WO2014119595A1 - Aggregated composite resin particles, and composition containing said particles - Google Patents
Aggregated composite resin particles, and composition containing said particles Download PDFInfo
- Publication number
- WO2014119595A1 WO2014119595A1 PCT/JP2014/051902 JP2014051902W WO2014119595A1 WO 2014119595 A1 WO2014119595 A1 WO 2014119595A1 JP 2014051902 W JP2014051902 W JP 2014051902W WO 2014119595 A1 WO2014119595 A1 WO 2014119595A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- particles
- resin particles
- raw material
- composite
- agglomerated
- Prior art date
Links
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/02—Diffusing elements; Afocal elements
- G02B5/0205—Diffusing elements; Afocal elements characterised by the diffusing properties
- G02B5/0236—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element
- G02B5/0242—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place within the volume of the element by means of dispersed particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Crystallography & Structural Chemistry (AREA)
Abstract
[Problem] The purpose of the present invention is to provide aggregated composite resin particles which can be used widely in various use applications including light-scattering films, inks, paints and resin molded articles, contains less impurities, has an excellent handling property, and also has excellent light scattering performance.
[Solution] The present invention provides aggregated composite resin particles, in each of which a vinyl polymer is complexed in a raw material aggregated particle that is an aggregate of fine resin particles, wherein some of the fine resin particles which exist in at least a surface layer part of the raw material aggregated particle are integrated together by the vinyl polymer.
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、光拡散性能に優れる複合凝集樹脂粒子とその製造方法、ならびに該粒子を含有する各種組成物に関する。
The present invention relates to composite agglomerated resin particles. Specifically, the present invention relates to composite agglomerated resin particles excellent in light diffusion performance, a method for producing the same, and various compositions containing the particles.
従来から、有機微粒子あるいは無機微粒子を含有させることによって光拡散性を付与した光拡散フィルムが知られている。それらのうち、光拡散剤として微粉ケイ酸等の無機微粒子を使用したものは、透明性が悪いために下地の色合いが白くかすむ現象（白ぼけ現象）が発生したり、フィルムの耐摩擦性、破壊強度に劣るという問題があった。
Conventionally, a light diffusion film imparted with light diffusibility by containing organic fine particles or inorganic fine particles is known. Among them, those using inorganic fine particles such as fine silicate as a light diffusing agent may cause a phenomenon in which the color of the ground becomes faint (white blurring phenomenon) due to poor transparency, the friction resistance of the film, There was a problem that it was inferior in breaking strength.
一方、光拡散剤として有機微粒子を使用した場合には、無機微粒子に比べて光拡散性能に劣るものの、透明性が良く、光線透過率の高いフィルムが得られる。そこで、有機微粒子の低い光拡散性能を補う目的で、例えば、有機微粒子内部に異なる組成の有機微粒子が微細に相分離した構造（ミクロ相分離構造）を有する光拡散性能に優れた光拡散剤用粒子が提案されている（特許文献１参照）。
On the other hand, when organic fine particles are used as the light diffusing agent, although the light diffusing performance is inferior to that of inorganic fine particles, a film having good transparency and high light transmittance can be obtained. Therefore, for the purpose of supplementing the low light diffusion performance of organic fine particles, for example, for light diffusing agents with excellent light diffusion performance having a structure (micro phase separation structure) in which organic fine particles of different composition are finely phase-separated inside organic fine particles Particles have been proposed (see Patent Document 1).
しかしながら、かかる光拡散剤用粒子においては、その内部に含まれる１００ｎｍ未満の粒子が光の透過を阻害し、バックライト等から照射される光の透過率を下げる恐れがある。また、かかる粒子中には、製造過程において使用された界面活性剤等の添加剤が残留しているため、フィルム成型時や長期使用時において物性低下、着色などの問題が起こる恐れがある。
However, in such a light diffusing agent particle, particles less than 100 nm contained in the particle may impede the transmission of light and reduce the transmittance of light irradiated from a backlight or the like. Further, in such particles, additives such as surfactants used in the production process remain, and thus there may be problems such as deterioration of physical properties and coloring during film molding or long-term use.
本発明は、かかる従来技術の現状に基づきなされたものであり、光拡散フィルム、インキ、塗料、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、光拡散性能に優れる複合凝集樹脂粒子を提供することを目的とする。
The present invention has been made based on the current state of the prior art, and can be widely used in various applications including light diffusion films, inks, paints, resin molded products, has few impurities, and has excellent handling properties. An object of the present invention is to provide composite agglomerated resin particles having excellent light diffusion performance.
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ビニル系重合体を複合して微小樹脂粒子を一体化することにより、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 studying the above object, the present inventors have achieved the above object by combining the vinyl polymer with the raw material aggregated particles formed by agglomerating the fine resin particles and integrating the fine resin particles. The present invention was 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ビニル系重合体が複合された凝集樹脂粒子であって、前記原料凝集粒子の少なくとも表層部に存在する前記微小樹脂粒子は前記ビニル系重合体によって一体化された状態となっていることを特徴とす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］ 原料凝集粒子を構成する微小樹脂粒子の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］ 乳化剤を含有しないことを特徴とする［１］～［３］のいずれかに記載の複合凝集樹脂粒子。
［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］ ビニル系重合体の含有量が原料凝集粒子の０．１～２００重量％であることを特徴とする［１］～［５］のいずれかに記載の複合凝集樹脂粒子。 [1] Aggregated resin particles in which a vinyl polymer is combined with raw material agglomerated particles obtained by agglomerating fine resin particles, and the fine resin particles present at least on the surface layer of the raw material agglomerated particles A composite agglomerated resin particle characterized by being integrated by coalescence.
[2] The composite agglomerated resin particle according to [1], having a bulk density of 0.20 to 0.50 g / cm 3 .
[3] The composite agglomerated resin particles according to [1] or [2], wherein the average particle diameter measured by SEM images of the fine resin particles constituting the raw material agglomerated particles is 100 to 600 nm.
[4] The composite agglomerated resin particle according to any one of [1] to [3], which does not contain an emulsifier.
[5] The composite agglomerated resin particle according to any one of [1] to [4], which does not contain an aggregating agent.
[6] The composite agglomerated resin particles according to any one of [1] to [5], wherein the content of the vinyl polymer is 0.1 to 200% by weight of the raw material agglomerated particles.
［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］ 原料凝集粒子を構成する微小樹脂粒子の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］ 乳化剤を含有しないことを特徴とする［１］～［３］のいずれかに記載の複合凝集樹脂粒子。
［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］ ビニル系重合体の含有量が原料凝集粒子の０．１～２００重量％であることを特徴とする［１］～［５］のいずれかに記載の複合凝集樹脂粒子。 [1] Aggregated resin particles in which a vinyl polymer is combined with raw material agglomerated particles obtained by agglomerating fine resin particles, and the fine resin particles present at least on the surface layer of the raw material agglomerated particles A composite agglomerated resin particle characterized by being integrated by coalescence.
[2] The composite agglomerated resin particle according to [1], having a bulk density of 0.20 to 0.50 g / cm 3 .
[3] The composite agglomerated resin particles according to [1] or [2], wherein the average particle diameter measured by SEM images of the fine resin particles constituting the raw material agglomerated particles is 100 to 600 nm.
[4] The composite agglomerated resin particle according to any one of [1] to [3], which does not contain an emulsifier.
[5] The composite agglomerated resin particle according to any one of [1] to [4], which does not contain an aggregating agent.
[6] The composite agglomerated resin particles according to any one of [1] to [5], wherein the content of the vinyl polymer is 0.1 to 200% by weight of the raw material agglomerated particles.
［７］ 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］～［６］のいずれかに記載の複合凝集樹脂粒子。
［８］ 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、水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］～［７］のいずれかに記載の複合凝集樹脂粒子。 [7] 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 0.25 to 3 of a water-soluble polymerization initiator. The composite agglomerated resin particle according to any one of [1] to [6], wherein the composite agglomerated resin particle is formed by polymerization in water using a weight percent.
[8] By polymerizing a vinyl monomer using a water-soluble polymerization initiator in an aqueous dispersion containing raw material aggregated particles obtained by agglomerating fine resin particles, The composite agglomerated resin particles according to any one of [1] to [7], wherein the composite agglomerated composites.
［８］ 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、水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］～［７］のいずれかに記載の複合凝集樹脂粒子。 [7] 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 0.25 to 3 of a water-soluble polymerization initiator. The composite agglomerated resin particle according to any one of [1] to [6], wherein the composite agglomerated resin particle is formed by polymerization in water using a weight percent.
[8] By polymerizing a vinyl monomer using a water-soluble polymerization initiator in an aqueous dispersion containing raw material aggregated particles obtained by agglomerating fine resin particles, The composite agglomerated resin particles according to any one of [1] to [7], wherein the composite agglomerated composites.
［９］ ［１］～［８］のいずれかに記載の複合凝集樹脂粒子を含有することを特徴とする塗料組成物。
［１０］ ［１］～［８］のいずれかに記載の複合凝集樹脂粒子を含有することを特徴とするインキ組成物。
［１１］ ［１］～［８］のいずれかに記載の複合凝集樹脂粒子を含有することを特徴とする樹脂成型品。 [9] A coating composition comprising the composite agglomerated resin particles according to any one of [1] to [8].
[10] An ink composition comprising the composite agglomerated resin particles according to any one of [1] to [8].
[11] A resin molded product comprising the composite agglomerated resin particles according to any one of [1] to [8].
［１０］ ［１］～［８］のいずれかに記載の複合凝集樹脂粒子を含有することを特徴とするインキ組成物。
［１１］ ［１］～［８］のいずれかに記載の複合凝集樹脂粒子を含有することを特徴とする樹脂成型品。 [9] A coating composition comprising the composite agglomerated resin particles according to any one of [1] to [8].
[10] An ink composition comprising the composite agglomerated resin particles according to any one of [1] to [8].
[11] A resin molded product comprising the composite agglomerated resin particles according to any one of [1] to [8].
本発明の複合凝集樹脂粒子は、疎な凝集構造を有しており、粒子内部には空隙が存在するため、粒子密度が低く、粒子の単位重量あたりの界面の面積が大きい。そのため、より高い光拡散効果が得られる。また、粒子形状が不定形状であるため、従来の樹脂粒子では得られなかった光拡散性能を持つことが期待される。また、ビニル系重合体で凝集した微小樹脂粒子が一体化されていることにより、水系溶剤や有機系溶剤中においても凝集状態を維持できるため、例えば、塗料などに添加混合して用いた場合であっても、所期のつや消し効果を発現させる塗膜を得ることができ、取り扱いについても微粉が発生しにくく、ハンドリング性が良好である。
The composite agglomerated resin particles of the present invention have a sparse agglomerated structure, and voids exist inside the particles, so that the particle density is low and the interface area per unit weight of the particles is large. Therefore, a higher light diffusion effect can be obtained. Further, since the particle shape is indefinite, it is expected to have light diffusion performance that cannot be obtained with conventional resin particles. In addition, since the fine resin particles aggregated with the vinyl polymer are integrated, the aggregated state can be maintained even in an aqueous solvent or an organic solvent. Even if it exists, the coating film which expresses the desired frosting effect can be obtained, it is hard to generate | occur | produce a fine powder also about handling, and handling property is favorable.
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ビニル系重合体が複合された凝集樹脂粒子であって、前記原料凝集粒子の少なくとも表層部に存在する前記微小樹脂粒子は前記ビニル系重合体によって一体化された状態となっていることを特徴とする。ここで、「一体化された状態」とは、微小樹脂粒子が単に凝集しているのではなく、ビニル系重合体によって微小樹脂粒子同士が接着された状態であって、水系溶媒中、有機系溶媒中のいずれにおいても、凝集状態を維持でき、一次粒子化しない状態を指す。
Hereinafter, the present invention will be described in detail. The composite agglomerated resin particle of the present invention is an agglomerated resin particle in which a vinyl polymer is compounded with raw material agglomerated particles obtained by agglomerating fine resin particles, and the fine resin present in at least a surface layer portion of the raw material agglomerated particles The particles are characterized by being integrated with the vinyl polymer. Here, the “integrated state” is a state in which the fine resin particles are not simply agglomerated but adhered to each other by the vinyl polymer, and the organic resin is in an aqueous solvent. In any of the solvents, the aggregated state can be maintained and the primary particles are not formed.
このような「一体化された状態」にある場合、複合凝集樹脂粒子を形成している微小樹脂粒子の外観は、図２に示すように、一つ一つの微小樹脂粒子の輪郭が明確でなく、互いに連結されたような状態になっている場合が多い。
In such an “integrated state”, the appearance of the fine resin particles forming the composite agglomerated resin particles is not clear as shown in FIG. In many cases, they are connected to each other.
また、本発明の複合凝集樹脂粒子において、「複合された状態」とは、原料凝集粒子をビニル系重合体の溶液に浸漬することで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。
Further, in the composite agglomerated resin particles of the present invention, the “combined state” means a state in which the vinyl polymer is adhered to the raw material agglomerated particles by immersing the raw material agglomerated particles in a solution of the vinyl polymer, Examples include a state obtained by polymerizing a vinyl monomer that is a raw material for a vinyl polymer in an aqueous dispersion of raw material aggregated particles.
また、本発明の複合凝集樹脂粒子の形状は、不定形であることが望ましい。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。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。
Also, the shape of the composite agglomerated resin particles of the present invention is preferably indefinite. Here, the shape of the composite aggregated resin particles is not the detailed shape of the composite aggregated resin particles, but 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 agglomerated resin particles of the present invention, the circularity of the 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.
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 agglomerated resin particles of the present invention, the circularity of the 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においては、上述のように微小樹脂粒子がビニル系重合体によって一体化された状態となっていることにより、取り扱いが容易で、乾燥状態においても複合凝集樹脂粒子がほぐれず、微小粒子が飛散しない。また、水系溶剤中においても、有機系溶剤中においても、微小粒子単位にまで再分散することがないため、水系塗料や溶剤系塗料などに添加して被膜とした場合、凝集状態を維持している複合凝集樹脂粒子の表面上に、様々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が不定形を有している場合、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。さらに、通常の球状粒子と比較して嵩密度も低いため、単位重量あたりの粒子数が多くなり、より多くの凹凸をフィルム表面に形成することも可能である。すなわち、通常の球状粒子によるフィルムの光拡散効果と比較して、例えば添加量を半分にしても同様の光拡散効果を得ることも可能になる。
In the composite agglomerated resin particles of the present invention, since the fine resin particles are integrated with the vinyl polymer as described above, the composite agglomerated resin particles are easily handled even in a dry state. And fine particles do not scatter. In addition, in water-based solvents and organic solvents, it does not re-disperse to fine particle units, so when added to water-based paints or solvent-based paints to form a film, the agglomerated state is maintained. On the surface of the composite agglomerated resin particles, surfaces having various angles are present without being unevenly distributed, and an effect of scattering incident light from any direction without any spots can be obtained. In addition, when 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. Furthermore, since the bulk density is lower than that of ordinary spherical particles, the number of particles per unit weight is increased, and more irregularities can be formed on the film surface. That is, compared with the light diffusing effect of a film with normal spherical particles, for example, the same light diffusing effect can be obtained even if the addition amount is halved.
さらに、複合されたビニル系重合体が親水性である場合には、水系溶剤中における分散安定性に優れたものとなり、水系塗料や水系樹脂などへの添加に適している。
Furthermore, when the composite vinyl polymer is hydrophilic, it has excellent dispersion stability in an aqueous solvent and is suitable for addition to an aqueous paint or aqueous resin.
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る。嵩密度が高すぎると、例えば塗膜状にしたときに表面に形成できる凹凸数が下がり、十分な光拡散性能が得られなくなる場合がある。
In the composite aggregated resin particles according the present invention, it is preferable that a bulk density of 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. If the bulk density is too high, the number of irregularities that can be formed on the surface, for example, when it is formed into a coating film decreases, and sufficient light diffusion performance may not be obtained.
また、本発明の複合凝集樹脂粒子の体積平均粒子径は、３～１５０μｍであることが好ましく、より好ましくは３～５０μｍ、さらに好ましくは３～３０μｍである。平均粒子径が３μｍ未満であると、塗膜状に加工した際に光の散乱により、全光線透過率が下がる場合があり、ＬＥＤ用の光拡散板などの光透過が必要な用途において望ましくない。一方、平均粒子径が１５０μｍ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に、十分なヘイズが得られなくなる場合がある。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。
The volume average particle diameter of the composite agglomerated resin particles of the present invention is preferably 3 to 150 μm, more preferably 3 to 50 μm, still more preferably 3 to 30 μm. If the average particle size is less than 3 μm, the total light transmittance may be reduced due to light scattering when processed into a coating film, which is not desirable in applications that require light transmission such as light diffusion plates for LEDs. . On the other hand, if the average particle diameter exceeds 150 μm, the number of particles is reduced even if the weight added to the coating film is the same, so that sufficient haze may not be obtained. Moreover, it becomes easy to generate | occur | produce a spot at the time of coating, and besides giving a rough surface to a coating-film surface, the possibility of causing the fall of a coating-film physical property 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、凝集剤を多く含有する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。
Further, it is desirable that the composite agglomerated resin particles of the present invention do not contain a flocculant. Here, the aggregating agent is an additive added to agglomerate primary particles, and examples thereof include a polymer aggregating agent and inorganic salts. The agglomerated 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.
また、本発明の複合凝集樹脂粒子は、乳化剤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す。乳化剤は一般的に、重合工程等で添加される。乳化剤を多く含有する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。
Further, it is desirable that the composite aggregated resin particles of the present invention do not contain an emulsifier. Here, the emulsifier refers to a surfactant. The emulsifier is generally added in a polymerization process or the like. If aggregated particles containing a large amount of emulsifier are added to the paint, the properties of the paint or coating film may be deteriorated.
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は、１００～６００ｎｍであることが好ましく、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、微小樹脂粒子同士の隙間がなくなるため、嵩密度が上昇する場合がある。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、かかる範囲の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 diameter is too small, the cohesive force becomes strong and there are no gaps between the fine resin particles, which may increase the bulk density. 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 the average particle diameter of this range also from a viewpoint of the effect of light scattering.
また、微小樹脂粒子の樹脂の種類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できる。従って、樹脂の種類は、目的に応じて任意に選択すればよい。なお、ここで言う内部ヘイズ値とは、凹凸などの表面構造ではなく、内部構造に由来するヘイズ値であり、上記のような塗膜であれば、塗料樹脂と微小樹脂粒子との屈折率差に主に由来している。
Further, the type of resin of the fine resin particles is not particularly limited. For example, the resin can be obtained by selecting a resin having a refractive index difference as small as possible from the coating resin to which the composite agglomerated resin particles are added. The internal haze value of the resulting coating film is lowered and the transparency is improved. Conversely, by selecting a resin having a large refractive index difference as the resin of the fine resin particles, the internal haze value of the obtained coating film increases, and various optical characteristics such as anti-glare and ultraviolet scattering can be obtained. Accordingly, the type of resin may be arbitrarily selected according to the purpose. The internal haze value referred to here is not the surface structure such as irregularities but the haze value derived from the internal structure. If the coating film is as described above, the refractive index difference between the coating resin and the fine resin particles Is mainly derived from.
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 such vinyl resins are employed include acrylic acid esters such as methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, dimethylaminoethyl acrylate, and diethylaminoethyl acrylate. Monomers, methacrylate monomers such as methyl methacrylate, ethyl methacrylate, lauryl methacrylate and dimethylaminoethyl methacrylate, styrene monomers such as styrene and p-methylstyrene, methyl vinyl ether, ethyl vinyl ether Alkyl vinyl ethers such as vinyl acetate, vinyl acetate monomers such as vinyl butyrate, N-alkyl substituted (meth) acrylamides such as N-methylacrylamide and N-ethylacrylamide, 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を採用することがより好ましい。なぜなら、かかる製造方法により得られる原料凝集粒子は、乳化剤および凝集剤のいずれも含有していないからである。
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, it is more preferable to employ raw material aggregated 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 or ethylene glycol dimethacrylate. This is because the raw material agglomerated particles obtained by such a production method contain neither an emulsifier nor a flocculant.
また、本発明における微小樹脂粒子の粒子径は、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。
In addition, the particle diameter 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 be adjusted by the polymerization conditions when the raw material agglomerated particles are produced, or the amount of the agglomerating agent if used.
本発明に採用するビニル系重合体は、上述したように、乾燥状態あるいは水系や有機系の溶媒中においても本発明の複合凝集樹脂粒子の凝集状態を維持させるためのものである。かかるビニル系重合体は、水系や有機系の溶媒に溶解しないものが好ましく、さらに溶媒に対する分散安定性を考慮する場合には、使用する溶媒に対して相性のよいものであることが望ましい。従って、ビニル系重合体の選択にあたっては、例えば、分散に使用する溶媒の溶解性パラメータなどを参考とすることができるが、一般的には、水系や有機系の溶媒に溶解しないという点については、ビニル系重合体として架橋構造を有するものを選択することなどが考えられる。また、水系溶媒中において優れた分散安定性を得るためには、ビニル系重合体として親水性のものを選択することなどが考えられる。
As described above, the vinyl polymer employed in the present invention is for maintaining the aggregated state of the composite aggregated resin particles of the present invention even in a dry state or in an aqueous or organic solvent. Such vinyl polymers are preferably those that do not dissolve in an aqueous or organic solvent, and are more compatible with the solvent used in consideration of dispersion stability in the solvent. Therefore, in selecting a vinyl polymer, for example, the solubility parameter of the solvent used for dispersion can be referred to, but generally, it is not soluble in an aqueous or organic solvent. It may be possible to select a vinyl polymer having a crosslinked structure. In order to obtain excellent dispersion stability in an aqueous solvent, it may be possible to select a hydrophilic polymer as the vinyl polymer.
また、後述するように、本発明に採用するビニル系重合体は、原料凝集粒子を含有する水分散液中において、水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、艶消し性能などの光学特性が低下する場合がある。ただし、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できる。
As will be described later, the vinyl polymer employed in the present invention is obtained by polymerizing a vinyl monomer using a water-soluble polymerization initiator in an aqueous dispersion containing raw material aggregated particles. It can be combined with aggregated particles. In this case, it is natural to select a vinyl monomer to be used so that a vinyl polymer to be combined is obtained, but also consider the affinity between the vinyl monomer and the fine resin particles. Should. That is, when the fine resin particles dissolve or vigorously swell when the vinyl monomer is added, optical properties such as matting performance may be deteriorated. However, the range of selection of the vinyl monomer can be expanded by introducing a crosslinked structure into the fine resin particles in advance to suppress dissolution and swelling.
以上に述べた本発明に採用する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。具体的には、ポリ（メタ）アクリル酸エステル、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、ポリエチレングリコールジ（メタ）アクリレートなどの架橋性モノマーを単独重合または共重合した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 vinyl polymer used in the present invention described above include homopolymers and copolymers such as vinyl monomers that can be used in the resin of the fine resin particles described above. Specifically, poly (meth) acrylic acid ester, polyvinyl acetate, a copolymer of plural types of (meth) acrylic acid ester, and a crosslinkable monomer such as polyethylene glycol di (meth) acrylate were homopolymerized or copolymerized. A polymer etc. are illustrated. The expression “(meth) acrylic acid” indicates both “methacrylic acid” and “acrylic acid”.
また、ビニル系重合体を原料凝集粒子に複合する量の上限は、原料凝集粒子の２００重量％以下であることが好ましく、１００重量％以下であることがより好ましく、５０重量％以下であることがさらに好ましい。ビニル系重合体が２００重量％を超えると、原料凝集粒子の内奥部においても微小樹脂粒子同士の間隙がビニル系重合体で満たされ、嵩密度が大きくなる場合がある。
Further, the upper limit of the amount of the vinyl polymer combined with the raw material aggregated particles is preferably 200% by weight or less, more preferably 100% by weight or less, and more preferably 50% by weight or less of the raw material aggregated particles. Is more preferable. If the vinyl polymer exceeds 200% by weight, the gap between the fine resin particles may be filled with the vinyl polymer even in the innermost part of the raw material aggregated particles, and the bulk density may increase.
一方、ビニル系重合体を原料凝集粒子に複合する量の下限は、原料凝集粒子の０．１重量％以上であることが好ましく、より好ましくは１．０重量％以上、さらに好ましくは５．０重量％以上である。ビニル系重合体が０．１重量％未満であると、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 vinyl polymer combined with the raw material aggregated particles is preferably 0.1% by weight or more of the raw material aggregated particles, more preferably 1.0% by weight or more, and further preferably 5.0%. % By weight or more. When the vinyl polymer is less than 0.1% by weight, the aggregation maintaining effect by the 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凝集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を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 a vinyl polymer with raw material agglomerated particles. From the viewpoint of the characteristics required for the above-described composite aggregated resin particles of the present invention, 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 a method in which droplets of a vinyl monomer are dispersed in water in which a water-soluble polymerization initiator is dissolved and polymerized 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％以上用いることが望ましい。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, lauryl acrylate, methyl methacrylate, ethyl methacrylate, 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. The ratio of the total monomer weight to the total charged weight is preferably 5 to 35% by 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, and redox can be used as long as it is a water-soluble polymerization initiator. Good. 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。
Such a water-soluble polymerization initiator is desirably 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、得られた原料凝集粒子に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, the obtained raw material aggregated particles can be pulverized as necessary to adjust to a desired particle diameter. In the pulverization process, a special apparatus is not required, 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、上述した製造方法においては、必要に応じて、原料凝集粒子を重合する段階あるいは重合後にポリビニルアルコールを添加してもよい。これにより、得られる原料凝集粒子の水分散液の分散安定性を向上させることができる。ポリビニルアルコールの添加量としては、原料凝集粒子１００重量部に対して、好ましくは０．００１～１重量部、より好ましくは０．０１～０．１重量部であることが望ましい。
Further, in the above-described production method, polyvinyl alcohol may be added as needed, at the stage of polymerizing the raw material aggregated particles or after polymerization. Thereby, the dispersion stability of the aqueous dispersion of the raw material aggregated particles obtained can be improved. The amount of polyvinyl alcohol added is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.1 part by weight, with respect to 100 parts by weight of the raw material aggregated particles.
以上のように、上記に詳述した製造方法は、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、この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。
As described above, since the production method described in detail above can obtain raw material aggregated particles in an appropriate aggregated state without using an emulsifier or an aggregating agent, the composite aggregated resin particles of the present invention can be obtained. It is a suitable method. However, in this production method, an emulsifier and a flocculant can be used as necessary.
また、かかる原料凝集粒子に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、水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。
In addition, as a method of combining the vinyl polymer with the raw material aggregated particles, for example, a method of polymerizing a vinyl monomer using a water-soluble polymerization initiator in an aqueous dispersion containing the raw material aggregated particles. Can be mentioned.
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、ビニル系単量体と水溶性重合開始剤を水分散液中に添加する方法としては、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は、上述した、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２００重量％以下、より好ましくは１００重量％以下、さらに好ましくは５０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０．１重量％以上、より好ましくは１．０重量％以上、さらに好ましくは５．０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 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 the vinyl monomer and the water-soluble polymerization initiator to the aqueous dispersion, the whole amount may be added at once, or may be dropped little by little while the polymerization proceeds. Further, the addition amount of the vinyl monomer is preferably 200% by weight or less, more preferably 100% by weight of the raw material aggregated particles as the upper limit from the viewpoint of the amount of the vinyl polymer combined with the raw material aggregated particles. % By weight or less, more preferably 50% by weight or less. The lower limit is preferably 0.1% by weight or more of the raw material aggregated particles, more preferably 1.0% by weight or more, and further preferably 5.0% by weight or more.
なお、かかる方法によって、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。架橋構造を有さない場合、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恐れがある。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 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 it does not have a cross-linked structure, there is a possibility that the fine resin particles are dissolved by the added vinyl monomer and the composite aggregated resin particles of the present invention cannot 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。
The application of the composite aggregated resin particles of the present invention will be described below, but such use is an example, and the composite aggregated resin particles of the present invention can be used for a wide variety of other applications.
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。これらのものに含有させるにあたっては、撹拌や混練などが行われる場合が多いが、そのような場合においても、本発明の複合凝集樹脂粒子は、ほとんどほぐれることなく凝集状態を維持できるため、上述したような光学特性を発現させることが可能である。
The composite agglomerated resin particles of the present invention can be used by being contained in resin molded products in addition to paints and ink compositions. When these are included, stirring and kneading are often performed, but even in such a case, the composite agglomerated resin particles of the present invention can maintain an agglomerated state with almost no loosening, and thus are described above. Such optical characteristics can be expressed.
本発明の塗料組成物あるいは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。
Examples of the method for producing the coating composition or ink composition of the present invention 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、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る。これらは、単独で用いられても二種以上が併用されてもよい。また、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. 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, etc. are mentioned. These may be used alone or in combination of two or more. Various known additives such as a leveling agent, a surface modifier, a defoaming agent, and a colorant such as a pigment 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複合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、混合させることによっても製造することができる。
For example, the above composition is prepared by dissolving the binder resin in an organic solvent and then adding the composite agglomerated resin particles of the present invention, and uniformly dispersing using a sand mill, a ball mill, an attritor, a high-speed rotating stirrer, a 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。
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 solventless, water-based and powder.
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、複合凝集樹脂粒子を含有する樹脂成型品を製造することができる。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の透明性に優れ、耐候性が良く、剛性のある樹脂が好ましく用いられる。
Also, the composite agglomerated resin particles of the present invention can be kneaded into a thermoplastic or thermosetting matrix resin and molded to produce a resin molded product containing the composite agglomerated resin 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、押し出すことにより、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によっても上記成型品を得ることができる。
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. The molded product can also be obtained by taking out as pellets after melt-kneading, and injection-molding the pellets 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、これらの実施例により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
上述した定義による粒子の円形度、体積平均粒子径を、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。 (1) Circularity and volume average particle diameter of sample particles The circularity and volume average particle diameter of the particles defined above were measured by a flow type particle image analyzer (FPIA-3000S: manufactured by Sysmex Corporation).
上述した定義による粒子の円形度、体積平均粒子径を、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。 (1) Circularity and volume average particle diameter of sample particles The circularity and volume average particle diameter of the particles defined above were measured by a flow type particle image analyzer (FPIA-3000S: manufactured by Sysmex Corporation).
（２）微小樹脂粒子の平均粒子径
原料凝集粒子の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 raw material aggregated particles, 20 fine resin particles were arbitrarily selected, each diameter was measured, and an average value was calculated.
原料凝集粒子の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 raw material aggregated particles, 20 fine resin particles were arbitrarily selected, each diameter was measured, and an average value was calculated.
（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、以下の式に従っ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, the weight B (g) was measured, and the bulk density was calculated according to the following formula.
Bulk density (g / cm 3 ) = B (g) / A (cm 3 )
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、以下の式に従っ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, the weight B (g) was measured, and the bulk density was calculated according to the following formula.
Bulk density (g / cm 3 ) = B (g) / A (cm 3 )
（４）ヘイズ値
試料粒子１２重量部とメチルエチルケトン２００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５１重量％）：ＤＩＣ株式会社製）１００重量部に添加し、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）上にバーコーターで塗工し、その後６０℃の熱風乾燥機中で３０分乾燥した。得られた塗膜のヘイズ値をヘイズメーター（ＮＤＨ ２０００：日本電色（株）製）によって測定した。 (4) Haze value 12 parts by weight of sample particles and 200 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: 51% by weight): manufactured by DIC Corporation). Stir for minutes. 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, and then dried in a hot air dryer at 60 ° C. for 30 minutes. The haze value of the obtained coating film was measured with a haze meter (NDH 2000: manufactured by Nippon Denshoku Co., Ltd.).
試料粒子１２重量部とメチルエチルケトン２００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５１重量％）：ＤＩＣ株式会社製）１００重量部に添加し、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）上にバーコーターで塗工し、その後６０℃の熱風乾燥機中で３０分乾燥した。得られた塗膜のヘイズ値をヘイズメーター（ＮＤＨ ２０００：日本電色（株）製）によって測定した。 (4) Haze value 12 parts by weight of sample particles and 200 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: 51% by weight): manufactured by DIC Corporation). Stir for minutes. 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, and then dried in a hot air dryer at 60 ° C. for 30 minutes. The haze value of the obtained coating film was measured with a haze meter (NDH 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重量部を溶解させた。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た。続いて、該水分散液に、該水分散液の固形分を１００重量部としてポリエチレングリコール＃４００ジメタクリレート（ＮＫ－エステル９Ｇ、新中村化学（株）製）３０重量部と２，２’－Ａｚｏｂｉｓ（１－ｉｍｉｎｏ－１－ｐｙｒｒｏｌｉｄｉｎｏ－２－ｍｅｔｈｙｌｐｒｏｐａｎｅ）ｄｉｈｙｄｒｏｃｈｌｏｒｉｄｅ０．３重量部を添加し、再度４５℃で２時間反応させた。次いで、濾別、水洗、乾燥した後、粗大粒子を除去するために分級して、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、上記の原料凝集粒子ＳＥＭ画像を図１に、複合凝集樹脂粒子のＳＥＭ画像を図２に示す。 [Example 1]
300 parts by weight of water was charged in the reaction vessel, and 0.6 parts by weight of 2,2′-Azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride was dissolved as a polymerization initiator. Next, 99 parts by weight of methyl methacrylate and 1 part by weight of ethylene glycol methacrylate were added as monomers and reacted at 45 ° C. for 2 hours with stirring to obtain an aqueous dispersion of raw material aggregated particles. Subsequently, 30 parts by weight of polyethylene glycol # 400 dimethacrylate (NK-ester 9G, manufactured by Shin-Nakamura Chemical Co., Ltd.) and 2,2′-, based on 100 parts by weight of the solid content of the aqueous dispersion, were added to the aqueous dispersion. Azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride 0.3 parts by weight was added and reacted again at 45 ° C. for 2 hours. Next, after filtering, washing with water, and drying, classification was performed to remove coarse particles, and composite agglomerated resin particles of Example 1 were obtained. The results of measuring the characteristics of the particles are shown in Table 1. Further, FIG. 1 shows the raw material aggregated particle SEM image, and FIG. 2 shows an SEM image of the composite aggregated resin particle.
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重量部を溶解させた。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た。続いて、該水分散液に、該水分散液の固形分を１００重量部としてポリエチレングリコール＃４００ジメタクリレート（ＮＫ－エステル９Ｇ、新中村化学（株）製）３０重量部と２，２’－Ａｚｏｂｉｓ（１－ｉｍｉｎｏ－１－ｐｙｒｒｏｌｉｄｉｎｏ－２－ｍｅｔｈｙｌｐｒｏｐａｎｅ）ｄｉｈｙｄｒｏｃｈｌｏｒｉｄｅ０．３重量部を添加し、再度４５℃で２時間反応させた。次いで、濾別、水洗、乾燥した後、粗大粒子を除去するために分級して、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、上記の原料凝集粒子ＳＥＭ画像を図１に、複合凝集樹脂粒子のＳＥＭ画像を図２に示す。 [Example 1]
300 parts by weight of water was charged in the reaction vessel, and 0.6 parts by weight of 2,2′-Azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride was dissolved as a polymerization initiator. Next, 99 parts by weight of methyl methacrylate and 1 part by weight of ethylene glycol methacrylate were added as monomers and reacted at 45 ° C. for 2 hours with stirring to obtain an aqueous dispersion of raw material aggregated particles. Subsequently, 30 parts by weight of polyethylene glycol # 400 dimethacrylate (NK-ester 9G, manufactured by Shin-Nakamura Chemical Co., Ltd.) and 2,2′-, based on 100 parts by weight of the solid content of the aqueous dispersion, were added to the aqueous dispersion. Azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride 0.3 parts by weight was added and reacted again at 45 ° C. for 2 hours. Next, after filtering, washing with water, and drying, classification was performed to remove coarse particles, and composite agglomerated resin particles of Example 1 were obtained. The results of measuring the characteristics of the particles are shown in Table 1. Further, FIG. 1 shows the raw material aggregated particle SEM image, and FIG. 2 shows an SEM image of the composite aggregated resin particle.
［実施例２］
実施例１で得た凝集状樹脂粒子をさらに目の細かい篩で分級し、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]
The aggregated resin particles obtained in Example 1 were classified with a finer sieve to obtain composite aggregated resin particles of Example 2. The results of measuring the characteristics of the particles are shown in Table 1.
実施例１で得た凝集状樹脂粒子をさらに目の細かい篩で分級し、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]
The aggregated resin particles obtained in Example 1 were classified with a finer sieve to obtain composite aggregated 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ポリエチレングリコール＃４００ジメタクリレート３０重量部を酢酸ビニル３０重量部に変更したこと以外は実施例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 aggregation of Example 3 was performed in the same manner as in Example 1 except that 30 parts by weight of polyethylene glycol # 400 dimethacrylate added to the aqueous dispersion of raw material aggregated particles was changed to 30 parts by weight of vinyl acetate. Resin particles were obtained. The results of measuring the characteristics of the particles are shown in Table 1.
実施例１において、原料凝集粒子の水分散液に添加するポリエチレングリコール＃４００ジメタクリレート３０重量部を酢酸ビニル３０重量部に変更したこと以外は実施例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 aggregation of Example 3 was performed in the same manner as in Example 1 except that 30 parts by weight of polyethylene glycol # 400 dimethacrylate added to the aqueous dispersion of raw material aggregated particles was changed to 30 parts by weight of vinyl acetate. Resin particles were 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ポリエチレングリコール＃４００ジメタクリレートの配合量を３０重量部から０．１重量部に変更したこと以外は実施例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]
Example 1 is the same as Example 1 except that the blending amount of polyethylene glycol # 400 dimethacrylate added to the aqueous dispersion of raw material aggregated particles is changed from 30 parts by weight to 0.1 parts by weight. 4 composite agglomerated resin particles were obtained. The results of measuring the characteristics of the particles are shown in Table 1.
実施例１において、原料凝集粒子の水分散液に添加するポリエチレングリコール＃４００ジメタクリレートの配合量を３０重量部から０．１重量部に変更したこと以外は実施例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]
Example 1 is the same as Example 1 except that the blending amount of polyethylene glycol # 400 dimethacrylate added to the aqueous dispersion of raw material aggregated particles is changed from 30 parts by weight to 0.1 parts by weight. 4 composite agglomerated 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ポリエチレングリコール＃４００ジメタクリレートの配合量を３０重量部から１０重量部に変更したこと以外は実施例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]
In Example 1, except that the blending amount of polyethylene glycol # 400 dimethacrylate added to the aqueous dispersion of raw material aggregated particles was changed from 30 parts by weight to 10 parts by weight, Composite aggregated resin particles were obtained. The results of measuring the characteristics of the particles are shown in Table 1.
実施例１において、原料凝集粒子の水分散液に添加するポリエチレングリコール＃４００ジメタクリレートの配合量を３０重量部から１０重量部に変更したこと以外は実施例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]
In Example 1, except that the blending amount of polyethylene glycol # 400 dimethacrylate added to the aqueous dispersion of raw material aggregated particles was changed from 30 parts by weight to 10 parts by weight, Composite aggregated resin 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ポリエチレングリコール＃４００ジメタクリレートの配合量を３０重量部から２５０重量部に変更したこと以外は実施例１と同様にして、実施例６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。 [Example 6]
In Example 1, except that the blending amount of polyethylene glycol # 400 dimethacrylate added to the aqueous dispersion of raw material aggregated particles was changed from 30 parts by weight to 250 parts by weight, Particles were obtained. The results of measuring the characteristics of the particles are shown in Table 1.
実施例１において、原料凝集粒子の水分散液に添加するポリエチレングリコール＃４００ジメタクリレートの配合量を３０重量部から２５０重量部に変更したこと以外は実施例１と同様にして、実施例６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。 [Example 6]
In Example 1, except that the blending amount of polyethylene glycol # 400 dimethacrylate added to the aqueous dispersion of raw material aggregated particles was changed from 30 parts by weight to 250 parts by weight, Particles were 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、原料凝集粒子の反応後にポリビニルアルコール０．０４重量部を添加したこと以外は実施例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, composite aggregated resin particles of Example 7 were obtained in the same manner as in Example 1 except that 0.04 parts by weight of polyvinyl alcohol was added after the reaction of the raw material aggregated particles. The results of measuring the characteristics of the particles are shown in Table 1.
実施例１において、原料凝集粒子の反応後にポリビニルアルコール０．０４重量部を添加したこと以外は実施例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, composite aggregated resin particles of Example 7 were obtained in the same manner as in Example 1 except that 0.04 parts by weight of polyvinyl alcohol was added after 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そのまま濾別、水洗、乾燥、分級して、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]
The aqueous dispersion of the raw material aggregated particles of Example 1 was directly filtered, washed with water, dried, and classified to obtain particles of Comparative Example 1. The results of measuring the characteristics of the particles are shown in Table 1.
実施例１の原料凝集粒子の水分散液をそのまま濾別、水洗、乾燥、分級して、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]
The aqueous dispersion of the raw material aggregated particles of Example 1 was directly filtered, washed with water, dried, and classified to obtain particles of Comparative Example 1. The results of measuring the characteristics of the particles are shown in Table 1.
表１に示すように、実施例１～７では、溶剤への分散安定性が高く、かつ、微粉の少ない複合凝集樹脂粒子が得られた。また、これらの粒子を溶剤塗料に添加して塗膜とした場合、比較例１の原料凝集粒子と比較して高いヘイズ値が得られた。すなわち、実施例１～７においては、ビニル系重合体を複合した効果によって、塗料に添加混合した際にも複合凝集樹脂粒子の凝集状態が維持されているため、高いヘイズ値が得られたものと考えられる。一方、比較例１では、ビニル系重合体を複合していないため、分級時や調合時に飛散するなど取り扱い性に劣り、溶剤中で凝集粒子がほぐれて、ヘイズ値が低くなったものと考えられる。なお、実施例６の複合凝集樹脂粒子は、ビニル系重合体の複合量が多いため、嵩密度が高く、他の実施例の複合凝集樹脂粒子と比較してヘイズ値が低くなった。
As shown in Table 1, in Examples 1 to 7, composite agglomerated resin particles having high dispersion stability in a solvent and few fine powders were obtained. Moreover, when these particles were added to the solvent paint to form a coating film, a higher haze value was obtained as compared with the raw material aggregated particles of Comparative Example 1. That is, in Examples 1 to 7, a high haze value was obtained because the agglomerated state of the composite agglomerated resin particles was maintained even when added to the paint due to the effect of compounding the vinyl polymer. it is conceivable that. On the other hand, in Comparative Example 1, since the vinyl polymer is not combined, it is inferior in handling properties such as scattering at the time of classification or preparation, and it is considered that the agglomerated particles are loosened in the solvent and the haze value is lowered. . In addition, since the composite aggregation resin particle of Example 6 had many composite amounts of a vinyl polymer, the bulk density was high and the haze value became low compared with the composite aggregation resin particle of another Example.
Claims (11)
- 微小樹脂粒子が凝集してなる原料凝集粒子にビニル系重合体が複合された凝集樹脂粒子であって、前記原料凝集粒子の少なくとも表層部に存在する前記微小樹脂粒子は前記ビニル系重合体によって一体化された状態となっていることを特徴とする複合凝集樹脂粒子。 Aggregated resin particles in which a vinyl polymer is combined with raw material agglomerated particles obtained by agglomerating fine resin particles, and the fine resin particles present at least on the surface layer of the raw material agglomerated particles are integrated by the vinyl polymer. Composite agglomerated resin particles, characterized in that they are in a converted state.
- 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。 2. The composite agglomerated resin particles according to claim 1, wherein the bulk density is 0.20 to 0.50 g / cm 3 .
- 原料凝集粒子を構成する微小樹脂粒子の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。 3. The composite agglomerated resin particles according to claim 1, wherein the average particle diameter measured by SEM images of the fine resin particles constituting the raw material agglomerated particles is 100 to 600 nm.
- 乳化剤を含有しない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 particle according to any one of claims 1 to 3, which does not contain an emulsifier.
- 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 an aggregating agent.
- ビニル系重合体の含有量が原料凝集粒子の０．１～２００重量％である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。 6. The composite agglomerated resin particles according to claim 1, wherein the content of the vinyl polymer is 0.1 to 200% 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１～６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 water solubility 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 any one of claims 1 to 6, 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、水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１～７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 obtained by agglomerating fine resin particles, a vinyl polymer is combined with the raw material aggregated particles by polymerizing a vinyl monomer using a water-soluble polymerization initiator. The composite agglomerated resin particle according to any one of claims 1 to 7, wherein
- 請求項１～８のいずれかに記載の複合凝集樹脂粒子を含有することを特徴とする塗料組成物。 A coating composition comprising the composite agglomerated resin particles according to any one of claims 1 to 8.
- 請求項１～８のいずれかに記載の複合凝集樹脂粒子を含有することを特徴とするインキ組成物。 An ink composition comprising the composite agglomerated resin particles according to any one of claims 1 to 8.
- 請求項１～８のいずれかに記載の複合凝集樹脂粒子を含有することを特徴とする樹脂成型品。 A resin molded product comprising the composite agglomerated resin particles according to any one of claims 1 to 8.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201480007406.0A CN104968689B (en) | 2013-02-04 | 2014-01-29 | Aggregated composite resin particles, and composition containing said particles |
| KR1020157017554A KR20150115727A (en) | 2013-02-04 | 2014-01-29 | Aggregated composite resin particles, and composition containing said particles |
| JP2014559706A JP6277962B2 (en) | 2013-02-04 | 2014-01-29 | Composite aggregated resin particles and composition containing the particles |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-019516 | 2013-02-04 | ||
| JP2013019516 | 2013-02-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2014119595A1 true WO2014119595A1 (en) | 2014-08-07 |
Family
ID=51262308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2014/051902 WO2014119595A1 (en) | 2013-02-04 | 2014-01-29 | Aggregated composite resin particles, and composition containing said particles |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6277962B2 (en) |
| KR (1) | KR20150115727A (en) |
| CN (1) | CN104968689B (en) |
| TW (1) | TWI582154B (en) |
| WO (1) | WO2014119595A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016070938A (en) * | 2014-09-30 | 2016-05-09 | 敏治 吉川 | Surface reflection material for non-contact type 3d scanner |
| JP2017137478A (en) * | 2016-02-01 | 2017-08-10 | 日本エクスラン工業株式会社 | Composite aggregation resin particle group, and method for producing particle group and composition containing particle group |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61241310A (en) * | 1985-04-18 | 1986-10-27 | Soken Kagaku Kk | Production of emulsion of crosslinked polymer |
| JP2006143968A (en) * | 2004-11-24 | 2006-06-08 | Gunma Univ | Method for producing polymeric particulate of irregular shape |
| JP2006274250A (en) * | 2005-03-01 | 2006-10-12 | Soken Chem & Eng Co Ltd | Colored monodisperse particles and its manufacturing method |
| JP2006335793A (en) * | 2005-05-31 | 2006-12-14 | Mitsubishi Rayon Co Ltd | Method for producing acrylic polymer powder and plastisol composition |
| JP2011074229A (en) * | 2009-09-30 | 2011-04-14 | Japan Exlan Co Ltd | Aggregation resin particle, manufacturing method for this particle, and coating composition and coating film containing the same |
| WO2013115165A1 (en) * | 2012-01-31 | 2013-08-08 | 日本エクスラン工業株式会社 | Composite aggregate resin particle and composition containing same particle |
-
2014
- 2014-01-22 TW TW103102203A patent/TWI582154B/en active
- 2014-01-29 JP JP2014559706A patent/JP6277962B2/en active Active
- 2014-01-29 KR KR1020157017554A patent/KR20150115727A/en not_active Application Discontinuation
- 2014-01-29 CN CN201480007406.0A patent/CN104968689B/en active Active
- 2014-01-29 WO PCT/JP2014/051902 patent/WO2014119595A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61241310A (en) * | 1985-04-18 | 1986-10-27 | Soken Kagaku Kk | Production of emulsion of crosslinked polymer |
| JP2006143968A (en) * | 2004-11-24 | 2006-06-08 | Gunma Univ | Method for producing polymeric particulate of irregular shape |
| JP2006274250A (en) * | 2005-03-01 | 2006-10-12 | Soken Chem & Eng Co Ltd | Colored monodisperse particles and its manufacturing method |
| JP2006335793A (en) * | 2005-05-31 | 2006-12-14 | Mitsubishi Rayon Co Ltd | Method for producing acrylic polymer powder and plastisol composition |
| JP2011074229A (en) * | 2009-09-30 | 2011-04-14 | Japan Exlan Co Ltd | Aggregation resin particle, manufacturing method for this particle, and coating composition and coating film containing the same |
| WO2013115165A1 (en) * | 2012-01-31 | 2013-08-08 | 日本エクスラン工業株式会社 | Composite aggregate resin particle and composition containing same particle |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016070938A (en) * | 2014-09-30 | 2016-05-09 | 敏治 吉川 | Surface reflection material for non-contact type 3d scanner |
| JP2017137478A (en) * | 2016-02-01 | 2017-08-10 | 日本エクスラン工業株式会社 | Composite aggregation resin particle group, and method for producing particle group and composition containing particle group |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI582154B (en) | 2017-05-11 |
| CN104968689B (en) | 2017-05-17 |
| JP6277962B2 (en) | 2018-02-14 |
| KR20150115727A (en) | 2015-10-14 |
| TW201439168A (en) | 2014-10-16 |
| CN104968689A (en) | 2015-10-07 |
| JPWO2014119595A1 (en) | 2017-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2013030977A1 (en) | Resin particle aggregate, method for manufacturing same and application of same | |
| KR20120003434A (en) | Irregularly shaped particles and method for producing same | |
| KR102029829B1 (en) | Composite aggregate resin particle and composition containing same particle | |
| WO2006093179A1 (en) | Porous monodispersed particles and method for production thereof, and use thereof | |
| TWI519608B (en) | Hybrid carbon black, coating composition and shielding material employing the same | |
| JP6134592B2 (en) | Resin particle solvent dispersion and use thereof | |
| JP5442592B2 (en) | Core shell particles | |
| JP6277962B2 (en) | Composite aggregated resin particles and composition containing the particles | |
| JP2010053171A (en) | Method for preparing nano-particle composite | |
| JP5696918B2 (en) | Aggregated resin particles, method for producing the particles, and coating composition and coating film containing the particles | |
| JP6877685B2 (en) | A composite agglomerated resin particle group, a method for producing the particle group, and a composition containing the particle group. | |
| JP5773234B2 (en) | Organic matte | |
| JP5747746B2 (en) | Method for producing nano-particle composite | |
| JP2010053172A (en) | Method for preparing nano-particle composite | |
| JP2009242695A (en) | Method for producing nanoparticle composite material | |
| JP6213458B2 (en) | INORGANIC COMPOSITE RESIN PARTICLE AND METHOD FOR PRODUCING THE SAME | |
| JP6123156B2 (en) | True spherical cross-linked polyacrylonitrile fine particles with large surface area | |
| JP6115588B2 (en) | Organic matte | |
| JP2019065134A (en) | Pore-forming material | |
| CN1436800A (en) | Polyacrylonitrile polymer fine particles | |
| KR20120029193A (en) | Spherical polymer powder having high refractive index and preparation method thereof | |
| JP2011074146A (en) | Method for producing dispersion liquid of nanoparticle composite, and resin composition containing the dispersion liquid of nanoparticle composite | |
| JP2015147827A (en) | Black colored porous resin beads, method for producing same, and product with texture of suppressed glossiness using the resin beads | |
| JP2001029822A (en) | Manufacture of antistatic coating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14746231 Country of ref document: EP Kind code of ref document: A1 |
|
| ENP | Entry into the national phase |
Ref document number: 20157017554 Country of ref document: KR Kind code of ref document: A |
|
| ENP | Entry into the national phase |
Ref document number: 2014559706 Country of ref document: JP Kind code of ref document: A |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 14746231 Country of ref document: EP Kind code of ref document: A1 |