JP5705525B2 - Zeolite composite particles - Google Patents
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本発明は、ゼオライト複合粒子群、特にはポリカルボン酸系ポリマーで処理されたゼオライト複合粒子群、及びこれを含有する粉末洗剤組成物、並びに前記ゼオライト複合粒子群の製造方法に関する。 The present invention relates to a zeolite composite particle group, in particular, a zeolite composite particle group treated with a polycarboxylic acid polymer, a powder detergent composition containing the same, and a method for producing the zeolite composite particle group.
衣料用粉末洗剤は、汚れを速やかに落とす優れた洗浄性能と、すばやく水に溶解・分散する溶解性能、過酷条件に保管されても品質劣化しない保存安定性能が求められる。これら洗浄性能及び保存安定性能を達成するために、優れたカチオン交換能と水蒸気吸着能を有する4A型ゼオライトが一般的に衣料用粉末洗剤に配合されている。 The powder detergent for clothing is required to have excellent cleaning performance for quickly removing dirt, dissolution performance for quick dissolution / dispersion in water, and storage stability performance that does not deteriorate the quality even when stored under severe conditions. In order to achieve these washing performance and storage stability performance, 4A-type zeolite having excellent cation exchange ability and water vapor adsorption ability is generally blended in a powder detergent for clothing.
しかし、ゼオライトは水に不溶性であることから、詰め込み洗濯のような過酷条件で洗濯された場合、すすぎ不足などで、衣類にシミ状の溶け残りが発生させる場合がある。この溶け残りを防止するためにゼオライト配合量を極端に低減した場合、流動性の低下、ブロッキングの発生等、保存安定性が低下する。またカチオン交換能不足による洗浄力低下など、物性、品質、洗浄力に悪影響を及ぼす。物性、品質、洗浄力に悪影響を与えずに衣類へのシミ状の溶け残りを低減させるためには、ゼオライトの水への分散性をいかに向上させるかが重要である。 However, since zeolite is insoluble in water, when washed under harsh conditions such as stuffed laundry, stain-like unmelted residue may be generated in clothing due to insufficient rinsing. When the blending amount of zeolite is extremely reduced in order to prevent this undissolved residue, the storage stability is deteriorated such as a decrease in fluidity and occurrence of blocking. In addition, the physical properties, quality and detergency are adversely affected, such as a decrease in detergency due to insufficient cation exchange capacity. In order to reduce stain residue in clothing without adversely affecting physical properties, quality, and detergency, it is important to improve the dispersibility of zeolite in water.
この点を改善すべく、ゼオライトに関し例えば特許文献1に特定のアクリル系のカルボン酸又はその塩とアクリル系のエステル体の共重合体を添加したゼオライト分散剤が提案されているが、ゼオライトスラリーの静置安定性の向上を意図したものであり、粉末洗剤組成物に配合されたゼオライトの分散性を改善するものではなく、また、この共重合体はシミ状の溶け残りを抑制する効果もない。 In order to improve this point, with respect to zeolite, for example, Patent Document 1 proposes a zeolite dispersant to which a specific acrylic carboxylic acid or a salt thereof and an acrylic ester copolymer are added. It is intended to improve the stationary stability, does not improve the dispersibility of the zeolite blended in the powder detergent composition, and the copolymer does not have the effect of suppressing spot-like undissolved residue. .
一方、特許文献2には、微結晶性ゼオライトと(コ)ポリマーカルボン酸塩との均一粉末混合物を造粒して、高密度のゼオライト含有粒子を製造することが記載されている。特許文献2では、粒子は噴霧乾燥微粉末ゼオライトを用いることが好ましいと記載されている。更に特許文献2の方法によると、処理後のゼオライト粒子は10μmよりも大きくなるため、該微粉末ゼオライトとポリマー粉末とからなる均一粉末混合物から造粒することで得られた高密度ゼオライト含有粒子は、シミ状の溶け残りを抑制する効果は得られない。 On the other hand, Patent Document 2 describes the production of high-density zeolite-containing particles by granulating a uniform powder mixture of microcrystalline zeolite and (co) polymer carboxylate. Patent Document 2 describes that it is preferable to use spray-dried fine powder zeolite for the particles. Furthermore, according to the method of Patent Document 2, since the treated zeolite particles are larger than 10 μm, the high-density zeolite-containing particles obtained by granulating from a uniform powder mixture comprising the fine powder zeolite and the polymer powder are In addition, the effect of suppressing stain-like undissolved residue cannot be obtained.
本発明の課題は、水への分散性を向上させたゼオライト複合粒子群、特にはポリカルボン酸系ポリマーで処理されたゼオライト複合粒子群及びそれを含有してなる粉末洗剤組成物を提供することにある。なおここで粒子群の“群”は粒子が複数存在することを意味し、ポリマー処理の際にゼオライト粒子群として処理することから、当然ながら結果として得られたものがゼオライト複合粒子群となる。 An object of the present invention is to provide a zeolite composite particle group having improved dispersibility in water, particularly a zeolite composite particle group treated with a polycarboxylic acid polymer, and a powder detergent composition containing the same. It is in. Here, the “group” of the particle group means that a plurality of particles exist, and since the zeolite is treated as a zeolite particle group during the polymer treatment, naturally, the resultant is the zeolite composite particle group.
本発明は、平均粒子径が0.1〜8μmであるゼオライト粒子群(a)を、重量平均分子量が2万〜30万で、カルボン酸基を有するモノマー構成単位を有するポリカルボン酸系ポリマー(b)の溶液と混合後、乾燥させて得られたゼオライト複合粒子群であって、
平均粒子径が0.5〜10μmであり、
前記ゼオライト粒子群(a)100質量部に対する前記ポリカルボン酸系ポリマー(b)の割合が5質量部以上である、
ゼオライト複合粒子群に関する。
The present invention relates to a zeolite particle group (a) having an average particle diameter of 0.1 to 8 μm, a polycarboxylic acid-based polymer having a monomer constituent unit having a weight average molecular weight of 20,000 to 300,000 and having a carboxylic acid group ( a zeolite composite particle group obtained by drying after mixing with the solution of b),
The average particle size is 0.5-10 μm,
The ratio of the polycarboxylic acid polymer (b) to 100 parts by mass of the zeolite particle group (a) is 5 parts by mass or more.
The present invention relates to a zeolite composite particle group.
また、本発明は、ゼオライト粒子群(a)及び重量平均分子量が2万〜30万で、カルボン酸基を有するモノマー構成単位を有するポリカルボン酸系ポリマー(b)からなるゼオライト複合粒子群であって、
平均粒子径が0.5〜10μmであり、
体積基準90%(D90)の粒子径が12μm以下であり、
前記ゼオライト粒子群(a)100質量部に対する前記ポリカルボン酸系ポリマー(b)の割合が5質量部以上であり、
ゼオライト粒子がポリカルボン酸系ポリマーで被覆されてなる、
ゼオライト複合粒子群に関する。
The present invention also relates to a zeolite particle group (a) and a zeolite composite particle group comprising a polycarboxylic acid polymer (b) having a monomer structural unit having a carboxylic acid group and a weight average molecular weight of 20,000 to 300,000. And
The average particle size is 0.5-10 μm,
The volume diameter of 90% (D90) is 12 μm or less,
The ratio of the polycarboxylic acid polymer (b) to 100 parts by mass of the zeolite particle group (a) is 5 parts by mass or more,
Zeolite particles are coated with a polycarboxylic acid polymer,
The present invention relates to a zeolite composite particle group.
また、本発明は、上記本発明のゼオライト複合粒子群を含有する粉末洗剤組成物に関する。 Moreover, this invention relates to the powder detergent composition containing the zeolite composite particle group of the said invention.
また、本発明は、平均粒子径0.1〜8μmのゼオライト粒子群(a)〔以下、(a)成分という〕を、重量平均分子量が2万〜30万で、カルボン酸基を有するモノマー構成単位を有するポリカルボン酸系ポリマー(b)〔以下、(b)成分という〕の溶液と混合後、乾燥させて、
平均粒子径が0.5〜10μmであり、前記ゼオライト粒子群(a)100質量部に対する前記ポリカルボン酸系ポリマー(b)の割合が5質量部以上である、ゼオライト複合粒子群を得る、
ゼオライト複合粒子群の製造方法に関する。
Further, the present invention relates to a zeolite particle group (a) [hereinafter referred to as component (a)] having an average particle size of 0.1 to 8 μm, having a weight average molecular weight of 20,000 to 300,000 and having a carboxylic acid group. After mixing with a solution of a polycarboxylic acid polymer (b) having a unit (hereinafter referred to as component (b)), it is dried,
An average particle diameter is 0.5 to 10 μm, and a zeolite composite particle group in which the ratio of the polycarboxylic acid polymer (b) to 100 parts by mass of the zeolite particle group (a) is 5 parts by mass or more is obtained.
The present invention relates to a method for producing a zeolite composite particle group.
本発明によれば、水への分散性を向上させたゼオライト複合粒子及びそれを含有してなる粉末洗剤組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the zeolite composite particle which improved the dispersibility to water, and the powder detergent composition formed by containing it can be provided.
<ゼオライト複合粒子群>
本発明のゼオライト複合粒子群は、(a)成分を(b)成分で処理してなる、微細なゼオライト粒子の複合粒子群である。
<Zeolite composite particles>
The zeolite composite particle group of the present invention is a composite particle group of fine zeolite particles obtained by treating the component (a) with the component (b).
(a)成分はゼオライト粒子の集合体であり、ゼオライトとしては、A型、X型、Y型、P型等が挙げられるが、中でも洗剤用ビルダーとして一般にカチオン交換能に優れるA型ゼオライトが好ましい。A型ゼオライトとは、X線回折パターンがJCPDS(Joint Committee on Powder Diffraction Standards)によって提示された4A型ゼオライト(No.38−241)に示される位置に回折ピークを有するものである。(a)成分は、ゼオライトとして市販されているものを使用できる。 Component (a) is an aggregate of zeolite particles, and examples of zeolite include A type, X type, Y type, and P type. Among them, A type zeolite that is generally excellent in cation exchange ability is preferable as a builder for detergents. . The A-type zeolite has a diffraction peak at the position indicated by the 4A-type zeolite (No. 38-241) whose X-ray diffraction pattern is presented by JCPDS (Joint Committee on Powder Diffraction Standards). As the component (a), those commercially available as zeolite can be used.
ゼオライトは、無水物の一般式がxM2O・ySiO2・Al2O3(ただし、Mはアルカリ金属を表し、x=0.5〜1.5、y=0.5〜6である)で表される。 Zeolite has an anhydrous general formula of xM 2 O.ySiO 2 .Al 2 O 3 (where M represents an alkali metal, x = 0.5 to 1.5, y = 0.5 to 6) It is represented by
本発明でいう(a)成分のゼオライト粒子群を構成しているゼオライト粒子とは、微粒子化されたゼオライト粒子が好ましく、一次粒子ゼオライトそのものが理想的である。しかしながら製造時の経済的観点から、本効果を阻害しない程度で純度の高いゼオライトである必要はなく、非晶質体や不純物を含んでいてもよい。また微粉体として、全くの一次粒子として存在することも難しい。本発明のゼオライトとしては、一次粒子ないし一次粒子が数個凝集しているものであってもよい。“数個凝集”とは顕微鏡下で数えられる数であり、あえて説明するなら一次粒子が10個以内、特には6個以内で凝集しているものである。 The zeolite particles constituting the zeolite particle group of component (a) in the present invention are preferably finely divided zeolite particles, and the primary particle zeolite itself is ideal. However, from an economical point of view at the time of production, it is not necessary to be a zeolite having a high purity so long as this effect is not hindered, and it may contain an amorphous material or impurities. Moreover, it is difficult to exist as a primary particle as a fine powder. The zeolite of the present invention may be one in which several primary particles or primary particles are aggregated. “Several agglomeration” is a number that can be counted under a microscope. If it is explained, the primary particles are agglomerated within 10 particles, particularly within 6 particles.
(a)成分の平均粒子径は0.1〜8μmであるが、本発明では、レーザー回折/散乱式粒度分布測定装置(株式会社堀場製作所製、「LA950」)を用いて、屈折率1.30の水を分散媒として、循環速度4、超音波強度7で超音波5分照射後の粒度分布を測定したときの体積中位粒径(D50)の値を、(a)成分についての平均粒子径とする。一般に体積基準のメジアン径という場合もある。(a)成分の平均粒子径は、洗剤等に配合した場合の被洗浄物(衣服等)への付着を防止する観点から8μm以下であり、(a)成分の同士の過剰な凝集を防止する観点から0.1μm以上である。(a)成分の平均粒子径は、下限値として1μm以上が好ましく、3μm以上がさらに好ましく、上限値として8μm以下が好ましく、5μm以下がより好ましい。更にこれら平均粒子径に加えて、粒度分布状況を示す上で、上記測定方法によるD90、すなわち体積基準で90%になる粒子径が12μm以下が好ましく、10μm以下であることがより好ましく、8μm以下であることがさらに好ましい。 The average particle size of the component (a) is 0.1 to 8 μm. In the present invention, a refractive index of 1. is used by using a laser diffraction / scattering particle size distribution measuring device (“LA950” manufactured by Horiba, Ltd.). The value of volume median particle size (D50) when measuring the particle size distribution after irradiation with ultrasonic waves for 5 minutes at a circulation speed of 4 and an ultrasonic intensity of 7, using 30 water as a dispersion medium, is the average of the component (a). The particle size. Generally, it may be called a volume-based median diameter. The average particle size of the component (a) is 8 μm or less from the viewpoint of preventing adhesion to an object to be cleaned (clothing, etc.) when blended in a detergent or the like, and prevents excessive aggregation of the components (a). From the viewpoint, it is 0.1 μm or more. The average particle diameter of the component (a) is preferably 1 μm or more as the lower limit, more preferably 3 μm or more, and preferably 8 μm or less, more preferably 5 μm or less as the upper limit. Furthermore, in addition to these average particle diameters, in order to show the particle size distribution situation, D90 by the above measurement method, that is, the particle diameter that becomes 90% on a volume basis is preferably 12 μm or less, more preferably 10 μm or less, and more preferably 8 μm or less. More preferably.
(b)成分は、カルボン酸基を有するモノマー構成単位が全モノマー構成単位中80〜100モル%、更に90〜100モル%であるものが好ましい。 The component (b) is preferably such that the monomer structural unit having a carboxylic acid group is 80 to 100 mol%, more preferably 90 to 100 mol%, of all monomer structural units.
また、(b)成分の重量平均分子量は、2万〜30万であり、好ましくは3万〜20万である。(b)成分の重量平均分子量は、ポリエチレングリコールを標準とし、アセトニトリルと水の混合溶液(リン酸緩衝液)を展開溶媒とし、ゲル浸透型液体クロマトグラフィーによって測定される。 Moreover, the weight average molecular weight of (b) component is 20,000-300,000, Preferably it is 30,000-200,000. The weight average molecular weight of the component (b) is measured by gel permeation liquid chromatography using polyethylene glycol as a standard and a mixed solution of acetonitrile and water (phosphate buffer) as a developing solvent.
(b)成分としては、アクリル酸及びメタクリル酸から選ばれる単量体のポリマーが挙げられる。具体的には、ポリアクリル酸、ポリメタクリル酸等、カルボン酸基を有するモノマーのホモポリマーや、アクリル酸とマレイン酸のコポリマーなどのカルボン酸系ポリマーが挙げることができる。これらの中で、アクリル酸/マレイン酸のモノマー比率が20/80〜80/20、更に30/70〜70/30のアクリル酸/マレイン酸コポリマーが好ましい。 (B) As a component, the polymer of the monomer chosen from acrylic acid and methacrylic acid is mentioned. Specific examples include homopolymers of monomers having a carboxylic acid group, such as polyacrylic acid and polymethacrylic acid, and carboxylic acid-based polymers such as copolymers of acrylic acid and maleic acid. Of these, acrylic acid / maleic acid copolymers having an acrylic acid / maleic acid monomer ratio of 20/80 to 80/20, more preferably 30/70 to 70/30 are preferred.
本発明のゼオライト複合粒子群は、洗剤等に配合した場合の被洗浄物(衣服等)へのシミ残りを防止する観点から、(a)成分100質量部に対する(b)成分の割合が5質量部以上である。(a)成分100質量部に対する(b)成分の割合は、ゼオライト複合粒子群の粉末物性の悪化を防止する観点から、50質量部以下が好ましく、30質量部以下より好ましく、10質量部以下がさらに好ましい。 In the zeolite composite particle group of the present invention, the proportion of the component (b) with respect to 100 parts by mass of the component (a) is 5% from the viewpoint of preventing stains remaining on an object to be cleaned (clothes, etc.) when blended in a detergent or the like. More than a part. The proportion of the component (b) relative to 100 parts by mass of the component (a) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and preferably 10 parts by mass or less from the viewpoint of preventing deterioration of the powder physical properties of the zeolite composite particles. Further preferred.
本発明のゼオライト複合粒子群は、平均粒子径が0.5μm〜10μmであるが、この平均粒子径は、一次粒子乃至一次粒子ゼオライトが数個凝集した実質的に単一のゼオライト粒子を(b)成分のポリマーによって被覆したゼオライト複合粒子から、ゼオライトが(b)成分のポリマーと伴に凝集された粒子の混合物の平均粒子径であり、以降、平均複合粒子径と呼ぶ。本発明では、レーザー回折/散乱式粒度分布測定装置(株式会社堀場製作所製、「LA950」)を用いて、屈折率1.30の水を分散媒として、循環速度4、超音波照射なしで1分間循環後、測定したときの体積中位粒径(D50)の値を、ゼオライト複合粒子群についての平均複合粒子径とする。本発明のゼオライト複合粒子群の平均複合粒子径は、ゼオライト複合粒子同士の更なる凝集を防止する観点から、0.5μm以上であり、2μm以上がより好ましく、5μm以上が更に好ましく、また、洗剤等に配合した場合の被洗浄物(衣服等)への付着を防止する観点から10μm以下であり、8μm以下が好ましく、6μm以下がより好ましい。更にこれら平均粒子径に加えて、粒度分布状況を示す上で、上記測定方法によるD90、すなわち体積基準で90%になる粒子径が12μm以下が好ましく、10μm以下であることがより好ましく、8μm以下であることがさらに好ましい。 The zeolite composite particle group of the present invention has an average particle diameter of 0.5 μm to 10 μm. The average particle diameter is substantially equal to a single zeolite particle in which several primary particles or primary particle zeolites are aggregated (b The average particle size of a mixture of particles obtained by agglomerating zeolite with the polymer of component (b) from the zeolite composite particles coated with component polymer), and hereinafter referred to as the average composite particle size. In the present invention, using a laser diffraction / scattering type particle size distribution measuring apparatus (“LA950” manufactured by Horiba, Ltd.), water having a refractive index of 1.30 is used as a dispersion medium, the circulation speed is 4, and there is no ultrasonic irradiation. After circulating for a minute, the value of the volume median particle size (D50) as measured is taken as the average composite particle size for the zeolite composite particle group. The average composite particle size of the zeolite composite particles of the present invention is 0.5 μm or more, more preferably 2 μm or more, further preferably 5 μm or more, from the viewpoint of preventing further aggregation of the zeolite composite particles, and a detergent. From the viewpoint of preventing adhesion to an object to be cleaned (clothing, etc.) when blended in the like, it is 10 μm or less, preferably 8 μm or less, and more preferably 6 μm or less. Furthermore, in addition to these average particle diameters, in order to show the particle size distribution situation, D90 by the above measurement method, that is, the particle diameter that becomes 90% on a volume basis is preferably 12 μm or less, more preferably 10 μm or less, and more preferably 8 μm or less. More preferably.
本発明のゼオライト複合粒子群は、ゼオライト複合粒子単体で観察すると、(b)成分のポリマーによってゼオライト粒子が被覆されている粒子であることが好ましく、理想的には一次粒子ゼオライトが該ポリマーで被覆されている粒子が好ましい。しかしながら一次粒子径をコアとする複合粒子だけからなる粒子群を得ることは困難であり、本発明の粒子径条件を満たす限り、凝集粒子がポリマーによって被覆されているゼオライト複合粒子であってもよく、一次粒子ゼオライトがポリマーによって凝集した粒子を形成したものを含んでいてもよい。 The zeolite composite particles of the present invention are preferably particles in which the zeolite particles are coated with the polymer of component (b) when observed as a single zeolite composite particle. Ideally, the primary particle zeolite is coated with the polymer. Particles are preferred. However, it is difficult to obtain a particle group composed only of composite particles having a primary particle size as a core, and may be zeolite composite particles in which aggregated particles are coated with a polymer as long as the particle size condition of the present invention is satisfied. The primary particle zeolite may include particles formed by agglomeration of the polymer.
被覆の確認はESCAなどの表面分析装置によって、複合粒子表面にゼオライトの構成元素である、Siなどが検出されないことで確認することができる。 The coating can be confirmed by the fact that Si, which is a constituent element of zeolite, is not detected on the surface of the composite particle by a surface analysis device such as ESCA.
しかしながら、本発明のゼオライト複合粒子群は、製造方法によっては凝集し過ぎたために、平均粒子径が大きくなってしまう場合や、粒径分布のブロードな凝集粒子が得られる場合がある。従って本発明の平均粒子径を満たす、好ましくは平均粒子径とD90の要件を満たすゼオライト複合粒子群を得るために分級、粉砕等によって平均粒子径を調整することが出来る。例えば、化学工学会編「化学工学便覧」(丸善、1988年)第五版826〜838頁に記載の粉砕機を用いることができる。湿式粉砕でも乾式粉砕でも良い。また、凝集粒径分布の均一化は、分級によっても行なわれる。分級法としては、例えば、化学工学会編「化学工学便覧」(丸善、1988年)第五版795〜809頁に記載の分級法を用いることができる。湿式分級でも乾式分級でも良い。 However, since the zeolite composite particles of the present invention are too agglomerated depending on the production method, there are cases where the average particle size becomes large or agglomerated particles having a broad particle size distribution may be obtained. Therefore, in order to obtain a zeolite composite particle group satisfying the average particle diameter of the present invention, preferably satisfying the requirements of the average particle diameter and D90, the average particle diameter can be adjusted by classification, pulverization or the like. For example, the pulverizer described in “Chemical Engineering Handbook” (Maruzen, 1988), 5th edition, pages 826-838, edited by the Society of Chemical Engineering, can be used. Wet grinding or dry grinding may be used. Further, the homogenization of the aggregate particle size distribution is also performed by classification. As the classification method, for example, a classification method described in “Chemical Engineering Handbook” (Maruzen, 1988), 5th edition, pages 795 to 809, edited by the Society of Chemical Engineers, can be used. Wet classification or dry classification may be used.
本発明のゼオライト複合粒子群は、嵩密度が400〜1200g/L、更には600〜1000g/Lであることが好ましい。 The zeolite composite particles of the present invention preferably have a bulk density of 400 to 1200 g / L, more preferably 600 to 1000 g / L.
本発明のゼオライト複合粒子群を構成する粒子は、(a)成分を構成する単一のゼオライト、好ましくは一次粒子ゼオライトと一次粒子のゼオライトが数個凝集したゼオライトの表面に(b)成分であるポリカルボン酸系ポリマーが接触して表面処理された個々の粒子又はそれらが凝集したものである。(b)成分は、必ずしもゼオライト粒子の表面の全部を覆わなくとも効果が得られるが、分散性の面から、ゼオライト粒子の表面を(b)成分で完全に被覆した状態が好ましい。なお、(b)成分で被覆した状態とは、ESCAなどの表面分析装置によって、最終的に得られたゼオライト複合粒子の表面にゼオライトの構成元素であるSiなどが検出されない状態のことをいう。 The particles constituting the zeolite composite particle group of the present invention are the component (b) on the surface of a single zeolite constituting the component (a), preferably a zeolite in which several primary particle zeolites and several primary particle zeolites are aggregated. Individual particles surface-treated with a polycarboxylic acid polymer or agglomerated thereof. Although the component (b) does not necessarily cover the entire surface of the zeolite particles, the effect can be obtained, but from the viewpoint of dispersibility, a state in which the surface of the zeolite particles is completely covered with the component (b) is preferable. In addition, the state coat | covered with (b) component means the state by which Si etc. which are constituent elements of a zeolite are not detected on the surface of the zeolite composite particle finally obtained by surface analysis apparatuses, such as ESCA.
本発明のゼオライト複合粒子群は、(a)成分を(b)成分の溶液、好ましくは水溶液と混合した後、乾燥(混合物からの溶媒の除去)することによって得られる。乾燥方法としては特に限定されないが、薄膜乾燥または噴霧乾燥、特には噴霧乾燥が好ましい。 The zeolite composite particles of the present invention can be obtained by mixing the component (a) with a solution of the component (b), preferably an aqueous solution, and then drying (removing the solvent from the mixture). The drying method is not particularly limited, but thin film drying or spray drying, particularly spray drying is preferable.
製造方法として、(a)成分を液体分散媒内で、超音波照射やミルなどの粉砕機により溶液中で一次粒子にまで粉砕して微細粒子群とする工程を有することが好ましい。この場合(a)成分を液体分散媒中で分散させ超音波照射等の粉砕処理を施した後(b)成分を添加し接触させる方法と、(a)成分と(b)成分が同時に存在する液体分散媒に対して粉砕処理を施す方法があるが、水溶液の場合(a)成分と(b)成分の共存下で粉砕処理を行なうと(b)成分によりゼオライト粒子の分散性がよくなるため、液体分散媒中で(a)成分と(b)成分との共存下で粉砕処理を行ない微粒子懸濁溶液を調整することが好ましい。処理後は、液体分散媒を乾燥させて、ゼオライト複合体の凝集物を得、それを乾式粉砕などして本発明の平均粒子径に整えることが好ましい。 The production method preferably includes a step of crushing the component (a) in a liquid dispersion medium to primary particles in a solution by a pulverizer such as ultrasonic irradiation or a mill to form a fine particle group. In this case, after the component (a) is dispersed in a liquid dispersion medium and subjected to grinding treatment such as ultrasonic irradiation, the component (b) is added and brought into contact, and the component (a) and the component (b) exist simultaneously. There is a method of pulverizing the liquid dispersion medium, but in the case of an aqueous solution, if the pulverization is performed in the presence of the component (a) and the component (b), the dispersibility of the zeolite particles is improved by the component (b). It is preferable to prepare a fine particle suspension by pulverizing in a liquid dispersion medium in the presence of the components (a) and (b). After the treatment, it is preferable to dry the liquid dispersion medium to obtain an aggregate of the zeolite composite, which is dry pulverized to adjust the average particle diameter of the present invention.
また、乾燥には、化学工学会編「化学工学便覧」(丸善、1999年)第六版769〜772頁に記載の表14・11〜12熱風乾燥機の特性・概要に記載の乾燥装置を用いることができる。このうち熱風搬送型の噴霧タイプと、過熱面未着型のドラムドライヤータイプなどの乾燥速度の速いものが好ましい。また熱風の代わりに、マイクロ波を利用する乾燥装置も好ましく用いられる。 In addition, for drying, the drying apparatus described in Tables 14 and 11-12, Characteristics and Overview of Hot Air Dryers, described in “Chemical Engineering Handbook” (Maruzen, 1999), 6th edition, pages 769-772, is edited. Can be used. Of these, those having a high drying speed, such as a hot air conveying spray type and a non-superheated drum dryer type, are preferred. Also, a drying device using microwaves is preferably used instead of hot air.
本発明のゼオライト複合粒子群は、ゼオライト一次粒子をポリカルボン酸系ポリマーで被覆することでゼオライト表面の負電荷がさらに高まる。その結果、例えば粉末洗剤に配合した場合は、洗浄水中で、布との静電反発力が高まり、ゼオライト粒子の衣類への付着が抑制される。そのため、シミ状の溶け残りが少なくなる。 In the zeolite composite particle group of the present invention, the negative charge on the zeolite surface is further increased by coating the zeolite primary particles with a polycarboxylic acid polymer. As a result, for example, when blended in a powder detergent, the electrostatic repulsion force with the cloth is increased in the washing water, and the adhesion of zeolite particles to clothing is suppressed. As a result, the amount of undissolved spots is reduced.
本発明のゼオライト複合粒子群を得るための好ましい製造方法の一例を挙げると、(a)成分100質量部に対して、(b)成分の溶液5〜50質量部を混合し、噴霧乾燥により乾燥させる方法が挙げられる。この場合、(b)成分の溶液は水溶液が好ましく、該水溶液における(b)成分の濃度は、(a)成分100質量部に対する(b)成分の割合が5質量部以上になるように設定される。この水溶液を混合する際に、ゼオライト粒子群が前記D50の要件、特には前記D50且つD90の要件を満たすことがより好ましい。なお混合時の水溶液の温度は限定されないが5〜60℃が好ましい。また、噴霧乾燥の温度は100〜300℃が好ましい。 An example of a preferable production method for obtaining the zeolite composite particle group of the present invention is as follows. 5 parts by mass of the component (b) solution is mixed with 100 parts by mass of the component (a) and dried by spray drying. The method of letting it be mentioned. In this case, the solution of component (b) is preferably an aqueous solution, and the concentration of component (b) in the aqueous solution is set so that the ratio of component (b) to 100 parts by mass of component (a) is 5 parts by mass or more. The When mixing this aqueous solution, it is more preferable that the zeolite particle group satisfies the requirements of D50, particularly the requirements of D50 and D90. In addition, the temperature of the aqueous solution at the time of mixing is not limited, but 5-60 degreeC is preferable. The spray drying temperature is preferably 100 to 300 ° C.
本発明のゼオライト複合粒子群は、(a)成分、(b)成分及び水以外の一般に洗浄剤に用いる剤を含有してもよい。また後述する粉末洗剤組成物用の添加剤とする場合、洗剤粒子の一部がゼオライト複合粒子に付着する可能性もある。例えば界面活性剤、ポリエチレングリコールなどの非イオン性ポリマー、蛍光染料、色素、香料、その他水溶性または水不溶性無機塩等を挙げることができる。その他成分は、(a)成分100質量部当たりに5質量部以下であり、更には3質量%以下、特には1質量%以下であるが、本発明のゼオライト複合粒子群は、実質的に(a)成分と(b)成分とからなることが好ましい。 The zeolite composite particle group of the present invention may contain agents generally used for cleaning agents other than the components (a), (b) and water. Moreover, when it is set as the additive for powder detergent compositions mentioned later, a part of detergent particle | grains may adhere to a zeolite composite particle. Examples thereof include surfactants, nonionic polymers such as polyethylene glycol, fluorescent dyes, pigments, fragrances, and other water-soluble or water-insoluble inorganic salts. The other component is 5 parts by mass or less per 100 parts by mass of the component (a), further 3% by mass or less, and particularly 1% by mass or less. It is preferable to consist of a) component and (b) component.
本発明のゼオライト複合粒子群は、通常のゼオライト同様、粉末洗剤組成物用の添加剤、なかでも洗剤用ビルダー、更に衣料洗剤用ビルダーとして好適に使用できる。また、カチオン交換体であるので、重金属等のイオン交換を行う機能を有するため、排水処理剤や水処理剤等にも利用できる。また、重金属又は貴金属触媒用の担体や塩基性触媒としても利用することができる。 The zeolite composite particle group of the present invention can be suitably used as an additive for a powder detergent composition, especially a detergent builder, and further a garment detergent builder, as in the case of ordinary zeolite. Further, since it is a cation exchanger, it has a function of exchanging heavy metals and the like, and therefore can be used for waste water treatment agents, water treatment agents and the like. It can also be used as a carrier or basic catalyst for heavy metal or noble metal catalysts.
<粉末洗剤組成物>
本発明の粉末洗剤組成物は、本発明のゼオライト複合粒子群を含有する。
<Powder detergent composition>
The powder detergent composition of the present invention contains the zeolite composite particles of the present invention.
本発明の粉末洗剤組成物は、界面活性剤、アルカリ剤、ビルダー等を含有するベース洗剤に本発明のゼオライト複合粒子群を混合して得られるもので、洗浄性能の観点からベース洗剤100質量部に対して、本発明のゼオライト複合粒子群を、1質量部以上混合することが好ましく、5質量部以上混合することがより好ましく、10質量部以上混合することが更に好ましい。また、粉末物性及び溶解性の観点から、50質量部以下混合することが好ましく、30質量部以下混合することがより好ましく、20質量部以下混合することが更に好ましい。 The powder detergent composition of the present invention is obtained by mixing the zeolite composite particles of the present invention with a base detergent containing a surfactant, an alkaline agent, a builder, etc., and from the viewpoint of cleaning performance, 100 parts by mass of the base detergent On the other hand, the zeolite composite particle group of the present invention is preferably mixed in an amount of 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more. Moreover, from a powder physical property and a soluble viewpoint, it is preferable to mix 50 mass parts or less, It is more preferable to mix 30 mass parts or less, It is still more preferable to mix 20 mass parts or less.
ベース洗剤は、通常添加される洗剤成分、例えば、各種の界面活性剤、アルカリ剤(アルカリ金属炭酸塩等)、ビルダー(本発明のゼオライト複合粒子群以外のもの)、酵素、漂白剤(過炭酸塩、過ホウ酸塩、漂白活性化剤等)、再汚染防止剤(カルボキシメチルセルロース等)、柔軟化剤、還元剤(亜硫酸塩等)、蛍光増白剤、抑泡剤(シリコーン等)、香料等を含有することができる。但し、酵素及び漂白剤(過炭酸塩、過ホウ酸塩、漂白活性化剤等)は、通常、別粒子として用いられる。 Base detergents are usually added detergent components such as various surfactants, alkali agents (alkali metal carbonates, etc.), builders (other than the zeolite composite particles of the present invention), enzymes, bleaching agents (percarbonate). Salt, perborate, bleach activator, etc.), anti-staining agent (carboxymethyl cellulose, etc.), softener, reducing agent (sulfite, etc.), fluorescent brightener, foam suppressor (silicone, etc.), fragrance Etc. can be contained. However, enzymes and bleaching agents (percarbonate, perborate, bleach activator, etc.) are usually used as separate particles.
本発明の粉末洗剤組成物の用途は特に限定されず、衣料用洗剤、食器用洗剤、住居用洗剤、自動車用洗剤、身体用洗剤、歯ミガキ、金属用洗浄剤等として好適に用いられる。特には衣料用洗剤が好適である。 The use of the powder detergent composition of the present invention is not particularly limited, and it is suitably used as a detergent for clothing, dishwashing detergent, residential detergent, automobile detergent, body detergent, tooth paste, metal detergent and the like. In particular, a detergent for clothing is suitable.
衣料用洗剤として好ましい組成の一例としては、本発明のゼオライト複合粒子群10〜50質量%、界面活性剤1〜50質量%、炭酸ナトリウム1〜50質量%、その他の成分(酵素等)0.1〜5質量%を含有するものが挙げられる。 As an example of a composition preferable as a detergent for clothes, the zeolite composite particle group of the present invention is 10 to 50% by mass, the surfactant is 1 to 50% by mass, the sodium carbonate is 1 to 50% by mass, other components (enzymes and the like) What contains 1-5 mass% is mentioned.
下記の実施例及び比較例における、平均複合粒子径、平均粒子径、布残留量は以下の方法により、測定ないし算出した。 In the following Examples and Comparative Examples, the average composite particle diameter, average particle diameter, and cloth residual amount were measured or calculated by the following methods.
またゼオライト複合粒子のゼオライト粒子がポリマーによって被覆されているかどうかの確認は、ESCAなどの表面分析装置により行った。 In addition, whether or not the zeolite particles of the zeolite composite particles were covered with a polymer was confirmed by a surface analyzer such as ESCA.
<ゼオライト複合粒子群の平均複合粒子径>
レーザー回折/散乱式粒度分布測定装置(株式会社堀場製作所製、「LA950」)を用いて、屈折率1.30の水を分散媒として、循環速度4、超音波照射なしで1分間循環後、測定したときの体積中位粒径(D50)の値をゼオライト複合粒子群の平均複合粒子径とした。
<Average composite particle size of zeolite composite particles>
Using a laser diffraction / scattering type particle size distribution measuring apparatus ("LA950" manufactured by Horiba, Ltd.), using water with a refractive index of 1.30 as a dispersion medium, circulating at a circulation rate of 4 for 1 minute without ultrasonic irradiation, The value of the volume median particle size (D50) when measured was taken as the average composite particle size of the zeolite composite particle group.
<(a)成分の平均粒子径>
レーザー回折/散乱式粒度分布測定装置(株式会社堀場製作所製、「LA950」)を用いて、屈折率1.30の水を分散媒として、循環速度4、超音波強度7で超音波5分照射後の粒度分布を測定したときの体積中位粒径(D50)の値をゼオライト粒子群〔(a)成分〕の平均粒子径とした。
<Average particle diameter of component (a)>
Using a laser diffraction / scattering type particle size distribution measuring apparatus (“LA950” manufactured by Horiba, Ltd.), water with a refractive index of 1.30 is used as a dispersion medium, and the ultrasonic wave is irradiated for 5 minutes at a circulation speed of 4 and an ultrasonic intensity of 7. The value of the volume median particle size (D50) when the subsequent particle size distribution was measured was defined as the average particle size of the zeolite particle group [component (a)].
<布残留性>
(1)試験布の調製
染色試材株式会社谷頭商店の黒染綿ブロード40(平織り黒布)を直径8cmの円状に切り取ったものを試験布とした。この試験布を、電気乾燥機で105℃で30分乾燥し、室温湿度制御室(25℃・50%Rh)で15分静置後、精密天秤で秤量する(初期質量の測定)。
<Cloth persistence>
(1) Preparation of test cloth Dyeing test material A black cloth-dyed cotton broad 40 (plain weave black cloth) from Tanigami Shoten Co., Ltd. was cut into a circular shape having a diameter of 8 cm to obtain a test cloth. This test cloth is dried at 105 ° C. for 30 minutes with an electric dryer, allowed to stand for 15 minutes in a room temperature and humidity control room (25 ° C., 50% Rh), and then weighed with a precision balance (measurement of initial mass).
(2)ゼオライト複合粒子群の布残留質量の測定
25℃にしたイオン交換水を1リットルビーカー(内径105mm、高さ150mmの円筒型、例えば岩城硝子株式会社製)の中に満たし、25℃の水温をウオーターバスにて一定に保った状態で、攪拌子(長さ35mm、直径8mm、例えば型式:ADVANTEC社製、テフロン(登録商標)丸型細型)にて水深に対する渦巻きの深さが略1/3となる回転数(1000rpm)で攪拌した。0.1666±0.0010gとなるように秤量したゼオライト複合粒子群を攪拌下に水中に投入・分散させ攪拌を続けた。投入から10分後に予め吸引ろ過器にセットしておいた試験布に分散液を流し吸引ろ過した。なお、吸引ろ過は、直径90mmのブフナーロートに予め質量を計っておいた試験布をセットして吸引瓶を用いて行った。吸引ろ過後、試験布を電気乾燥機で105℃で30分乾燥し、室温湿度制御室(25℃・50%Rh)で15分静置後、評価布に付着したゼオライト複合粒子群の量を精密天秤で秤量し、評価布質量−初期質量により求めた。
(2) Measurement of cloth residual mass of zeolite composite particle group Ion exchange water adjusted to 25 ° C was filled in a 1 liter beaker (inner diameter 105 mm, height 150 mm cylindrical type, for example, manufactured by Iwaki Glass Co., Ltd.) With the water temperature kept constant in a water bath, the swirl depth with respect to the water depth is approximately 1 with a stirrer (length: 35 mm, diameter: 8 mm, for example, model: ADVANTEC, Teflon (registered trademark) round thin type). Stirring was performed at a rotation speed of 1000 rpm (1000 rpm). The zeolite composite particle group weighed so as to be 0.1666 ± 0.0010 g was charged and dispersed in water with stirring, and stirring was continued. Ten minutes after the addition, the dispersion was poured into a test cloth that had been set in a suction filter in advance, and suction filtered. In addition, the suction filtration was performed using a suction bottle with a test cloth previously weighed in a Buchner funnel having a diameter of 90 mm. After suction filtration, the test cloth is dried with an electric dryer at 105 ° C. for 30 minutes, left in a room temperature humidity control room (25 ° C., 50% Rh) for 15 minutes, and then the amount of zeolite composite particles attached to the evaluation cloth Was weighed with a precision balance, and determined from the evaluation fabric mass-initial mass.
(3)粉末洗剤組成物の布残留質量の測定
ゼオライト複合粒子群の布残留質量の測定において、ゼオライト複合粒子群を粉末洗剤組成物に置き換えて行った。その際、粉末洗剤組成物は、0.666±0.0010gとなるように秤量して投入した。
(3) Measurement of cloth residual mass of powder detergent composition In the measurement of the cloth residual mass of the zeolite composite particle group, the zeolite composite particle group was replaced with the powder detergent composition. At that time, the powder detergent composition was weighed and added so as to be 0.666 ± 0.0010 g.
(4)布残留率の算出
以下の式により布残留率を算出した。
布残留率(%)=(T/S)×100
S:ゼオライト複合粒子群又は粉末洗剤組成物の投入質量(g)
T:ゼオライト複合粒子群又は粉末洗剤組成物の布残留質量(g)
(4) Calculation of cloth residual ratio The cloth residual ratio was calculated by the following formula.
Cloth residual ratio (%) = (T / S) × 100
S: input mass (g) of zeolite composite particles or powder detergent composition
T: cloth residual mass (g) of zeolite composite particles or powder detergent composition
実施例1
20mLスクリュー管に、ゼオライト粒子群(平均粒子径4.0μm(D50)、6.2μm(D90))2gと重量平均分子量50000のポリアクリル酸Na水溶液8gを投入し、10gのゼオライト・ポリマー分散液を作製した。ポリマー水溶液の濃度はゼオライト粒子群100質量部に対しポリマーの固形分が5.3質量部になるようにイオン交換水で調整した。次に作製したゼオライト・ポリマー分散液を、超音波洗浄機の水槽にスクリュー管を浸けて超音波にかけ、ゼオライトの平均粒子径が4.0μm、D90が6.2μmになった事を、レーザー回折/散乱式粒度分布測定装置(株式会社堀場製作所製、「LA950」、以下、LA950と表記する)で確認した後、直径20cmの蒸発皿にゼオライト・ポリマー分散液を滴下し、電子レンジで約8gの水分を乾燥させた。乾燥後、蒸発皿に付着したポリマー処理ゼオライト含有固体をスパーテルでかき取り、平均複合粒子径が5.4μm、D90が7.9μmになるように乳鉢で粉砕しゼオライト複合粒子群を得た。この試料を用いて、布残留性評価を行った結果を表1に示す。
Example 1
A 20 mL screw tube was charged with 2 g of a zeolite particle group (average particle size: 4.0 μm (D50), 6.2 μm (D90)) and 8 g of a polyacrylic acid Na aqueous solution having a weight average molecular weight of 50000, and 10 g of a zeolite polymer dispersion. Was made. The concentration of the aqueous polymer solution was adjusted with ion-exchanged water so that the solid content of the polymer was 5.3 parts by mass with respect to 100 parts by mass of the zeolite particle group. Next, the zeolite-polymer dispersion thus prepared was subjected to ultrasonic waves by immersing a screw tube in a water tank of an ultrasonic cleaner, and the fact that the average particle diameter of zeolite was 4.0 μm and D90 was 6.2 μm was confirmed by laser diffraction. / After confirming with a scattering type particle size distribution analyzer (Horiba, Ltd., “LA950”, hereinafter referred to as LA950), a zeolite-polymer dispersion is dropped into an evaporating dish with a diameter of 20 cm, and about 8 g in a microwave oven. The moisture was dried. After drying, the polymer-treated zeolite-containing solid adhering to the evaporating dish was scraped with a spatula and pulverized in a mortar so that the average composite particle size was 5.4 μm and D90 was 7.9 μm, to obtain a zeolite composite particle group. Table 1 shows the results of the cloth residue evaluation using this sample.
実施例2
ポリマーの種類を重量平均分子量170000のポリアクリル酸Naにし、実施例1と同様の方法でサンプルを作製し、同じ手法で評価を行った。評価結果を表1に示す。
Example 2
The polymer type was changed to polyacrylic acid Na having a weight average molecular weight of 170,000, samples were prepared in the same manner as in Example 1, and evaluation was performed in the same manner. The evaluation results are shown in Table 1.
実施例3
ポリマーの種類を重量平均分子量50000のアクリル酸/マレイン酸コポリマーNa(アクリル酸/マレイン酸=50/50、モル比)にし、実施例1と同様の方法でサンプルを作製し、同じ手法で評価を行った。評価結果を表1に示す。
Example 3
The polymer type was changed to acrylic acid / maleic acid copolymer Na (acrylic acid / maleic acid = 50/50, molar ratio) having a weight average molecular weight of 50000, a sample was prepared in the same manner as in Example 1, and the evaluation was performed in the same manner. went. The evaluation results are shown in Table 1.
実施例4
ポリマーの種類を重量平均分子量70000のアクリル酸/マレイン酸コポリマーNa(アクリル酸/マレイン酸=50/50、モル比)にし、実施例1と同様の方法でサンプルを作製し、同じ手法で評価を行った。評価結果を表1に示す。
Example 4
Acrylic acid / maleic phosphate copolymer Na (acrylic acid / maleic acid = 50/50 molar ratio) of the weight average molecular weight 70,000 types of polymer to, to prepare a sample in the same manner as in Example 1, evaluated by the same method Went. The evaluation results are shown in Table 1.
実施例5〜9
実施例1と同様の方法で、但し重量平均分子量50000のポリアクリル酸Naの添加量を表1のように変更して、サンプルを作製し、同じ手法で評価を行った。評価結果を表1に示す。
Examples 5-9
Samples were prepared in the same manner as in Example 1, except that the amount of polyacrylic acid Na having a weight average molecular weight of 50000 was changed as shown in Table 1 and evaluated by the same method. The evaluation results are shown in Table 1.
比較例1
20mLスクリュー管に、ゼオライト粒子群(ゼオビルダー社製)(平均粒子径4.0μm、D90が6.2μm)2gとイオン交換水8gを投入し、10gのゼオライト分散液を作製した。次に作製したゼオライト分散液を超音波にかけ平均粒子径が4.0μm、D90が6.2μmになった事を、LA950で確認した後、直径20cmの蒸発皿にゼオライト分散液を滴下し、電子レンジで約8gの水分を乾燥させた。乾燥後、蒸発皿に付着したゼオライトをスパーテルでかき取り、平均複合粒子径が5.4μm、D90が7.9μmになるように乳鉢で粉砕しゼオライト複合粒子群を得た。この試料を用いて、布残留性評価を行った結果を表1に示す。
Comparative Example 1
A 20 mL screw tube was charged with 2 g of a zeolite particle group (manufactured by Zeobuilder) (average particle size: 4.0 μm, D90: 6.2 μm) and 8 g of ion-exchanged water to prepare 10 g of a zeolite dispersion. Next, the prepared zeolite dispersion was subjected to ultrasonic waves, and it was confirmed by LA950 that the average particle size was 4.0 μm and D90 was 6.2 μm. Then, the zeolite dispersion was dropped into an evaporating dish having a diameter of 20 cm. About 8 g of water was dried in the range. After drying, the zeolite adhering to the evaporating dish was scraped with a spatula and pulverized in a mortar so that the average composite particle size was 5.4 μm and D90 was 7.9 μm, to obtain a zeolite composite particle group. Table 1 shows the results of the cloth residue evaluation using this sample.
比較例2
20mLスクリュー管に、ゼオライト粒子群(ゼオビルダー社製)(平均粒子径4.0μm、D90が6.2μm)2gと重量平均分子量1200のポリアクリル酸Na水溶液8gを投入し、10gのゼオライト・ポリマー分散液を作製した。ポリマー水溶液の濃度はゼオライト粒子群100質量部に対しポリマーの固形分が5.3質量部になるようにイオン交換水で調整した。次に作製したゼオライト・ポリマー分散液を超音波にかけ平均粒子径が4.0μm、D90が6.2μmになった事を、LA950で確認した後、直径20cmの蒸発皿にゼオライト・ポリマー分散液を滴下し、電子レンジで約8gの水分を乾燥させた。乾燥後、蒸発皿に付着したポリマー処理ゼオライト含有固体をスパーテルでかき取り、平均複合粒子径が5.4μm、D90が7.9μmになるように乳鉢で粉砕しゼオライト複合粒子群を得た。この試料を用いて、布残留性評価を行った結果を表1に示す。
Comparative Example 2
A 20 mL screw tube was charged with 2 g of a zeolite particle group (manufactured by Zeobuilder) (average particle size: 4.0 μm, D90: 6.2 μm) and 8 g of a polyacrylic acid Na aqueous solution having a weight average molecular weight of 1200. 10 g of zeolite polymer dispersion A liquid was prepared. The concentration of the aqueous polymer solution was adjusted with ion-exchanged water so that the solid content of the polymer was 5.3 parts by mass with respect to 100 parts by mass of the zeolite particle group. Next, the prepared zeolite-polymer dispersion was subjected to ultrasonic waves, and it was confirmed by LA950 that the average particle size was 4.0 μm and D90 was 6.2 μm. Then, the zeolite-polymer dispersion was placed in a 20 cm diameter evaporating dish. It was dripped, and about 8 g of water was dried with a microwave oven. After drying, the polymer-treated zeolite-containing solid adhering to the evaporating dish was scraped with a spatula and pulverized in a mortar so that the average composite particle size was 5.4 μm and D90 was 7.9 μm, to obtain a zeolite composite particle group. Table 1 shows the results of the cloth residue evaluation using this sample.
比較例3
ポリマーの種類を重量平均分子量2500のポリアクリル酸Naにし、比較例1と同様の方法でサンプルを作製し、同じ手法で評価を行った。評価結果を表1に示す。
Comparative Example 3
The polymer type was changed to polyacrylic acid Na having a weight average molecular weight of 2500, a sample was prepared by the same method as in Comparative Example 1, and evaluation was performed by the same method. The evaluation results are shown in Table 1.
比較例4
ポリマーの種類を重量平均分子量3500のポリアクリル酸Naにし、比較例1と同様の方法でサンプルを作製し、同じ手法で評価を行った。評価結果を表1に示す。
Comparative Example 4
The polymer type was changed to polyacrylic acid Na having a weight average molecular weight of 3500, a sample was prepared by the same method as in Comparative Example 1, and evaluation was performed by the same method. The evaluation results are shown in Table 1.
比較例5
ポリマーの種類を重量平均分子量4000のポリアクリル酸Naにし、比較例1と同様の方法でサンプルを作製し、同じ手法で評価を行った。評価結果を表1に示す。
Comparative Example 5
The polymer type was changed to polyacrylic acid Na having a weight average molecular weight of 4000, a sample was prepared by the same method as in Comparative Example 1, and evaluation was performed by the same method. The evaluation results are shown in Table 1.
比較例6
ポリマーの種類を重量平均分子量5000のアクリル酸/マレイン酸コポリマーNa(アクリル酸/マレイン酸=50/50、モル比)にし、比較例1と同様の方法でサンプルを作製し、同じ手法で評価を行った。評価結果を表1に示す。
Comparative Example 6
Samples were prepared in the same manner as in Comparative Example 1, and the evaluation was made in the same manner with the polymer type being acrylic acid / maleic acid copolymer Na (acrylic acid / maleic acid = 50/50, molar ratio) having a weight average molecular weight of 5000. went. The evaluation results are shown in Table 1.
比較例7
ポリマーの種類を重量平均分子量10000のアクリル酸/マレイン酸コポリマーNa(アクリル酸/マレイン酸=50/50、モル比)にし、比較例1と同様の方法でサンプルを作製し、同じ手法で評価を行った。評価結果を表1に示す。
Comparative Example 7
The polymer type was changed to acrylic acid / maleic acid copolymer Na (acrylic acid / maleic acid = 50/50, molar ratio) having a weight average molecular weight of 10,000, a sample was prepared in the same manner as in Comparative Example 1, and the evaluation was performed in the same manner. went. The evaluation results are shown in Table 1.
比較例8
実施例1と同様の方法で、但し重量平均分子量50000のポリアクリル酸Naの添加量を表1のように変更して、サンプルを作製し、同じ手法で評価を行った。評価結果を表1に示す。
Comparative Example 8
Samples were prepared in the same manner as in Example 1, except that the amount of polyacrylic acid Na having a weight average molecular weight of 50000 was changed as shown in Table 1 and evaluated by the same method. The evaluation results are shown in Table 1.
比較例9
特開平4−501730号公報の実施例1に準じた方法によりゼオライト複合粒子群を製造した。具体的には、造粒機(5Lレディゲミキサー)に、ゼオライト(平均粒子径4.0μm、D90が6.2μm)69.5質量部(ゼオライトとポリマーと水の合計100質量部中の割合、以下本例において同様)と粉末状ポリマー(ソカランCP5、BASF社製、アクリル酸/マレイン酸コポリマーNa、重量平均分子量70000)8.8質量部の割合で合計300g仕込み、主軸回転数11で20秒間粉体混合した。次いで、21.7質量部の水を270秒間で滴下し、滴下混合しながら5分間造粒した。造粒後、105℃で電気乾燥機で全質量が5%減量するまで乾燥した。乾燥後、約15%の粗粒を目開き1.4mmの篩で篩取った。得られたゼオライト複合粒子群の平均複合粒子径は571μm、D90は625μmであった。これを用いて比較例1と同じ手法で評価を行った。評価結果を表1に示す。
Comparative Example 9
A zeolite composite particle group was produced by a method according to Example 1 of JP-A-4-501730. Specifically, 69.5 parts by mass of zeolite (average particle size: 4.0 μm, D90: 6.2 μm) (a ratio in a total of 100 parts by mass of zeolite, polymer, and water) was added to a granulator (5 L Leedige mixer). In the following, the same applies to this example) and a powdery polymer (Socharan CP5, manufactured by BASF, acrylic acid / maleic acid copolymer Na, weight average molecular weight 70,000) at a ratio of 8.8 parts by mass, a total of 300 g was charged, and the spindle rotation speed was 11 Powder mixed for 2 seconds. Next, 21.7 parts by mass of water was added dropwise over 270 seconds, and granulated for 5 minutes while mixing dropwise. After granulation, it was dried at 105 ° C. with an electric dryer until the total mass was reduced by 5%. After drying, about 15% of coarse particles were sieved with a sieve having a mesh size of 1.4 mm. The average composite particle size of the obtained zeolite composite particle group was 571 μm, and D90 was 625 μm. Using this, evaluation was performed in the same manner as in Comparative Example 1. The evaluation results are shown in Table 1.
(比較例9の平均粒子径の測定)
JIS Z 8801のに規定の篩を用いて求めた。即ち目開きが2000μm、1400μm、1000μm、710μm、500μm、355μm、250μm、180μm、125μmである9段の篩と受け皿を用いて、ロータップマシン(HEIKO SEISAKUSHO製、タッピング:156回/分、ローリング:290回/分)に取り付け、100gの試料を10分間振動して篩い分けを行った後、受け皿、125μm、180μm、250μm、355μm、500μm、710μm、1000μm、1400μm、2000μmの順番に受け皿及び各篩い上に重量頻度を積算していくと、積算の重量頻度が50%以上となる最初の篩の目開きをaμmとし、またaμmよりも一段大きい篩の目開きをbμmとした時、受け皿からaμmの篩までの重量頻度の積算をc%、またaμmの篩上の重量頻度をd%とした場合、平均粒子径は、以下の式で算出される。
平均粒子径=10A
(Measurement of average particle diameter of Comparative Example 9)
It calculated | required using the sieve prescribed | regulated to JISZ8801. That is, using a 9-stage sieve and a saucer having openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm, and 125 μm, a low tap machine (made by HEIKO SEISAKUSHO, tapping: 156 times / minute, rolling: 290 times / minute), 100 g of the sample was shaken for 10 minutes and sieved, and then the pan and each sieve in the order of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, 2000 μm When the weight frequency is accumulated on the top, the opening of the first sieve where the accumulated weight frequency is 50% or more is aμm, and the opening of the sieve that is one step larger than aμm is bμm. C% on the frequency of weight up to the sieve, and on the aμm sieve If the amount frequency was d%, the average particle diameter is calculated by the following equation.
Average particle size = 10 A
実施例10
20Lのぺール缶に、ゼオライト粒子群(ゼオビルダー社製)(平均粒子径4.0μm、D90が6.2μm)4kgと重量平均分子量50000のポリアクリル酸Na水溶液16kg投入し、20kgのゼオライト・ポリマー分散液を5個、計100L作製した。ポリマー水溶液の濃度はゼオライトに対しポリマーの固形分が5質量%になるようにイオン交換水で調整し、次に、噴霧乾燥装置(坂本技研株式会社、SPRAY DRYER、MODEL TRS−5W2N)を用い、2流体ノズルを使用したエアー噴霧圧0.5MPa、送風量9kg/min、送風温度140℃、送液速度7kg/hrの条件で、ゼオライト・ポリマー分散液を噴霧乾燥し粉末(粒状組成物)を得た。次に得られた噴霧乾燥生地を(株)ダルトン社のアトマイザー型式 E II W 7.5で粉砕条件ハンマー周速60Hz、フィード周速10Hz、スクリーン0.7φで粉砕し、その後、ステンレス製のパットに移し、105℃の電気乾燥機で棚乾燥を行い、VLが1%以下になるよう約8時間棚乾燥した後、再度、アトマイザーで粉砕し、平均複合粒子径が4.0μm、D90が5.8μmのゼオライト複合粒子群を得た。この試料を用いて、布残留性評価を行った結果を表2に示す。
Example 10
Into a 20 L pail, 4 kg of zeolite particle group (Zeobuilder) (average particle size 4.0 μm, D90 is 6.2 μm) and 16 kg of polyacrylic acid Na aqueous solution with a weight average molecular weight of 50,000 were charged, and 20 kg of zeolite polymer A total of 100 L of five dispersions were prepared. The concentration of the polymer aqueous solution is adjusted with ion-exchanged water so that the solid content of the polymer is 5% by mass with respect to the zeolite, and then using a spray drying apparatus (Sakamoto Giken Co., Ltd., SPRAY DRYER, MODEL TRS-5W2N), The zeolite polymer dispersion is spray-dried under the conditions of an air spray pressure of 0.5 MPa using a two-fluid nozzle, a blowing rate of 9 kg / min, a blowing temperature of 140 ° C., and a feed rate of 7 kg / hr to obtain a powder (granular composition). Obtained. Next, the resulting spray-dried dough was pulverized with an atomizer model E II W 7.5 manufactured by Dalton Co., Ltd., with a hammer peripheral speed of 60 Hz, a feed peripheral speed of 10 Hz, and a screen of 0.7 φ, and then a stainless steel pad. And then shelf-dried with an electric dryer at 105 ° C., and shelf-dried for about 8 hours so that the VL becomes 1% or less, and then pulverized again with an atomizer, the average composite particle size is 4.0 μm, and D90 is 5 A zeolite composite particle group of .8 μm was obtained. Table 2 shows the results of cloth residue evaluation using this sample.
実施例11
ポリマーの種類を重量平均分子量50000のアクリル酸/マレイン酸コポリマーNa(アクリル酸/マレイン酸=50/50、モル比)にし、実施例10と同様の方法で平均複合粒子径が4.0μm、D90が5.8μmのゼオライト複合粒子群を得た。この試料を用いて、布残留性評価を行った結果を表2に示す。
Example 11
The polymer type was acrylic acid / maleic acid copolymer Na (acrylic acid / maleic acid = 50/50, molar ratio) having a weight average molecular weight of 50000, and the average composite particle size was 4.0 μm and D90 in the same manner as in Example 10. Obtained a zeolite composite particle group having a particle size of 5.8 μm. Table 2 shows the results of cloth residue evaluation using this sample.
実施例12
ポリマーの種類を重量平均分子量70000のアクリル酸/マレイン酸コポリマーNa(アクリル酸/マレイン酸=50/50、モル比)にし、実施例10と同様の方法で平均複合粒子径が4.0μm、D90が5.8μmのゼオライト複合粒子群を得た。この試料を用いて、布残留性評価を行った結果を表2に示す。
Example 12
Acrylic acid / maleic phosphate copolymer Na (acrylic acid / maleic acid = 50/50 molar ratio) of the weight average molecular weight 70,000 types of polymer, the average composite particle size 4.0μm in the same manner as in Example 10, A zeolite composite particle group with D90 of 5.8 μm was obtained. Table 2 shows the results of cloth residue evaluation using this sample.
比較例10
20Lのぺール缶にゼオライト粒子群(ゼオビルダー社製)(平均粒子径4.1μm、D90が6.2μm)4kgと、イオン交換水を16kg秤量し20kgのゼオライト分散液を5個、計100L作製した。次に作製したゼオライト分散液を、実施例10と同じ方法で平均複合粒子径が4.2μm、D90が6.2μmのゼオライト複合粒子群を得た、この試料を用いて、布残留性評価を行った結果を表2に示す。
Comparative Example 10
4kg of zeolite particle group (Zeobuilder Co., Ltd.) (average particle size 4.1μm, D90 = 6.2μm) in a 20L pail can and 16kg of ion-exchanged water were weighed and 5 pieces of 20kg zeolite dispersion were prepared to make 100L in total. did. Next, a zeolite composite particle group having an average composite particle size of 4.2 μm and D90 of 6.2 μm was obtained from the prepared zeolite dispersion by the same method as in Example 10. Using this sample, cloth residue evaluation was performed. The results are shown in Table 2.
実施例1〜12は前記の方法でポリマーによるゼオライト粒子の被覆の有無を確認したところ被覆されていることが確認できた。しかし比較例1、8、9、10は、ESCAによる表面分析を行ったところゼオライトの成分であるSiが検出された。 In Examples 1 to 12, the presence or absence of coating of the zeolite particles with the polymer was confirmed by the above method, and it was confirmed that the particles were coated. However, in Comparative Examples 1, 8, 9, and 10, when surface analysis was performed by ESCA, Si, which is a component of zeolite, was detected.
実施例13〜15及び比較例11〜12
レディゲミキサーFKM−130D((株)マツボー製)高速ミキサーを用いて、表3に示す組成の粉末洗剤組成物を35kg単位で製造した。このミキサーは攪拌羽根と解砕/分散用チョッパーに相当する剪断機を具備するものである。操作は以下のように実施した。得られた粉末洗剤組成物について、布残留性評価を行った結果を表3に示す。
Examples 13-15 and Comparative Examples 11-12
Using a Redige mixer FKM-130D (manufactured by Matsubo Co., Ltd.) high-speed mixer, powder detergent compositions having the compositions shown in Table 3 were produced in units of 35 kg. This mixer is equipped with a shearing machine corresponding to a stirring blade and a crushing / dispersing chopper. The operation was performed as follows. Table 3 shows the results of the cloth residue evaluation of the obtained powder detergent composition.
<粉体混合>
固体成分である、炭酸ナトリウム(ライト灰:セントラル硝子(株)製、平均粒径56.1μm)12.03重量部、硫酸ナトリウム(中性無水芒硝:四国化成(株)製、平均粒径110μm)4.10重量部及び蛍光染料0.11重量部を、レディゲミキサーにより、攪拌羽根回転数130rpm(周速度3.4m/s)、剪断機回転数2850rpm(周速度27m/s)の条件で1分間混合した。
<Powder mixing>
Solid component, sodium carbonate (light ash: manufactured by Central Glass Co., Ltd., average particle size 56.1 μm) 12.03 parts by weight, sodium sulfate (neutral anhydrous sodium sulfate: manufactured by Shikoku Kasei Co., Ltd., average particle size 110 μm) ) 4.10 parts by weight and 0.11 part by weight of the fluorescent dye were measured using a Redige mixer under conditions of stirring blade rotation speed 130 rpm (circumferential speed 3.4 m / s) and shearing machine rotation speed 2850 rpm (circumferential speed 27 m / s). For 1 minute.
<中和>
ミキサーを前記と同条件で作動させながら、予め混合させておいたLAS−S 5.80重量部及び98%硫酸0.40重量部を4分間で加えた。この間、ミキサージャケットには25℃の水を通して冷却した。この段階で、温度は最高75℃に達した。尚、この段階を通して、反応混合物は粒状であった。
<Neutralization>
While operating the mixer under the same conditions as described above, 5.80 parts by weight of LAS-S and 0.40 part by weight of 98% sulfuric acid which had been mixed in advance were added over 4 minutes. During this time, the mixer jacket was cooled by passing water at 25 ° C. At this stage, the temperature reached a maximum of 75 ° C. Throughout this stage, the reaction mixture was granular.
LAS−S添加後、引き続きミキサーを同条件で1分間作動させ、さらに脂肪酸(炭素数14〜18、タイター40〜50℃)を0.48重量部添加し、ミキサーを同条件で1分間作動させ、中和反応及び造粒操作を完結した。 After addition of LAS-S, the mixer is continuously operated for 1 minute under the same conditions, 0.48 parts by weight of fatty acid (14 to 18 carbon atoms, 40 to 50 ° C.) is added, and the mixer is operated for 1 minute under the same conditions. The neutralization reaction and the granulation operation were completed.
また、LAS−S添加開始直後より、中和反応完結までの間、通気(毎分300L)を行った。 Further, aeration (300 L / min) was performed immediately after the start of LAS-S addition until the completion of the neutralization reaction.
<液体成分の添加>
さらに非イオン性界面活性剤(炭素数12〜14の1級アルコールにEOを平均6モル付加させたもの)2.10重量部添加し、1分間混合後、続いて表3のゼオライト複合粒子群8.70重量部を加え、さらに2分間ミキサーを作動させた。
<Addition of liquid components>
Further, 2.10 parts by weight of a nonionic surfactant (primary alcohol having 12 to 14 carbon atoms added with 6 mol of EO on average) was added, mixed for 1 minute, and then the zeolite composite particles shown in Table 3 8.70 parts by weight were added and the mixer was run for an additional 2 minutes.
<アフターブレンド>
回転ドラムを用いて、酵素0.18重量部と前記で得られた洗剤組成物を混合し、更に香料0.07重量部を噴霧し、高嵩密度粉末洗剤組成物(嵩密度860g/L)を得た。
<After blend>
Using a rotating drum, 0.18 parts by weight of the enzyme and the detergent composition obtained above were mixed and 0.07 parts by weight of the fragrance was sprayed to obtain a high bulk density powder detergent composition (bulk density 860 g / L). Got.
ここで用いた成分は以下のものである。
・LAS−S:直鎖アルキルベンゼンスルホン酸ナトリウムの酸前駆体、花王株式会社製「ネオペレックスGS」
・LAS−Na:アルキル基の炭素数12〜14の直鎖アルキルベンゼンスルホン酸ナトリウム
・非イオン性界面活性剤:炭素数12〜14の1級アルコールにEOを平均6モル付加させたもの。
・脂肪酸:炭素数14〜18のアルキル基を有する脂肪酸、花王株式会社製「ルナックP−95」
・脂肪酸ナトリウム:炭素数14〜18のアルキル基を有する脂肪酸ナトリウム
・蛍光染料:チバガイギー社製「チノパールCBS−X」と住友化学工業株式会社製「ホワイテックスSA」とを1/1(質量比)で配合
・酵素:セルラーゼK(特開昭63−264699号公報記載)
The components used here are as follows.
LAS-S: acid precursor of linear alkylbenzene sulfonate sodium, “Neopelex GS” manufactured by Kao Corporation
LAS-Na: linear alkylbenzene sulfonate having 12 to 14 carbon atoms in the alkyl group Nonionic surfactant: A mixture of primary alcohols having 12 to 14 carbon atoms with an average of 6 mol of EO.
Fatty acid: Fatty acid having an alkyl group having 14 to 18 carbon atoms, “Lunac P-95” manufactured by Kao Corporation
・ Fatty acid sodium: Fatty acid sodium having an alkyl group having 14 to 18 carbon atoms ・ Fluorescent dye: Ciba Geigy's “Chino Pearl CBS-X” and Sumitomo Chemical Co., Ltd. “Wytex SA” 1/1 (mass ratio) Formulated with: Enzyme: Cellulase K (described in JP-A-63-264699)
表中の成分(一部)は以下のものである。
・LAS−Na:アルキル基の炭素数12〜14の直鎖アルキルベンゼンスルホン酸ナトリウム
・脂肪酸ナトリウム:炭素数14〜18のアルキル基を有する脂肪酸のナトリウム塩
The components (partial) in the table are as follows.
LAS-Na: linear alkylbenzene sulfonate having 12 to 14 carbon atoms in alkyl group Fatty acid sodium: sodium salt of fatty acid having an alkyl group having 14 to 18 carbon atoms
Claims (11)
平均粒子径が2〜10μmであり、
前記ゼオライト粒子群(a)100質量部に対する前記ポリカルボン酸系ポリマー(b)の割合が5質量部以上である、
ゼオライト複合粒子群。 A zeolite particle group (a) having an average particle diameter of 1 to 8 μm is mixed with an aqueous solution of a polycarboxylic acid polymer (b) having a weight average molecular weight of 20,000 to 300,000 and having a monomer structural unit having a carboxylic acid group. Thereafter, a zeolite composite particle group obtained by drying,
Average particle size of 2 10 .mu.m,
The ratio of the polycarboxylic acid polymer (b) to 100 parts by mass of the zeolite particle group (a) is 5 parts by mass or more.
Zeolite composite particles.
平均粒子径が2〜10μmであり、
体積基準90%(D90)の粒子径が12μm以下であり、
前記ゼオライト粒子群(a)100質量部に対する前記ポリカルボン酸系ポリマー(b)の割合が5質量部以上であり、
ゼオライト粒子がポリカルボン酸系ポリマーで被覆されてなる、
ゼオライト複合粒子群。 A zeolite composite particle group comprising a zeolite particle group (a) and a polycarboxylic acid-based polymer (b) having a monomer constituent unit having a carboxylic acid group and a weight average molecular weight of 20,000 to 300,000,
Average particle size of 2 10 .mu.m,
The volume diameter of 90% (D90) is 12 μm or less,
The ratio of the polycarboxylic acid polymer (b) to 100 parts by mass of the zeolite particle group (a) is 5 parts by mass or more,
Zeolite particles are coated with a polycarboxylic acid polymer,
Zeolite composite particles.
平均粒子径が2〜10μmであり、前記ゼオライト粒子群(a)100質量部に対する前記ポリカルボン酸系ポリマー(b)の割合が5質量部以上である、ゼオライト複合粒子群を得る、
ゼオライト複合粒子群の製造方法。 After mixing the zeolite particle group (a) having an average particle diameter of 1 to 8 μm with an aqueous solution of a polycarboxylic acid polymer (b) having a weight average molecular weight of 20,000 to 300,000 and having a monomer constituent unit having a carboxylic acid group Dry,
Obtaining a zeolite composite particle group having an average particle diameter of 2 to 10 μm and a ratio of the polycarboxylic acid polymer (b) to 5 parts by mass or more with respect to 100 parts by mass of the zeolite particle group (a);
A method for producing a zeolite composite particle group.
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