JP4298084B2 - Matting agent - Google Patents
Matting agent Download PDFInfo
- Publication number
- JP4298084B2 JP4298084B2 JP26226799A JP26226799A JP4298084B2 JP 4298084 B2 JP4298084 B2 JP 4298084B2 JP 26226799 A JP26226799 A JP 26226799A JP 26226799 A JP26226799 A JP 26226799A JP 4298084 B2 JP4298084 B2 JP 4298084B2
- Authority
- JP
- Japan
- Prior art keywords
- matting agent
- fine particles
- average particle
- particle diameter
- crosslinked polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Description
【発明の属する技術分野】
本発明は、塗料の艶消し剤、各種の表面処理剤、各種フィラー等に使用されるマット剤に関する。
【従来の技術】
微粒子集合体は、塗料や各種の表面処理剤に広く使用されており、材質も無機物および有機物の両者において広く検討されている。
例えば無機材料の微粒子集合体においては、特開平１０−２３１１１９号公報に記載されている様な多孔性アルミナ、特開平１０−２５９０２３号公報に記載されている様な酸化チタン多孔体、特開平１０−１８２４９１号公報に記載されている様な多孔質炭酸カルシウムなどが知られている。
しかしながら、無機材料は基本的に真比重が有機材料に比べて大きく、マット剤としての性能を単位重量当たりで比較すると、有機材料の方が優れている。また、塗料やフィルムなど基材との親和性も低いという欠点を有している。
一方、有機材料の微粒子集合体においては、真比重が無機材料に比べて小さく塗料やフィルムなどの基材との親和性も高いという利点を有しているものの、空隙率が高く嵩比重の小さい集合体を作ることが困難であった。また、無機材料に比べて耐熱性、耐溶剤性や強度が劣るという問題点もあった。
これらの問題点を解決できる方法として、架橋重合体微粒子を集合体とする方法が考えられるが、これまで有効な方法は見い出だせていなかった。例えば、特開平２−７０７４１号公報に記載されている様に、不飽和カルボン酸を含む重合体を中和膨潤させ種粒子として用い、それと異なる組成の重合体を第２段階として乳化重合することにより集合体を得る方法などが知られている。しかし、この方法では第２段階の重合において新粒子が生成しない条件を選択する必要があり重合組成や重合条件に限りがあると共に、集合体の強度が弱く破壊されやすいという問題がある。
以上の様に従来においては、真比重が軽く基材との親和性も高いという有機材料の特長を生かした有機微粒子集合体からなるマット剤は知られていなかった。
【発明が解決しようとする課題】
本発明は上記の状況に着目してなされたものであり、嵩比重が小さく、耐熱性や耐溶剤性の高い、架橋重合体微粒子の集合体を含んでなるマット剤を提供することを目的とするものである。
【課題を解決するための手段】
本発明は、平均粒子径０．０１〜１μｍの架橋重合体微粒子が集合してなる平均粒子径２〜２００μｍの球状粒子を含んでなるマット剤であることを要旨とするものである。
前記球状粒子は、例えば、平均粒子径０．０１〜１μｍの架橋重合体微粒子を含むエマルジョンを、噴霧乾燥して得られる粒子である。
【発明の実施の形態】
本発明に用いる球状粒子は、その材質、製法は特に限定されず、例えば、ジビニルベンゼンおよび／またはトリメチロールプロパントリ（メタ）アクリレートを含むビニル系単量体混合物を重合して得られる架橋微粒子を、噴霧式乾燥方法によって乾燥させる方法により効率良く得られることを、本発明者らは、先に見いだしている（特願平１０−２２０４１８号）。該方法によれば、耐熱性や強度が高く、原料微粒子の形状を保持した比表面積の大きい微粒子集合体が得られることができる。
また前記球状粒子の原料となる架橋重合体微粒子は、架橋重合体を含んでなる微粒子であれば、その組成および製法は特に限定されないが、例えば架橋性単量体を含むビニル系単量体の混合物を、従来公知の方法で乳化重合することにより製造することが可能である。
前記ビニル系単量体に含まれる架橋性単量体としては、ジビニルベンゼンおよび／またはトリメチロールプロパントリ（メタ）アクリレート等が挙げられる。前記ビニル系単量体の混合物中に含まれてもいても良い架橋性単量体以外の非架橋性単量体としては、１分子内に１個の重合性不飽和結合を有する単量体であれば特に限定されず、例えば、スチレンやαメチルスチレンなどの芳香族ビニル化合物、（メタ）アクリル酸、（メタ）アクリル酸メチルや（メタ）アクリル酸エチルや（メタ）アクリル酸ブチルなどの（メタ）アクリル酸エステル類、酢酸ビニルやプロピオン酸ビニルなどのビニルエステル類、（メタ）アクリロニトリルなどのビニルシアン化合物、塩化ビニルや塩化ビニリデンなどのハロゲン化ビニル化合物、ブタジエンなどの共役ジエン類などが用いられる。
ビニル系単量体混合物中の架橋性単量体の比率が高いほど、得られる微粒子の耐熱性や強度が高くなるので好ましいが、高すぎると粒子間の融着が起こりにくく、集合体とするのが困難である。
そのため、前記架橋性単量体としてジビニルベンゼンを用いる場合には、ビニル系単量体混合物中のジビニルベンゼンの重量比率は、通常２〜１０重量％の範囲であり、好ましくは３〜８重量％である。
また前記架橋性単量体としてトリメチロールプロパントリ（メタ）アクリレートを用いた場合には、ビニル系単量体混合物中のトリメチロールプロパントリ（メタ）アクリレートの重量比率は、通常５〜３０重量％の範囲であり、好ましくは８〜２０重量％の範囲である。
前記架橋重合体の混合物を乳化重合方法により製造する方法は特に限定されるものではなく、一般的には、界面活性剤を用い、固形分濃度が５〜６０重量％の範囲、開始剤として無機過酸化物あるいはレドックス系開始剤を使用し、重合温度２０〜１００℃の範囲で実施することが可能である。
前記乳化重合方法により、平均粒子径０．０１〜１μｍの範囲の架橋重合体微粒子が簡便で効率良く得られる。
得られた架橋重合体微粒子を集合体とする方法は、特に限定されないが、噴霧式乾燥方法によって乾燥して粒子間の融着を起こす方法が、集合体の粒子径や形状の制御が容易であり推奨される。噴霧式乾燥方法とは、一般的にスプレードライヤーや気流乾燥機を用いて、ガス気流と共に水分散体を噴霧して粒子を乾燥させる方法のことを言う。
前記噴霧式乾燥方法における固形分濃度、供給速度、乾燥温度などは適宜に調節することにより、粒子径、粒子形状、かさ比重などを調整することが可能であり、特に上記の条件に限定する必要はないが、例えば前記固形分濃度は、通常５〜６０重量％であり、より好ましくは１０〜５０重量％であり、前記乾燥温度は、噴霧入口温度が１００〜２００℃の範囲、粉体の出口温度が３０〜１００℃の範囲である。
本発明のマット剤の主体である微粒子集合体は、例えば架橋重合体微粒子の形状を保持しながら該架橋重合体微粒子が相互に連結した集合体である。前記微粒子集合体は、粒子が球状で粒度分布もシャープである特長を有している。また前記微粒子集合体は、比表面積が大きくかさ比重が小さいという特長を有している。さらに前記微粒子集合体は、従来の微粒子集合体に比べ、強度が高いという特長を有している。
また、本発明のマット剤の主体である微粒子集合体の平均粒子径は、２〜２００μｍの範囲である。好ましくは、５〜１００μｍの範囲である。この範囲を外れた集合体では、マット剤に用いた場合に効果が低下する傾向にある。
本発明のマット剤は、樹脂、塗料、接着剤、コーティング用樹脂などに配合して使用することができる。また、使用に際して従来公知のマット剤と併用しても何等差し支えはないが、前記微粒子集合体がマット剤中に通常１０重量％以上、好ましくは２０重量％以上の範囲で含有される。
本発明のマット剤を、塗料用添加剤として用いる場合には、通常塗料に０．１〜１０重量％配合することにより、艶消し剤としても使用することができる。本発明のマット剤は、粒子１個当たりの重量が小さいので、従来のマット剤に比べ少量の配合で効果を得ることができる。
本発明のマット剤を、樹脂用添加剤として用いる場合には、通常各種の樹脂に０．１〜５重量％配合することにより、艶消し剤、光拡散剤、アンチブロッキング剤あるいは充填剤として使用することができる。粒子１個当たりの重量が小さいので、少量の添加で大きな効果が得られると共に、比表面積が大きいので、粒子１個当たりの効果も大きい。
本発明のマット剤を、紙用添加剤として用いる場合には、比表面積が大きいので、紙面に付着したインク滴が速やかに吸収されるという特徴があり、印刷した場合に鮮明な画像を得ることができる。通常は高分子バインダーに対して１０〜３００重量部配合し、マット化層の厚さを１〜５０μｍとする。
本発明のマット剤を、ハロゲン化銀写真感光材料用マット剤として用いる場合には、粒子が球状で粒度分布もシャープであるので、ハロゲン化銀写真感光材料用マット剤としても有用である。通常の使用量は感光材料に対して０．０１〜１ｇ／ｍ2である。
【実施例】
以下、実施例により本発明を詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
製造例
撹拌機、温度計および還流冷却器付きの２Ｌセパラブルフラスコに、純水（４３３ｇ）とハイテノールＮ０８（第一工業製薬製アニオン界面活性剤、０．９ｇ）とを仕込み、窒素置換を行いながら、撹拌下に７０℃まで昇温した。７０℃に昇温後、メチルメタクリレート（５７ｇ）を添加し、その５分後に、過硫酸カリウムの２％水溶液（７０ｇ）を添加した。
予め調製しておいたプレエマルション（メチルメタクリレート：６０８ｇ、ジビニルベンゼン：３５ｇ、純水：７５２ｇ、ハイテノールＮ０８：３４ｇ）を、過硫酸カリウム添加の２０分後より７０℃にて等速度で４時間かけて添加した。
添加終了後、７５℃まで昇温し２時間の熟成を行い、その後、４０℃まで冷却して架橋重合体エマルションを得た。このエマルションの平均粒子径を光散乱式粒度分布計で測定した所、０．２μｍであった。
次いで、該エマルションをヤマト科学製のスプレードライヤーで、
供給速度：１４ml/min、
噴霧圧：２．３kg/cm2、
風量：０．３m3/min、
加熱部入口温度：１５０℃、
加熱部出口温度：６０℃
の条件下にて乾燥して粉体を得た。
得られた該粉体をマルチサイザーII型（コールター社製）で測定したところ、平均粒子径は１４μｍであった。また、該粉体は電子顕微鏡（ＳＥＭ）観察によると、架橋重合体微粒子からなる原料微粒子が形状を保持したまま相互に連結してなる微粒子集合体であった。
実施例１
水４５ｇにノニオン系界面活性剤（三洋化成製「ノニポール」、固形分２５重量％）０．５ｇを溶解させ、この水溶液に、製造例で得られた微粒子集合体１５ｇをマット剤として添加しよく撹拌し分散させた。
次いで該分散液にポリウレタン系水分散塗料（第一工業製薬製「スーパーフレックスＥ４７００」、固形分４０重量％）６０ｇを加え均一に撹拌して塗料組成物を得た。
該塗料組成物をスプレー式塗布機にて、ＡＢＳ樹脂製プレートに膜厚が約８０μｍになる様に塗布し、８０℃にて１時間乾燥させた。
乾燥後の塗膜の厚さは約３０μｍであり、塗膜の６０度グロスは８５であった。
比較例１
製造例で得られた微粒子集合体の代わりに、シリカ粉末（トクヤマ製「レオロシールＭＴ−１０」）を用いた以外は、実施例と同様の操作を繰り返して塗膜を得た。
乾燥後の塗膜の厚さは約３０μｍであり、乾燥後の塗膜の６０度グロスは７５であった。
【発明の効果】
本発明のマット剤は、嵩比重が小さく、耐熱性や耐溶剤性の高い特徴を有するので、樹脂、塗料、接着剤、コーティング用樹脂などに用いるマット剤として有用である。
具体的には本発明のマット剤を、塗料用添加剤として用いる場合には、艶消し剤の機能も発現させることができ、従来のマット剤に比べ少量の配合で効果を得ることができる。
また本発明のマット剤を、樹脂用添加剤として用いる場合には、艶消し剤、光拡散剤、アンチブロッキング剤あるいは充填剤としての機能も発現させることができ、少量の添加で大きな効果が得られると共に、比表面積が大きいので、粒子１個当たりの効果が大きい。
また本発明のマット剤を、紙用添加剤として用いる場合には、比表面積が大きいので、紙面に付着したインク滴が速やかに吸収されるという特徴があり、印刷した場合に鮮明な画像を得ることができる。
また本発明のマット剤は、粒子が球状で粒度分布もシャープであるので、ハロゲン化銀写真感光材料用マット剤としても有用である。BACKGROUND OF THE INVENTION
The present invention relates to a matting agent used for matting agents for paints, various surface treatment agents, various fillers and the like.
[Prior art]
Fine particle aggregates are widely used in paints and various surface treatment agents, and their materials are widely studied for both inorganic and organic materials.
For example, in the fine particle aggregate of inorganic material, porous alumina as described in JP-A-10-231119, titanium oxide porous body as described in JP-A-10-259023, Porous calcium carbonate and the like as described in Japanese Patent No. 182491 are known.
However, the inorganic material basically has a larger true specific gravity than the organic material, and the organic material is superior in terms of performance as a matting agent per unit weight. In addition, it has a drawback of low affinity with a substrate such as paint or film.
On the other hand, fine particle aggregates of organic materials have the advantage that the true specific gravity is smaller than that of inorganic materials and the affinity with substrates such as paints and films is high, but the porosity is high and the bulk specific gravity is small. It was difficult to make an assembly. There is also a problem that heat resistance, solvent resistance and strength are inferior to those of inorganic materials.
As a method for solving these problems, a method in which crosslinked polymer fine particles are aggregated can be considered, but no effective method has been found so far. For example, as described in JP-A-2-70741, a polymer containing an unsaturated carboxylic acid is neutralized and swollen and used as seed particles, and a polymer having a composition different from that is emulsion polymerized as the second stage. A method for obtaining an aggregate by using the above method is known. However, in this method, it is necessary to select conditions under which new particles are not generated in the second-stage polymerization, and there are problems that the polymerization composition and polymerization conditions are limited, and the strength of the aggregate is weak and easily broken.
As described above, heretofore, a matting agent composed of an organic fine particle aggregate that takes advantage of the characteristics of an organic material that has a low true specific gravity and a high affinity with a substrate has not been known.
[Problems to be solved by the invention]
The present invention has been made paying attention to the above situation, and has an object to provide a matting agent having an aggregate of crosslinked polymer fine particles having a small bulk specific gravity and high heat resistance and solvent resistance. To do.
[Means for Solving the Problems]
The gist of the present invention is that it is a matting agent comprising spherical particles having an average particle diameter of 2 to 200 μm formed by aggregation of crosslinked polymer fine particles having an average particle diameter of 0.01 to 1 μm.
The spherical particles are, for example, particles obtained by spray-drying an emulsion containing crosslinked polymer fine particles having an average particle diameter of 0.01 to 1 μm.
DETAILED DESCRIPTION OF THE INVENTION
The material and production method of the spherical particles used in the present invention are not particularly limited. For example, crosslinked fine particles obtained by polymerizing a vinyl monomer mixture containing divinylbenzene and / or trimethylolpropane tri (meth) acrylate are used. The inventors of the present invention have previously found that it can be efficiently obtained by a drying method using a spray-type drying method (Japanese Patent Application No. 10-220418). According to this method, it is possible to obtain a fine particle aggregate having high heat resistance and strength, and having a large specific surface area while retaining the shape of the raw material fine particles.
The crosslinked polymer fine particles used as the raw material for the spherical particles are not particularly limited in composition and production method as long as they are fine particles containing a crosslinked polymer. For example, vinyl monomer containing a crosslinkable monomer is used. The mixture can be produced by emulsion polymerization by a conventionally known method.
Examples of the crosslinkable monomer contained in the vinyl monomer include divinylbenzene and / or trimethylolpropane tri (meth) acrylate. Non-crosslinkable monomers other than the crosslinkable monomer that may be contained in the mixture of vinyl monomers include monomers having one polymerizable unsaturated bond in one molecule. If it is, it will not specifically limit, For example, aromatic vinyl compounds, such as styrene and alpha methyl styrene, (meth) acrylic acid, (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid butyl, etc. (Meth) acrylic acid esters, vinyl esters such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as (meth) acrylonitrile, vinyl halide compounds such as vinyl chloride and vinylidene chloride, conjugated dienes such as butadiene, etc. Used.
The higher the ratio of the crosslinkable monomer in the vinyl monomer mixture, the higher the heat resistance and strength of the resulting fine particles, but this is preferable. Is difficult.
Therefore, when divinylbenzene is used as the crosslinkable monomer, the weight ratio of divinylbenzene in the vinyl monomer mixture is usually in the range of 2 to 10% by weight, preferably 3 to 8% by weight. It is.
When trimethylolpropane tri (meth) acrylate is used as the crosslinkable monomer, the weight ratio of trimethylolpropane tri (meth) acrylate in the vinyl monomer mixture is usually 5 to 30% by weight. The range is preferably 8 to 20% by weight.
The method for producing the mixture of the crosslinked polymers by the emulsion polymerization method is not particularly limited. Generally, a surfactant is used, the solid content concentration is in the range of 5 to 60% by weight, and the inorganic is used as the initiator. A peroxide or a redox initiator can be used and the polymerization can be carried out at a temperature in the range of 20 to 100 ° C.
By the emulsion polymerization method, crosslinked polymer fine particles having an average particle diameter in the range of 0.01 to 1 μm can be obtained simply and efficiently.
The method of using the obtained crosslinked polymer fine particles as an aggregate is not particularly limited, but the method of causing fusion between particles by drying by a spray-type drying method is easy to control the particle diameter and shape of the aggregate. Recommended. The spray-type drying method generally refers to a method in which particles are dried by spraying a water dispersion together with a gas stream using a spray dryer or a stream dryer.
The particle size, particle shape, bulk specific gravity, etc. can be adjusted by appropriately adjusting the solid content concentration, the supply speed, the drying temperature, etc. in the spray-type drying method, and it is particularly necessary to limit to the above conditions. However, for example, the solid content concentration is usually 5 to 60% by weight, more preferably 10 to 50% by weight, and the drying temperature is within the range of the spray inlet temperature of 100 to 200 ° C. The outlet temperature is in the range of 30-100 ° C.
The fine particle aggregate that is the main component of the matting agent of the present invention is, for example, an aggregate in which the crosslinked polymer fine particles are connected to each other while maintaining the shape of the crosslinked polymer fine particles. The fine particle aggregate is characterized in that the particles are spherical and the particle size distribution is sharp. The fine particle aggregate has a feature that the specific surface area is large and the bulk specific gravity is small. Further, the fine particle aggregate has a feature that the strength is higher than that of the conventional fine particle aggregate.
Moreover, the average particle diameter of the fine particle aggregate which is the main component of the matting agent of the present invention is in the range of 2 to 200 μm. Preferably, it is the range of 5-100 micrometers. When the aggregate is out of this range, the effect tends to decrease when used in a matting agent.
The matting agent of the present invention can be used by blending with a resin, a paint, an adhesive, a coating resin, or the like. Further, there is no problem even if it is used in combination with a conventionally known matting agent, but the fine particle aggregate is usually contained in the matting agent in an amount of 10% by weight or more, preferably 20% by weight or more.
When the matting agent of the present invention is used as an additive for paints, it can be used as a matting agent by blending 0.1 to 10% by weight with the usual paint. Since the matting agent of the present invention has a small weight per particle, the effect can be obtained with a small amount of blending compared with the conventional matting agent.
When the matting agent of the present invention is used as an additive for a resin, it is usually used as a matting agent, a light diffusing agent, an antiblocking agent or a filler by blending it with various resins in an amount of 0.1 to 5% by weight. can do. Since the weight per particle is small, a large effect can be obtained by adding a small amount, and since the specific surface area is large, the effect per particle is also large.
When the matting agent of the present invention is used as a paper additive, the specific surface area is large, so that ink drops adhering to the paper surface are quickly absorbed, and a clear image can be obtained when printed. Can do. Usually, 10 to 300 parts by weight is blended with respect to the polymer binder, and the thickness of the matted layer is 1 to 50 μm.
When the matting agent of the present invention is used as a matting agent for silver halide photographic light-sensitive materials, it is useful as a matting agent for silver halide photographic light-sensitive materials because the grains are spherical and the particle size distribution is sharp. The usual amount used is 0.01 to 1 g / m 2 with respect to the photosensitive material.
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
Production Example A 2 L separable flask equipped with a stirrer, a thermometer and a reflux condenser was charged with pure water (433 g) and Haitenol N08 (Daiichi Kogyo Seiyaku Anionic Surfactant, 0.9 g), and replaced with nitrogen. While performing, the temperature was raised to 70 ° C. with stirring. After raising the temperature to 70 ° C., methyl methacrylate (57 g) was added, and 5 minutes later, a 2% aqueous solution of potassium persulfate (70 g) was added.
A pre-emulsion prepared beforehand (methyl methacrylate: 608 g, divinylbenzene: 35 g, pure water: 752 g, Haitenol N08: 34 g) was added at a constant rate at 70 ° C. for 4 hours after 20 minutes from the addition of potassium persulfate. Added over time.
After completion of the addition, the temperature was raised to 75 ° C., aging was performed for 2 hours, and then cooled to 40 ° C. to obtain a crosslinked polymer emulsion. It was 0.2 micrometer when the average particle diameter of this emulsion was measured with the light scattering type particle size distribution analyzer.
Next, the emulsion was sprayed by Yamato Kagaku,
Supply speed: 14ml / min,
Spray pressure: 2.3 kg / cm 2
Air volume: 0.3m 3 / min,
Heating part inlet temperature: 150 ° C.
Heater outlet temperature: 60 ° C
The powder was dried under the above conditions.
When the obtained powder was measured with Multisizer II type (manufactured by Coulter, Inc.), the average particle size was 14 μm. Further, the powder was a fine particle aggregate formed by interconnecting raw material fine particles composed of crosslinked polymer fine particles while maintaining the shape, as observed by an electron microscope (SEM).
Example 1
0.5 g of nonionic surfactant (“Nonipol” manufactured by Sanyo Chemical Co., Ltd., 25% by weight solids) is dissolved in 45 g of water, and 15 g of the fine particle aggregate obtained in the production example may be added as a matting agent to this aqueous solution. Stir and disperse.
Next, 60 g of a polyurethane-based water-dispersed paint (“Superflex E4700” manufactured by Daiichi Kogyo Seiyaku Co., Ltd., solid content: 40% by weight) was added to the dispersion and stirred uniformly to obtain a paint composition.
The coating composition was applied to an ABS resin plate with a spray coater so that the film thickness was about 80 μm, and dried at 80 ° C. for 1 hour.
The thickness of the coating film after drying was about 30 μm, and the 60 ° gloss of the coating film was 85.
Comparative Example 1
A coating film was obtained by repeating the same operation as in Example, except that silica powder (“Lelosil MT-10” manufactured by Tokuyama) was used instead of the fine particle aggregate obtained in the production example.
The thickness of the coating film after drying was about 30 μm, and the 60-degree gloss of the coating film after drying was 75.
【The invention's effect】
The matting agent of the present invention is useful as a matting agent used for resins, paints, adhesives, coating resins and the like because of its low bulk specific gravity and high heat resistance and solvent resistance.
Specifically, when the mat agent of the present invention is used as an additive for paints, the function of a matting agent can be expressed, and the effect can be obtained with a small amount of blending compared to a conventional mat agent.
Further, when the matting agent of the present invention is used as an additive for resin, it can also exhibit functions as a matting agent, a light diffusing agent, an antiblocking agent or a filler, and a large effect can be obtained with a small amount of addition. In addition, since the specific surface area is large, the effect per particle is large.
Further, when the matting agent of the present invention is used as a paper additive, the specific surface area is large, so that ink droplets adhering to the paper surface are quickly absorbed, and a clear image is obtained when printed. be able to.
The matting agent of the present invention is also useful as a matting agent for silver halide photographic light-sensitive materials because the grains are spherical and the particle size distribution is sharp.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26226799A JP4298084B2 (en) | 1999-09-16 | 1999-09-16 | Matting agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26226799A JP4298084B2 (en) | 1999-09-16 | 1999-09-16 | Matting agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001081335A JP2001081335A (en) | 2001-03-27 |
| JP4298084B2 true JP4298084B2 (en) | 2009-07-15 |
Family
ID=17373426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26226799A Expired - Fee Related JP4298084B2 (en) | 1999-09-16 | 1999-09-16 | Matting agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4298084B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7829626B2 (en) * | 2006-03-15 | 2010-11-09 | Rohm And Haas Company | Aqueous compositions comprising polymeric duller particle |
-
1999
- 1999-09-16 JP JP26226799A patent/JP4298084B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001081335A (en) | 2001-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4313664B2 (en) | Protruding conductive particles, coated conductive particles, and anisotropic conductive material | |
| JP3513985B2 (en) | Method for producing curable polymer aqueous dispersion and aqueous curable polymer dispersion | |
| JP4298084B2 (en) | Matting agent | |
| TWI287024B (en) | Grain aggregate and producing method thereof, and light-diffusing agent | |
| JPH02140272A (en) | Crosslinked hollow polymer pigment and coating composition using the pigment | |
| JP2842623B2 (en) | Manufacturing method of polymer double coated particles | |
| JPH0519241B2 (en) | ||
| JP3523075B2 (en) | Fine particle aggregate and its manufacturing method | |
| JP2001335735A (en) | Undercoating composition | |
| JP3401851B2 (en) | Method for microencapsulation of solid particles | |
| WO1991014741A1 (en) | Plastic pigment and production thereof | |
| JP4092073B2 (en) | Aqueous emulsion for adhesive and composition thereof | |
| WO1991000873A1 (en) | Aqueous emulsion | |
| JPH11263802A (en) | Aqueous resin composition, its preparation and coated article | |
| JP2001517721A (en) | Thermally film-forming material with polymerizable component (reactive plastisol) | |
| JPH0623364B2 (en) | Water dispersion type pressure sensitive adhesive composition | |
| JP2002030151A (en) | Particle agglomerate and its production method | |
| CN1436800A (en) | Polyacrylonitrile polymer fine particles | |
| JP2001089689A (en) | Matting agent for printing ink, printing ink composition comprising the same and its use | |
| JP2004002525A (en) | Aqueous adhesive composition and method for producing the same | |
| JPS59179676A (en) | Preparation of pressure-sensitive adhesive tape | |
| JPH04110302A (en) | Aqueous resin dispersion composition | |
| JP2001081263A (en) | Carrier material | |
| JP3211353B2 (en) | Plastic film coating agent | |
| JP2606320B2 (en) | Hollow polymer particles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060606 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20081222 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090113 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090313 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20090313 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090407 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090415 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120424 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120424 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130424 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140424 Year of fee payment: 5 |
|
| LAPS | Cancellation because of no payment of annual fees |