％以下であることがさらに好ましい。油溶性ビニル系重合体が１５重量％以上となる場合には、有機溶剤への溶解に時間がかかって再分散が容易でなくなる上、再分散液中には溶解した油溶性ビニル系重合体が多く含まれることになり、場合によっては再分散液の特性等の低下を招く恐れがある。また、油溶性ビニル系重合体が１５重量％以上となるようにビニル系単量体を添加して重合させた場合には、微小樹脂粒子がビニル系単量体によって膨潤し、微小樹脂粒子同士の結着や合一によって、有機溶剤への再分散が困難となる場合がある。   Further, the upper limit of the amount of the oil-soluble vinyl polymer employed in the present invention combined with the raw material aggregated particles is preferably less than 15% by weight of the raw material aggregated particles, and more preferably less than 5% by weight. More preferably, it is 3% by weight or less. When the oil-soluble vinyl polymer is 15% by weight or more, it takes a long time to dissolve in an organic solvent and re-dispersion is not easy, and the re-dispersed liquid contains dissolved oil-soluble vinyl polymer. In some cases, the properties of the re-dispersed liquid may be deteriorated. When the vinyl monomer is added and polymerized so that the oil-soluble vinyl polymer is 15% by weight or more, the fine resin particles are swollen by the vinyl monomer, and the fine resin particles In some cases, re-dispersion in an organic solvent may be difficult due to binding or coalescence.

一方、油溶性ビニル系重合体を原料凝集粒子に複合する量の下限としては、原料凝集粒子の０．０１重量％以上とすることが好ましく、より好ましくは０．１重量％以上、さらに好ましくは０．５重量％以上である。油溶性ビニル系重合体が０．０１重量％未満となる場合には、油溶性ビニル系重合体による凝集維持効果がほとんど得られず、微粉が発生しやすくなり、取り扱いにくいものとなる場合がある。   On the other hand, the lower limit of the amount of the oil-soluble vinyl polymer combined with the raw material aggregated particles is preferably 0.01% by weight or more of the raw material aggregated particles, more preferably 0.1% by weight or more, and still more preferably. 0.5% by weight or more. When the oil-soluble vinyl polymer is less than 0.01% by weight, the effect of maintaining aggregation by the oil-soluble vinyl polymer is hardly obtained, fine powder is likely to be generated, and it may be difficult to handle. .

以上に述べてきた本発明の複合凝集樹脂粒子は、原料凝集粒子に油溶性ビニル系重合体を複合させることによって得ることができる。かかる原料凝集粒子は上述した本発明の複合樹脂粒子に求められる特性の観点から、微小樹脂粒子が凝集前の形状維持しつつ凝集したものであることが望ましい。このような原料凝集粒子の製造方法としては、目的の原料凝集粒子が得られる限り特に限定されない。一例として、水溶性重合開始剤の溶解した水中にビニル系単量体の液滴を分散させ、加熱・撹拌しながら重合する方法で原料凝集粒子を形成させることが可能である。該方法では、特別な操作や添加物を加えることなく、微小樹脂粒子が凝集した原料凝集粒子が得られる。このようにして得られた原料凝集粒子は粉砕・分級することで任意の粒子径に調整することも可能である。   The composite agglomerated resin particles of the present invention described above can be obtained by combining an oil-soluble vinyl polymer with raw material agglomerated particles. From the viewpoint of the characteristics required for the composite resin particles of the present invention described above, the raw material aggregated particles are desirably those in which the fine resin particles are aggregated while maintaining the shape before aggregation. The method for producing such raw material aggregated particles is not particularly limited as long as the desired raw material aggregated particles are obtained. As an example, raw material aggregated particles can be formed by dispersing vinyl monomer droplets in water in which a water-soluble polymerization initiator is dissolved, and polymerizing the mixture while heating and stirring. In this method, raw material aggregated particles in which fine resin particles are aggregated can be obtained without adding any special operation or additive. The raw material aggregated particles thus obtained can be adjusted to an arbitrary particle size by pulverization and classification.

かかる方法において使用されるビニル系単量体としては、２０℃における水に対する溶解性が３重量％未満、好ましくは２重量％未満のビニル系単量体を用いることが望ましく、かかるビニル系単量体を全単量体重量に対して９０重量％以上、好ましくは９５重量％以上用いる。かかるビニル単量体の代表的な例としては、アクリル酸メチル、アクリル酸エチル、アクリル酸２−エチルヘキシル、アクリル酸ラウリル等のアクリル酸エステル系単量体、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ラウリル等のメタクリル酸エステル系単量体、スチレン、ｐ−メチルスチレン等のスチレン系単量体、メチルビニルエーテル、エチルビニルエーテル等のアルキルビニルエーテル、酢酸ビニル、酪酸ビニル等のビニルエステル系単量体、ジビニルベンゼン、エチレングリコールジ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレートなどを挙げることができる。かかる単量体が９０重量％未満の場合、微小樹脂粒子が凝集しなくなる場合がある。これは、水に対する溶解性が３重量％以上のビニル系単量体の使用量が多くなることで、かかる単量体が優先的に重合し、分散剤的な役割を果たすためと考えられる。また、全仕込み重量に対する全単量体重量の割合としては、５〜３５重量％であることが望ましい。   As the vinyl monomer used in such a method, it is desirable to use a vinyl monomer having a solubility in water at 20 ° C. of less than 3% by weight, preferably less than 2% by weight. The body is used in an amount of 90% by weight or more, preferably 95% by weight or more based on the total monomer weight. Representative examples of such vinyl monomers include acrylate monomers such as methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate, methyl methacrylate, ethyl methacrylate, and methacrylic acid. Methacrylic acid ester monomers such as lauryl, styrene monomers such as styrene and p-methylstyrene, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl ester monomers such as vinyl acetate and vinyl butyrate, divinyl Examples include benzene, ethylene glycol di (meth) acrylate, polyethylene glycol mono (meth) acrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate. That. When the monomer is less than 90% by weight, the fine resin particles may not aggregate. This is presumably because the amount of vinyl monomer having a solubility in water of 3% by weight or more increases the amount of such a monomer that preferentially polymerizes and acts as a dispersant. Moreover, as a ratio of the total monomer weight with respect to the total preparation weight, it is desirable that it is 5-35 weight%.

重合開始剤としては水溶性重合開始剤であれば、アゾ系、過硫酸塩系、過酸化物系、レドックス系などいずれの種類の開始剤でも採用でき、光開始剤でも、熱開始剤でもよい。代表的な例としては、２，２’−Ａｚｏｂｉｓ（２−ｍｅｔｈｙｌｐｒｏｐｉｏｎａｍｉｄｉｎｅ）ｄｉｈｙｄｒｏｃｈｌｏｒｉｄｅ、２，２’−Ａｚｏｂｉｓ（１−ｉｍｉｎｏ−１−ｐｙｒｒｏｌｉｄｉｎｏ−２−ｍｅｔｈｙｌｐｒｏｐａｎｅ）ｄｉｈｙｄｒｏｃｈｌｏｒｉｄｅ、ｔ−Ｂｕｔｙｌｈｙｄｒｏｐｅｒｏｘｉｄｅ、過硫酸アンモニウム、過硫酸カリウム、過酸化水素／鉄（ＩＩ）イオン系などを挙げることができる。   As the polymerization initiator, any type of initiator such as azo, persulfate, peroxide, redox, etc. can be adopted as long as it is a water-soluble polymerization initiator, and it may be a photoinitiator or a thermal initiator. . Representative examples include 2,2′-Azobis (2-methylpropionamidine) dihydrochloride, 2,2′-Azobis (1-imino-1-pyrrolidino-2-methylpropylane) dihydrochloride, t-Butylhydrogen sulfate, Examples thereof include potassium and hydrogen peroxide / iron (II) ion systems.

かかる水溶性重合開始剤は、全単量体重量に対して０．２５〜３重量％、好ましくは０．２５〜２重量％用いることが望ましい。かかる範囲内とすることにより、微小樹脂粒子が凝集した状態であり、かつ、塊状化していない適度な大きさの粒子を得ることができる。   The water-soluble polymerization initiator is used in an amount of 0.25 to 3% by weight, preferably 0.25 to 2% by weight, based on the total monomer weight. By setting it within such a range, it is possible to obtain particles having a moderate size in which the fine resin particles are in an aggregated state and are not agglomerated.

以上のようにして、本発明に採用する原料凝集粒子を得ることができるが、必要に応じて粉砕処理を施し、所望の粒子径に調整することも可能である。かかる粉砕処理においては特別な装置を必要とせず、ブレードミル、バンバリーミキサー、ニーダーミキサー、ロールなどの汎用の粉砕装置を用いることができる。また、粉砕処理に際しては、粒子を乾燥させておく必要はなく、重合終了後などの湿潤状態で粉砕することも可能である。   As described above, the raw material aggregated particles employed in the present invention can be obtained. However, if necessary, the raw material aggregated particles can be pulverized and adjusted to a desired particle size. Such a pulverization process does not require a special apparatus, and a general-purpose pulverization apparatus such as a blade mill, a Banbury mixer, a kneader mixer, or a roll can be used. In the pulverization treatment, it is not necessary to dry the particles, and the particles can be pulverized in a wet state such as after the polymerization.

また、上記に詳述した製造方法においては、乳化剤や凝集剤を使用しないでも適度な凝集状態の原料凝集粒子を得ることが可能であるため、本発明の複合凝集樹脂粒子を得るうえで適した方法である。ただし、本製造方法においては必要に応じて乳化剤や凝集剤を用いることも可能である。   Further, in the production method described in detail above, since it is possible to obtain raw material aggregated particles in an appropriate aggregated state without using an emulsifier or a flocculant, it is suitable for obtaining the composite aggregated resin particles of the present invention. Is the method. However, in this production method, an emulsifier and a flocculant can be used as necessary.

また、油溶性ビニル系重合体を複合させる方法としては、例えば、原料凝集粒子を含有する水分散液中において、油溶性重合開始剤を用いてビニル系単量体を重合させる方法を挙げることができる。   Examples of a method of combining an oil-soluble vinyl polymer include a method of polymerizing a vinyl monomer using an oil-soluble polymerization initiator in an aqueous dispersion containing raw material aggregated particles. it can.

かかる方法において、原料凝集粒子を含有する水分散液としては、上記に詳述した原料凝集粒子の製造方法において重合により生成する原料凝集粒子の分散液をそのまま使用してもよい。また、ビニル系単量体と油溶性重合開始剤を水分散液中に添加する方法としては、これらを別々に添加する方法、ビニル系単量体に油溶性重合開始剤を溶解させたものを添加する方法、前記二者の方法について溶媒で希釈したものを添加する方法などを採用でき、一度に全量投入してもよく、重合を進めながら少しずつ滴下してもよい。また、ビニル系単量体の添加量としては、上述した、油溶性ビニル系重合体を原料凝集粒子に複合する量の観点から、上限としては、原料凝集粒子の好ましくは１５重量％未満、より好ましくは５重量％未満、さらに好ましくは３重量％以下である。下限としては、原料凝集粒子の好ましくは０．０１重量％以上、より好ましくは０．１重量％以上、さらに好ましくは０．５重量％以上である。   In this method, as the aqueous dispersion containing the raw material aggregated particles, the raw material aggregated particle dispersion produced by the polymerization in the raw material aggregated particle production method described in detail above may be used as it is. In addition, as a method of adding a vinyl monomer and an oil-soluble polymerization initiator into an aqueous dispersion, a method of adding them separately, a method in which an oil-soluble polymerization initiator is dissolved in a vinyl monomer A method of adding, a method of adding a solution diluted with a solvent with respect to the above-mentioned two methods, etc. can be adopted, and the whole amount may be added at once, or it may be added dropwise little by little while the polymerization proceeds. In addition, the addition amount of the vinyl monomer is, as described above, from the viewpoint of the amount of the oil-soluble vinyl polymer combined with the raw material aggregated particles, and the upper limit is preferably less than 15% by weight of the raw material aggregated particles. Preferably it is less than 5 weight%, More preferably, it is 3 weight% or less. The lower limit is preferably 0.01% by weight or more of the raw material aggregated particles, more preferably 0.1% by weight or more, and further preferably 0.5% by weight or more.

なお、かかる方法によって、油溶性ビニル系重合体を複合させる場合、原料凝集粒子を構成する微小樹脂粒子としては架橋構造を有するものであることが望ましい。架橋構造がない場合、加えられたビニル系単量体により微小樹脂粒子が溶解し、本発明の複合凝集樹脂粒子が得られない場合がある。架橋構造の導入方法としては、上記に詳述した原料凝集粒子の製造方法などの場合であれば、ビニル基を２個以上有するビニル系単量体を共重合する方法などを挙げることができる。   When the oil-soluble vinyl polymer is combined by such a method, it is desirable that the fine resin particles constituting the raw material aggregated particles have a crosslinked structure. When there is no cross-linked structure, the fine resin particles are dissolved by the added vinyl monomer, and the composite aggregated resin particles of the present invention may not be obtained. Examples of a method for introducing a crosslinked structure include a method of copolymerizing a vinyl monomer having two or more vinyl groups in the case of the raw material aggregated particle production method described in detail above.

以下に本発明の複合凝集樹脂粒子の用途を記載するが、かかる用途は一例であり、本発明の複合凝集樹脂粒子は、その他の幅広い用途にも用いることができる。   Although the use of the composite aggregation resin particle of this invention is described below, this use is an example and the composite aggregation resin particle of this invention can be used also for the other wide use.

本発明の複合凝集樹脂粒子は、塗料、インキ組成物のほか樹脂成型品などに含有させて用いることができる。塗料、インキ組成物を製造する方法としては、本発明の複合凝集樹脂粒子及びバインダ樹脂を有機溶剤に添加する方法が挙げられる。上記バインダ樹脂は特に限定されず、例えば、熱可塑性樹脂、熱硬化性樹脂、光硬化性樹脂が挙げられ、具体的には、例えば、アクリル系樹脂、ポリエステル樹脂、ポリ塩化ビニル、ポリウレタン、シリコーン樹脂、メラミン樹脂などが挙げられる。なお、塗膜に透明性を付与する場合には、アクリル系樹脂、アクリルーシリコーン系樹脂などを好適に用いることが好ましい。   The composite agglomerated resin particles of the present invention can be used by being contained in a resin molded product in addition to a paint and an ink composition. Examples of the method for producing the paint and ink composition include a method of adding the composite aggregated resin particles and binder resin of the present invention to an organic solvent. The binder resin is not particularly limited, and examples thereof include thermoplastic resins, thermosetting resins, and photocurable resins. Specifically, for example, acrylic resins, polyester resins, polyvinyl chloride, polyurethane, silicone resins And melamine resin. In addition, when providing transparency to a coating film, it is preferable to use acrylic resin, acrylic-silicone resin, etc. suitably.

上記有機溶剤は、バインダ樹脂を溶解するものであれば、特に限定されず、例えば、トルエン、キシレン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチレングリコールモノメチルエーテル（メチルセロソルブ）、エチレングリコールモノエチルエーテル（エチルセロソルブ）、酢酸エチル、酢酸ブチル、イソプロピルアルコール、アセトン、アニソールなどが挙げられ、単独で用いられても二種以上が併用されてもよい。又、塗料、インキ組成物には、レベリング剤、表面改質剤、脱泡剤、顔料などの着色剤などの公知の各種添加剤が添加されてもよい。   The organic solvent is not particularly limited as long as it dissolves the binder resin. For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl) Cellosolve), ethyl acetate, butyl acetate, isopropyl alcohol, acetone, anisole, and the like. These may be used alone or in combination of two or more. In addition, various known additives such as leveling agents, surface modifiers, defoaming agents, and coloring agents such as pigments may be added to the paint and ink composition.

上記組成物は、例えば、有機溶剤にバインダ樹脂を溶解した後に本発明の凝集樹脂粒子を添加して、サンドミル、ボールミル、アトライター、高速回転撹拌装置、三本ロールなどを用いて均一に分散、混合させても製造することができる。   The above composition is, for example, by adding the aggregated resin particles of the present invention after dissolving the binder resin in an organic solvent, and uniformly dispersing using a sand mill, ball mill, attritor, high-speed rotary stirrer, triple roll, etc. It can also be produced by mixing.

本発明の複合凝集樹脂粒子は、上記のような溶剤系の塗料、インキ組成物に限定されず無溶剤系、水性、粉体など各種塗料、インキ組成物にも用いることができる。特に、水系塗料に添加した場合には、上述したように、ほぐれることなく凝集状態を維持するので、塗膜に優れたつや消し性を効果的に発現させることができる。   The composite agglomerated resin particles of the present invention are not limited to solvent-based paints and ink compositions as described above, and can also be used in various paints and ink compositions such as solvent-free, water-based, and powder. In particular, when added to a water-based paint, as described above, the aggregated state is maintained without being loosened, so that excellent mattness can be effectively exhibited in the coating film.

また、本発明の複合凝集樹脂粒子は熱可塑性または熱硬化性マトリックス樹脂に練り込んで成型することにより１次粒子に再分散化した微小樹脂粒子を含有する樹脂成型品を製造することが出来る。これらのマトリックス樹脂としてはポリメチルメタクリレート樹脂、ＭＳ樹脂、ポリカーボネート樹脂、ポリエステル樹脂など透明性に優れ、耐候性が良く、剛性のある樹脂が好ましく用いられる。   In addition, the composite agglomerated resin particles of the present invention can be molded into a thermoplastic or thermosetting matrix resin to form a resin molded product containing fine resin particles redispersed into primary particles. As these matrix resins, resins having excellent transparency, good weather resistance, and rigidity such as polymethyl methacrylate resin, MS resin, polycarbonate resin, and polyester resin are preferably used.

本発明の樹脂成型品は、樹脂と複合凝集樹脂粒子とを混合機で混合し、溶融混練機で混練した後、押し出すことでシート状の樹脂成型品を得ることができる。また溶融混練後、ペレットとして取り出し、このペレットを溶融後射出成型することでも上記成型品を得ることが出来る。   The resin molded product of the present invention can be obtained by mixing a resin and composite agglomerated resin particles with a mixer, kneading with a melt kneader, and then extruding the resin molded product. Further, the molded product can be obtained by taking out as a pellet after melt-kneading and then injection-molding the pellet after melting.

以下、実施例および比較例により本発明の効果を説明するが、本発明の範囲はこれら実施例のみに限定されるものではない。   Hereinafter, the effects of the present invention will be described with reference to examples and comparative examples, but the scope of the present invention is not limited to these examples.

（１）試料粒子の円形度、体積平均粒子径および１０％粒子径
上述した定義による粒子の円形度、体積平均粒子径および１０％粒子径をフロー式粒子像分析装置（ＦＰＩＡ−３０００Ｓ：シスメックス（株）製）によって測定した。なお、１０％粒子径は、粒度分布測定結果を体積基準で微粒側から積算して求めたものである。(1) Circularity, volume average particle diameter, and 10% particle diameter of sample particles The circularity, volume average particle diameter, and 10% particle diameter of the particles according to the above-described definition are measured using a flow particle image analyzer (FPIA-3000S: Sysmex ( Measured by the company). The 10% particle size is obtained by integrating the particle size distribution measurement results from the fine particle side on a volume basis.

（２）微小樹脂粒子の平均粒子径
試料粒子のＳＥＭ画像において、微小樹脂粒子を任意に２０個選び出して、それぞれの直径を測定し平均値を算出した。(2) Average particle diameter of fine resin particles In the SEM image of the sample particles, 20 fine resin particles were arbitrarily selected, and each diameter was measured to calculate an average value.

（３）嵩密度
体積が既知の容器Ａ（ｃｍ３）に粒子を充填し、その重量Ｂ（ｇ）を測定して嵩密度を算出した。
嵩密度（ｇ／ｃｍ３）＝Ｂ（ｇ）／Ａ（ｃｍ３）(3) Bulk density A container A (cm 3 ) having a known volume was filled with particles, and its weight B (g) was measured to calculate the bulk density.
Bulk density (g / cm 3 ) = B (g) / A (cm 3 )

（４）再分散性
試料粒子１０重量部とメチルエチルケトン５０重量部を油性トップコート塗料（アクリディック（アクリル樹脂、樹脂濃度３０重量％）：ＤＩＣ株式会社製）１００重量部に加え、ホモジナイザーで１０分間撹拌した。得られた塗料組成物をＰＥＴフィルム（コスモシャイン＃Ａ４３００（厚さ１００μｍ：東洋紡績（株）製）上にバーコーター＃２６で塗工し、その後６０℃の熱風乾燥機中で３０分乾燥した。光学顕微鏡を用いてかかる塗膜を観察し、以下に示す基準で再分散性を判定した。
○：凝集粒子がない
△：凝集粒子がわずかにある
×：凝集粒子がある(4) Redispersibility 10 parts by weight of sample particles and 50 parts by weight of methyl ethyl ketone are added to 100 parts by weight of an oil-based topcoat paint (Acridic (acrylic resin, resin concentration: 30% by weight): manufactured by DIC Corporation), and 10 minutes by a homogenizer. Stir. The obtained coating composition was coated on a PET film (Cosmo Shine # A4300 (thickness 100 μm: manufactured by Toyobo Co., Ltd.) with a bar coater # 26, and then dried in a hot air dryer at 60 ° C. for 30 minutes. The coating film was observed using an optical microscope, and redispersibility was determined according to the following criteria.
○: No aggregated particles Δ: There are few aggregated particles ×: There are aggregated particles

（５）２０°、６０°、８５°グロス値
試料粒子３重量部と水５０重量部を水性トップコート塗料（水溶性つやだしニス（アクリル樹脂、樹脂濃度３０重量％）：和信ペイント（株）製）１００重量部に加え、ホモジナイザーで１０分間撹拌した。得られた塗料組成物を用いて隠蔽率試験紙上に塗膜サンプルを作成し、光沢度計（ＶＧ ２０００：日本電色（株）製）によって測定した。(5) 20 °, 60 °, and 85 ° gloss values 3 parts by weight of sample particles and 50 parts by weight of water were used as an aqueous top coat paint (water-soluble glossy varnish (acrylic resin, resin concentration 30% by weight): Wasshin Paint Co., Ltd. (Made) In addition to 100 weight part, it stirred for 10 minutes with the homogenizer. A coating film sample was prepared on the concealment rate test paper using the obtained coating composition, and measured with a gloss meter (VG 2000: manufactured by Nippon Denshoku Co., Ltd.).

［実施例１］
反応槽に水３００重量部を仕込み、重合開始剤として２，２’−Ａｚｏｂｉｓ（１−ｉｍｉｎｏ−１−ｐｙｒｒｏｌｉｄｉｎｏ−２−ｍｅｔｈｙｌｐｒｏｐａｎｅ）ｄｉｈｙｄｒｏｃｈｌｏｒｉｄｅ０．６重量部を溶解させる。次いで単量体としてメタクリル酸メチル９９重量部とエチレングリコールメタクリレート１重量部を加えて、撹拌しながら４５℃で２時間反応させ、原料凝集粒子の水分散液を得る。続いて、該水分散液に、該水分散液の固形分を１００重量部としてメタクリル酸メチル３重量部と２，２’―アゾビス（２−メチルバレロニトリル）０．３重量部を加え、再度４５℃で２時間反応させる。次いで、粗大粒子を除去するため分級した後、遠心脱水することにより、実施例１の複合凝集樹脂粒子を得た。該粒子の特性を測定した結果を表１に示す。また、該粒子のＳＥＭ画像を図１および図２に示す。[Example 1]
300 parts by weight of water is charged into the reaction vessel, and 0.6 part by weight of 2,2′-Azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride is dissolved as a polymerization initiator. Next, 99 parts by weight of methyl methacrylate and 1 part by weight of ethylene glycol methacrylate are added as monomers, and the mixture is reacted at 45 ° C. for 2 hours with stirring to obtain an aqueous dispersion of raw material aggregated particles. Subsequently, 3 parts by weight of methyl methacrylate and 0.3 part by weight of 2,2′-azobis (2-methylvaleronitrile) are added to the aqueous dispersion with the solid content of the aqueous dispersion as 100 parts by weight, and again. React at 45 ° C. for 2 hours. Subsequently, after classifying in order to remove coarse particles, centrifugal dehydration was performed to obtain composite agglomerated resin particles of Example 1. The results of measuring the characteristics of the particles are shown in Table 1. In addition, SEM images of the particles are shown in FIGS.

［実施例２］
反応槽に水３００重量部を仕込み、重合開始剤として過硫酸カリウム０．６重量部を溶解させる。次いで単量体としてメタクリル酸メチル９９重量部とエチレングリコールメタクリレート１重量部を加えて、撹拌しながら４５℃で２時間反応させ、原料凝集粒子の水分散液を得る。続いて、該水分散液に、該水分散液の固形分を１００重量部としてスチレン３重量部と２，２’―アゾビス（２−メチルバレロニトリル）０．３重量部を加え、再度４５℃で２時間反応させる。次いで、粗大粒子を除去するため分級した後、遠心脱水することにより、実施例２の複合凝集樹脂粒子を得た。該粒子の特性を測定した結果を表１に示す。[Example 2]
300 parts by weight of water is charged into the reaction vessel, and 0.6 part by weight of potassium persulfate is dissolved as a polymerization initiator. Next, 99 parts by weight of methyl methacrylate and 1 part by weight of ethylene glycol methacrylate are added as monomers, and the mixture is reacted at 45 ° C. for 2 hours with stirring to obtain an aqueous dispersion of raw material aggregated particles. Subsequently, 3 parts by weight of styrene and 0.3 part by weight of 2,2′-azobis (2-methylvaleronitrile) were added to the aqueous dispersion with the solid content of the aqueous dispersion as 100 parts by weight, and again at 45 ° C. For 2 hours. Subsequently, after classifying in order to remove coarse particles, centrifugal dehydration was performed to obtain composite agglomerated resin particles of Example 2. The results of measuring the characteristics of the particles are shown in Table 1.

［実施例３］
実施例１において、原料凝集粒子の水分散液に添加するメタクリル酸メチル３重量部を酢酸ビニル３重量部に変更すること以外は実施例１と同様にして、実施例３の複合凝集樹脂粒子を得た。該粒子の特性を測定した結果を表１に示す。[Example 3]
In Example 1, the composite aggregated resin particles of Example 3 were obtained in the same manner as in Example 1 except that 3 parts by weight of methyl methacrylate added to the aqueous dispersion of raw material aggregated particles was changed to 3 parts by weight of vinyl acetate. Obtained. The results of measuring the characteristics of the particles are shown in Table 1.

［実施例４］
実施例１において、原料凝集粒子の水分散液に添加するメタクリル酸メチル３重量部をアクリル酸２−エチルヘキシル３重量部に変更すること以外は実施例１と同様にして、実施例４の複合凝集樹脂粒子を得た。該粒子の特性を測定した結果を表１に示す。[Example 4]
In Example 1, the composite aggregation of Example 4 was performed in the same manner as in Example 1 except that 3 parts by weight of methyl methacrylate added to the aqueous dispersion of raw material aggregated particles was changed to 3 parts by weight of 2-ethylhexyl acrylate. Resin particles were obtained. The results of measuring the characteristics of the particles are shown in Table 1.

［実施例５］
実施例１において、原料凝集粒子の水分散液に添加するメタクリル酸メチル３重量部をメタクリル酸メチル０．１重量部に変更すること以外は実施例１と同様にして実施例５の複合凝集樹脂粒子を得た。該粒子の特性を測定した結果を表１に示す。[Example 5]
The composite agglomerated resin of Example 5 is the same as Example 1 except that 3 parts by weight of methyl methacrylate added to the aqueous dispersion of raw material aggregated particles is changed to 0.1 parts by weight of methyl methacrylate. Particles were obtained. The results of measuring the characteristics of the particles are shown in Table 1.

［実施例６］
実施例１において、原料凝集粒子の水分散液に添加するメタクリル酸メチル３重量部をメタクリル酸メチル１５重量部に変更すること以外は実施例１と同様にして実施例６の複合凝集樹脂粒子を得た。該粒子の特性を測定した結果を表１に示す。[Example 6]
In Example 1, the composite aggregated resin particles of Example 6 were obtained in the same manner as in Example 1 except that 3 parts by weight of methyl methacrylate added to the aqueous dispersion of the raw material aggregated particles was changed to 15 parts by weight of methyl methacrylate. Obtained. The results of measuring the characteristics of the particles are shown in Table 1.

［実施例７］
実施例１において、原料凝集粒子の合成に使用するエチレングリコールメタクリレート１重量部をトリメチロールプロパントリメタクリレート１重量部に変更すること以外は実施例１と同様にして実施例７の複合凝集樹脂粒子を得た。該粒子の特性を測定した結果を表１に示す。[Example 7]
In Example 1, the composite aggregated resin particles of Example 7 were prepared in the same manner as in Example 1 except that 1 part by weight of ethylene glycol methacrylate used for the synthesis of the raw material aggregated particles was changed to 1 part by weight of trimethylolpropane trimethacrylate. Obtained. The results of measuring the characteristics of the particles are shown in Table 1.

［実施例８］
実施例１において、原料凝集粒子の反応前にポリビニルアルコール０．０４重量部を添加すること以外は実施例１と同様にして実施例８の複合凝集樹脂粒子を得た。該粒子の特性を測定した結果を表１に示す。[Example 8]
In Example 1, composite aggregated resin particles of Example 8 were obtained in the same manner as in Example 1 except that 0.04 parts by weight of polyvinyl alcohol was added before the reaction of the raw material aggregated particles. The results of measuring the characteristics of the particles are shown in Table 1.

［比較例１］
実施例１の原料凝集粒子の水分散液を粗大粒子を除去するため分級した後、遠心脱水することにより、比較例１の粒子を得た。該粒子の特性を測定した結果を表１に示す。[Comparative Example 1]
After classifying the aqueous dispersion of the raw material aggregated particles of Example 1 to remove coarse particles, centrifugal dehydration was performed to obtain particles of Comparative Example 1. The results of measuring the characteristics of the particles are shown in Table 1.

［比較例２］
実施例１において、原料凝集粒子の水分散液に添加するメタクリル酸メチル３重量部をメタクリル酸メチル２０重量部に変更すること以外は実施例１と同様にして比較例２の粒子を得た。該粒子の特性を測定した結果を表１に示す。[Comparative Example 2]
In Example 1, particles of Comparative Example 2 were obtained in the same manner as in Example 1 except that 3 parts by weight of methyl methacrylate added to the aqueous dispersion of raw material aggregated particles was changed to 20 parts by weight of methyl methacrylate. The results of measuring the characteristics of the particles are shown in Table 1.

［参考例１］
実施例１における原料樹脂粒子の製造方法において、メタクリル酸メチル９９重量部とエチレングリコールメタクリレート１重量部を用いる代わりに、メタクリル酸メチル８５重量部と２−ヒドロキシエチルメタクリレート１５重量部を用いること以外は同様にして重合を行ったところ微小樹脂粒子の水分散体が得られ、原料凝集粒子は得られなかった。[Reference Example 1]
In the method for producing raw material resin particles in Example 1, instead of using 99 parts by weight of methyl methacrylate and 1 part by weight of ethylene glycol methacrylate, 85 parts by weight of methyl methacrylate and 15 parts by weight of 2-hydroxyethyl methacrylate are used. When polymerization was carried out in the same manner, an aqueous dispersion of fine resin particles was obtained, and raw material aggregated particles were not obtained.

実施例１〜８では有機溶剤への再分散性に優れ、かつ、微粉の少ない複合凝集樹脂粒子が得られた。また、これらの粒子を水系塗料に添加して塗膜とした場合、２０°、６０°、８５°のいずれの角度におけるグロス値も低いレベルとなり、見る角度によらない高い艶消し効果を得ることができた。一方、比較例１の粒子は１０％粒子径が小さいが、これはビニル系重合体を複合しておらず、凝集粒子がほぐれて微粉が増加したことによると思われる。このため、該粒子は分級時や調合時に飛散するなど取り扱い性のよくないものであった。比較例２の粒子はビニル系重合体の複合量が多いため、微小樹脂粒子同士が融着しており、再分散性ができないものであった。
In Examples 1 to 8, composite agglomerated resin particles having excellent redispersibility in an organic solvent and few fine powders were obtained. Moreover, when these particles are added to a water-based paint to form a coating film, the gloss value at any angle of 20 °, 60 °, and 85 ° is low, and a high matte effect regardless of the viewing angle is obtained. I was able to. On the other hand, the particles of Comparative Example 1 have a small particle size of 10%, but this seems to be because the vinyl polymer was not combined and the aggregated particles were loosened and the fine powder increased. For this reason, the particles have poor handling properties such as scattering during classification and preparation. Since the particles of Comparative Example 2 contained a large amount of vinyl polymer, the fine resin particles were fused together, and redispersibility was not possible.

Claims (12)

微小樹脂粒子が凝集してなる原料凝集粒子に油溶性ビニル系重合体が複合された凝集樹脂粒子であって、全体としては不定形の形状を有しており、かつ含有されている前記微小樹脂粒子は凝集前の形状を維持している複合凝集樹脂粒子。 Agglomerated resin particles in which oil-soluble vinyl-based polymers are combined with raw material agglomerated particles obtained by agglomerating fine resin particles, and the microresin has an irregular shape as a whole and is contained therein Composite agglomerated resin particles that maintain the shape before agglomeration. 嵩密度が０．２０〜０．５０ｇ／ｃｍ３であることを特徴とする請求項１に記載の複合凝集樹脂粒子。 The bulk density resin is 0.20-0.50g / cm3, The composite aggregation resin particle of Claim 1 characterized by the above-mentioned. 含有されている微小樹脂粒子のＳＥＭ画像によって測定した平均粒子径が１００〜６００ｎｍであることを特徴とする請求項１または２に記載の複合凝集樹脂粒子。 The composite agglomerated resin particles according to claim 1 or 2, wherein an average particle size measured by an SEM image of the contained fine resin particles is 100 to 600 nm. 粒度分布測定結果を体積基準で微粒側から積算した場合の１０％粒子径が１μｍ以上であることを特徴とする請求項１〜３のいずれかに記載の複合凝集樹脂粒子。 The composite agglomerated resin particles according to any one of claims 1 to 3, wherein a 10% particle diameter when the particle size distribution measurement results are integrated from the fine particle side on a volume basis is 1 µm or more. 凝集剤を含有しないことを特徴とする請求項１〜４のいずれかに記載の複合凝集樹脂粒子。 The composite agglomerated resin particle according to any one of claims 1 to 4, which does not contain a flocculant. 乳化剤を含有しないことを特徴とする請求項１〜５のいずれかに記載の複合凝集樹脂粒子。 The composite agglomerated resin particle according to any one of claims 1 to 5, which does not contain an emulsifier. 油溶性ビニル系重合体の含有量が原料凝集粒子の１５重量％未満であることを特徴とする請求項１〜６のいずれかに記載の複合凝集樹脂粒子。 The composite agglomerated resin particles according to any one of claims 1 to 6, wherein the content of the oil-soluble vinyl polymer is less than 15% by weight of the raw material agglomerated particles. 原料凝集粒子が、全単量体重量に対して、水に対する溶解性が３重量％未満であるビニル系単量体９０〜１００重量％と、水溶性重合開始剤０．２５〜３重量％を用いて、水中で重合することにより形成されたものであることを特徴とする請求項１〜７のいずれかに記載の複合凝集樹脂粒子。 The raw material aggregated particles comprise 90 to 100% by weight of a vinyl monomer having a solubility in water of less than 3% by weight and 0.25 to 3% by weight of a water-soluble polymerization initiator based on the total monomer weight. The composite agglomerated resin particles according to claim 1, wherein the composite agglomerated resin particles are formed by polymerization in water. 微小樹脂粒子が凝集してなる原料凝集粒子を含有する水分散液中において、油溶性重合開始剤を用いてビニル系単量体を重合させることによって、前記原料凝集粒子に油溶性ビニル系重合体を複合させたものであることを特徴とする請求項１〜８のいずれかに記載の複合凝集樹脂粒子。 In an aqueous dispersion containing raw material aggregated particles formed by agglomerating fine resin particles, an oil-soluble vinyl polymer is added to the raw material aggregated particles by polymerizing a vinyl monomer using an oil-soluble polymerization initiator. The composite agglomerated resin particles according to claim 1, wherein the composite agglomerated resin particles are combined. 請求項１〜９のいずれかに記載の複合凝集樹脂粒子を含有する塗料組成物。 The coating composition containing the composite aggregation resin particle in any one of Claims 1-9. 請求項１〜９のいずれかに記載の複合凝集樹脂粒子を含有するインキ組成物。 An ink composition containing the composite agglomerated resin particles according to claim 1. 請求項１〜９のいずれかに記載の複合凝集樹脂粒子を含有する樹脂成型品。
The resin molded product containing the composite aggregation resin particle in any one of Claims 1-9.
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