TWI394714B

TWI394714B - Surface- modified precipitated silicas

Info

Publication number: TWI394714B
Application number: TW093112935A
Authority: TW
Inventors: Hans Dieter Christian; Jurgen Schubert; Uwe Schmeier
Original assignee: Evonik Degussa Gmbh
Priority date: 2003-05-14
Filing date: 2004-05-07
Publication date: 2013-05-01
Also published as: TW200505790A; MY137950A; DE102004012090A1; CN102161845A; CN102161845B

Description

經表面處理之沉澱矽石Surface treated precipitated vermiculite

本發明係關於經表面處理之沉澱矽石，其表面用聚合物處理而改良，而使其特別適合作為減光劑，且關於彼之製法。The present invention relates to a surface-treated precipitated vermiculite whose surface is modified with a polymer to make it particularly suitable as a light-reducing agent, and to which it is produced.

表面的改良沉澱矽石係長久已知的，且供作生產功能增進材料而用於乳矽酮橡膠、噴墨應用或塗層材料(作為減光劑)。The surface of the modified precipitated vermiculite is known for a long time and is used as a production function promoting material for chyle ketone rubber, inkjet applications or coating materials (as a light reducing agent).

如此EP 0 922 671敘述製備疏水性沉澱矽石的沉澱，其中將聚乙烯蠟乳液加入慣常的、乾燥的沉澱矽石，接著在分級磨機或對衝型射流液體床磨機之中將其碾磨。Thus, EP 0 922 671 describes the preparation of a precipitate of hydrophobic precipitated vermiculite in which a polyethylene wax emulsion is added to a conventional, dry precipitated vermiculite, which is then milled in a classifier mill or a hedging jet liquid bed mill. .

DE 25 13 608敘述一種將細微分散的矽石作疏水化之方法，經由於200至300℃的溫度下，在流化狀態之中使用有機矽烷處理乾燥的矽石。DE 25 13 608 describes a process for the hydrophobization of finely divided vermiculite by treating the dried vermiculite with organodecane in a fluidized state at a temperature of from 200 to 300 °C.

為簡化疏水化方法，EP 0 341 383提出將矽酮油乳液引入沉澱矽石的懸浮液中。In order to simplify the hydrophobization process, EP 0 341 383 proposes to introduce an oxime oil emulsion into a suspension of precipitated vermiculite.

DE 24 35 860描述相似的方法，其中將沉澱矽石的懸浮液與視需要預先壓縮的有機鹵素矽烷反應。於經由過濾將固體已分離之後，將其加熱到300至400℃的溫度，且接著碾磨。A similar process is described in DE 24 35 860, in which a suspension of precipitated vermiculite is reacted with an organohalogen decane which is pre-compressed as required. After the solid has been separated by filtration, it is heated to a temperature of 300 to 400 ° C and then milled.

沉澱矽石頻繁地用於塗覆表面的減光。如此減光的塗層膜，從各種角度觀察應當展現最小的光澤。因為親水性沉澱矽石可能在塗層材料中傾向有嚴重的沈降，且因此再攪動若非不可能也將是困難的，通常使用蠟塗覆的沉澱矽石作為減光劑。矽石表面的蠟塗層可實質上改良沈降行為。若減光劑完全沉降，該沈降將是最小的，其可再次攪動而不會耗費許多能量。Precipitated vermiculite is frequently used for dimming the coated surface. The coating film thus dimmed should exhibit minimal gloss when viewed from various angles. Because of hydrophilicity Precipitated vermiculite may tend to have severe settling in the coating material, and thus re-agitation will be difficult if not impossible, typically using wax coated precipitated vermiculite as a light reducing agent. The wax coating on the vermiculite surface can substantially improve the settling behavior. If the lightening agent is completely settled, the settling will be minimal, which can be agitated again without consuming a lot of energy.

當使用澄淸塗層材料，必須使塗層材料的透明度不因加入減光劑而有所影響。When a clear coating material is used, the transparency of the coating material must not be affected by the addition of the light reducing agent.

因此，本發明之目的在提供經表面處理之矽石，當彼在澄淸塗層材料中用作為減光劑，將導致塗層材料性質的改良。本發明同樣地提供一種製備經表面處理之矽石的方法。Accordingly, it is an object of the present invention to provide a surface treated vermiculite which, when used as a light reducing agent in a ruthenium coating material, will result in an improvement in the properties of the coating material. The present invention likewise provides a method of preparing a surface treated vermiculite.

出人意外地據發現本發明矽石的可改良塗層材料的透明度，且具有與那些以聚乙烯蠟(PE蠟)塗覆的矽石至少同樣良好的沈降性質。因此其具有優於會頻繁引起澄淸塗層材料的霧狀的經蠟塗覆的減光劑。Surprisingly, it has been found that the vermiculite of the present invention has improved transparency of the coating material and has at least as good settling properties as those of the vermiculite coated with polyethylene wax (PE wax). It therefore has a wax-coated dimmer that is superior to the mist that would frequently cause a clear coating material.

據發現可經由用特別的聚合物塗覆而改良沉澱矽石，其塗層材料的折射率在介於1,4000至1,5000，且將本發明沉澱矽石加入其中的塗層可展現顯著的透明度。相較於其中包含慣常的，PE-蠟塗覆的矽石減光劑且帶有折射率在介於1,4000至1,5000的塗層材料，其中包含本發明矽石作為減光劑的相同塗層材料，可展現大幅改良的透明度，甚至在液體形式中，且沈降性質也很顯著。使用慣常減光劑作減光的澄淸塗層材料，一般在液體形式中呈霧狀，而使用本發明沉澱矽石作減光的澄淸塗層材料甚至在液體形式中也是澄淸且透明的。It has been found that the precipitated vermiculite can be modified by coating with a special polymer having a refractive index of from 1,4000 to 150,000, and the coating to which the precipitated vermiculite of the present invention is added can exhibit remarkable Transparency. Compared to a conventional, PE-wax coated vermiculite light-reducing agent and having a coating material having a refractive index between 1,4000 and 150,000, including the vermiculite of the present invention as a light-reducing agent The same coating material exhibits a greatly improved transparency, even in liquid form, and the settling properties are significant. Use customary subtraction The ruthenium coating material which is used for the reduction of the light agent is generally in the form of a mist in a liquid form, and the ruthenium coating material which is reduced by the use of the precipitated vermiculite of the present invention is also clear and transparent even in a liquid form.

本發明據此提供一種表面已使用聚合物處理之沉澱矽石；當相較於內含5%經以聚乙烯蠟處理的參考沉澱矽石之相同塗層材料時，在內含有5重量%此類經處理之沉澱矽石的澄淸塗層材料至少可使透光度改進20%，該塗層材料的折射率n_D 20=1.4492。The present invention accordingly provides a precipitated vermiculite having a surface treated with a polymer; when compared to the same coating material containing 5% of the reference precipitated vermiculite treated with polyethylene wax, it contains 5% by weight of this The clear coating material of the treated precipitated vermiculite can at least improve the transmittance by 20%, and the refractive index of the coating material is n _D 20 = 1.4492.

本發明進一步提供該經表面處理之沉澱矽石之製備方法，其中包括：a)於弱酸至鹼性的條件之下使用酸化劑沉澱鹼金屬矽酸鹽溶液，b)進一步加入酸化劑將pH設定在7至2，以生成矽石懸浮液，c)經由過濾而分離此沉澱固體，及d)經由緩慢乾燥而乾燥此固體，例如採用旋轉管乾燥器或板乾燥器，或經由快速乾燥而乾燥此固體，例如採用噴霧乾燥器、旋轉快速乾燥器，使此產物的殘餘濕氣含量在少於10%，其中包括步驟e)使用聚合物處理此沉澱矽石，選擇聚合物的用量及本質而使經處理之沉澱矽石在相較於內含5%經以聚乙蠟處理的參考沉澱矽石之相同塗層材料時，在內含有5重量%此類經處理之沉澱矽石的澄淸塗層材料至少可使透光度改進20%，該塗層材料的折射率n_D 20=1.4492。The invention further provides a preparation method of the surface-treated precipitated vermiculite, which comprises: a) precipitating an alkali metal citrate solution with an acidifying agent under weak acid to alkaline conditions, b) further adding an acidifying agent to set the pH At 7 to 2 to form a vermiculite suspension, c) to separate the precipitated solid by filtration, and d) to dry the solid via slow drying, for example using a rotary tube dryer or a plate dryer, or drying by rapid drying The solid, for example using a spray dryer, a rotary quick dryer, has a residual moisture content of less than 10%, including step e) treating the precipitated vermiculite with a polymer, selecting the amount and nature of the polymer. The treated precipitated vermiculite is contained in an amount of 5% by weight of such treated precipitated vermiculite compared to the same coating material containing 5% of the reference precipitated vermiculite treated with polyethene wax. The coating material can at least improve the transmittance by 20%, and the coating material has a refractive index n _D 20 = 1.4492.

本發明經表面處理之矽石為沉澱矽石，其上已塗覆聚合物，且結果可使得當相較於內含5%經以聚乙烯蠟處理的參考沉澱矽石之相同塗層材料時，在內含有5重量%此類經處理之沉澱矽石的澄清塗層材料至少可使透光度改進20%，該塗層材料的折射率n_D 20=1.4492。此透光度改進宜至少為25%，尤其是30%。經以聚乙烯蠟處理的參考沉澱矽石宜為ACEMATT OK 412，Degussa的商業產品，其具有依據12/02產品資訊傳單上的規格說明，其全文在此加入作為參考文獻。作為參考的沉澱矽石，其也可能使用具有相同未處理矽石的沉澱矽石，且用聚乙烯蠟作塗覆。The surface treated vermiculite of the present invention is a precipitated vermiculite on which a polymer has been coated, and as a result, when compared to the same coating material containing 5% of the reference precipitated vermiculite treated with polyethylene wax. The clear coating material containing 5% by weight of such treated precipitated vermiculite can at least improve the transmittance by 20%, and the coating material has a refractive index n _D 20 = 1.4492. This improvement in transparency is preferably at least 25%, especially 30%. The reference precipitated vermiculite treated with polyethylene wax is preferably ACEMATT OK 412, a commercial product of Degussa, having specifications according to the 12/02 product information leaflet, which is incorporated herein by reference in its entirety. As a reference precipitated vermiculite, it is also possible to use precipitated vermiculite having the same untreated vermiculite and coated with polyethylene wax.

依據12/02的產品資訊傳單，ACEMATT^® OK 412具有如下的物理化學(PC,physiochemical)數據： 1)基於乾燥物質2)基於點燃物質According to the product information leaflet of 12/02, ACEMATT ^® OK 412 has the following physical chemistry (PC, physiochemical) data: 1) based on dry matter 2) based on igniting substance

進一步由以下物理化學數據說明本發明矽石：顆粒分佈d50：1-50μm，優先範圍在1-40μm、1-30μm、2-20μm、及3-15μmFurther, the present invention describes the vermiculite of the present invention: particle distribution d50: 1-50 μm, preferential range of 1-40 μm, 1-30 μm, 2-20 μm, and 3-15 μm

油吸收值DBP：100-600g/100g，優先範圍在150-500g/100g、200-450g/100g、及250-400g/100gOil absorption value DBP: 100-600g/100g, preferential range is 150-500g/100g, 200-450g/100g, and 250-400g/100g

C含量：1-20%，優先範圍在1-10%及2-8%C content: 1-20%, priority range is 1-10% and 2-8%

西爾斯數(Sears number)V₂ ：<25ml/5gSears number V ₂ :<25ml/5g

作為表面處理用的聚合物，有可能使用聚有機矽氧烷或改良的聚有機矽氧烷。此改良的聚有機矽氧烷尤其是聚醚-改良的與丙烯酸酯-及/或聚丙烯酸酯-改良的聚有機矽氧烷。亦可使用聚烷氧基矽氧烷。As the polymer for surface treatment, it is possible to use a polyorganosiloxane or a modified polyorganosiloxane. The modified polyorganosiloxane is especially a polyether-modified acrylate- and/or polyacrylate-modified polyorganosiloxane. Polyalkoxy oxiranes can also be used.

一項本發明較佳的具體實施例中，使用具有以下通用結構的聚有機矽氧烷：其中Y=-OH、-OR或Y=H₅ C₂ -O-(C₂ H₄ O)_m -，H₇ C₃ -O-(C₃ H₆ O)_m -或 R=烷基，尤其是甲基或乙基，R₂ =烷基，R₃ =烷基，a=0-100，b=0-100，c=0-100，d=0-100，m=0-100且k=0-100。In a preferred embodiment of the invention, a polyorganosiloxane having the following general structure is used: Wherein Y=-OH, -OR or Y=H ₅ C ₂ -O-(C ₂ H ₄ O) _m -, H ₇ C ₃ -O-(C ₃ H ₆ O) _m - or R = alkyl, especially methyl or ethyl, R ₂ = alkyl, R ₃ = alkyl, a = 0-100, b = 0-100, c = 0-100, d = 0-100, m =0-100 and k=0-100.

本發明另一項較佳的具體實施例使用具有以下通用結構的聚有機矽氧烷：其中R₁ 為甲基基團或 Another preferred embodiment of the invention uses a polyorganosiloxane having the following general structure: Wherein R ₁ is a methyl group or

及/或且單元a之總和=0至100，單元b之總和=0至15，在基團R₁ 甲中基對烷氧基基團之比例少於50：且若a=0時b ≧1，且b=0時≧5。更詳細地，尤其是關於製備此類聚矽氧烷，可見於DE 36 27 782 A1。該專利申請案的全文在此加入作為參考文獻。And/or And the sum of the units a = 0 to 100, the sum of the units b = 0 to 15, the ratio of the base to alkoxy groups in the group R ₁ methyl is less than 50: and if a = 0, b ≧ 1, and When b=0, ≧5. In more detail, in particular with regard to the preparation of such polyoxyalkylenes, it can be found in DE 36 27 782 A1. The entire disclosure of this patent application is incorporated herein by reference.

烷基基團為意指帶有1至100個碳原子的直鏈或支鏈烷基基團，較佳帶有1至25，更佳帶有1至10個碳原子，以及帶有1至15個碳原子的環烷基基團。此烷基基團可含有一或更多雙鍵或三鍵，且各個原子可取代為雜原子如O、N或S。The alkyl group means a straight or branched alkyl group having 1 to 100 carbon atoms, preferably 1 to 25, more preferably 1 to 10 carbon atoms, and 1 to A cycloalkyl group of 15 carbon atoms. The alkyl group may contain one or more double or triple bonds, and each atom may be substituted with a hetero atom such as O, N or S.

在本發明方法的步驟a)與b)中，所使用的水溶性鹼金屬矽酸鹽溶液宜為矽酸鈉(水玻璃)，其密度在約1.343kg/l，其重量分率為27.3%的SiO₂ 與7.9%的Na₂ O。所使用的酸化劑可為任何無機酸，特別為濃硫酸(96%H₂ SO₄ )、或CO₂ 。In steps a) and b) of the process according to the invention, the water-soluble alkali metal citrate solution used is preferably sodium citrate (water glass) having a density of about 1.343 kg/l and a weight fraction of 27.3%. SiO ₂ with 7.9% Na ₂ O. The acidulant used can be any mineral acid, especially concentrated sulfuric acid (96% H ₂ SO ₄ ), or CO ₂ .

在步驟a)中In step a)

於攪拌下將各成分，例如記述於DE 31 44 299中的各成分相互混合。DE 31 44 299之全文在此加入作為參考文獻。視需要可將酸化劑與水玻璃同時加入水或矽酸鈉的起始用料中。應確保維持在弱酸至鹼性pH下進行沉澱。pH尤其宜在6-12。視需要可在固定的pH或固定的鹼數之下進行沉澱。The components, for example the components described in DE 31 44 299, are mixed with each other with stirring. The entire text of DE 31 44 299 is incorporated herein by reference. The acidifying agent and water glass may be simultaneously added to the starting material of water or sodium citrate as needed. It should be ensured that precipitation is maintained at a weak acid to alkaline pH. The pH is especially preferably 6-12. Precipitation can be carried out at a fixed pH or a fixed number of bases as needed.

在步驟b)中In step b)

加入酸化劑，在此案例中尤其是酸化劑已用於沉澱中，以設定pH在酸性或中性的範圍(pH 7至2)。An acidulant is added, in this case in particular an acidulant has been used in the precipitation to set the pH in the acidic or neutral range (pH 7 to 2).

在步驟c)中In step c)

矽石存在於懸浮液中，視需要於等待時間0至90分鐘之後，較佳為15至60分鐘，經由過濾而分離，且用去離子水淸洗使其到達中性。The vermiculite is present in the suspension, optionally after a waiting time of 0 to 90 minutes, preferably 15 to 60 minutes, separated by filtration, and rinsed with deionized water to reach neutrality.

在步驟d)中In step d)

經由快速乾燥將此固體乾燥，例如採用噴霧乾燥器、旋轉快速乾燥器，或經由緩慢乾燥將此固體乾燥，例如採用旋轉管乾燥器或板乾燥器，使此產物的殘餘濕氣含量在少於10%。Drying the solid via rapid drying, for example using a spray dryer, rotary spin dryer, or drying the solid via slow drying, for example using a rotary tube dryer or a plate dryer, such that the product has a residual moisture content of less than 10%.

可即時在不同點進行表面處理(步驟e))。Surface treatment can be performed at different points in time (step e)).

在具體實施例1)之中In the specific embodiment 1)

於本發明的方法步驟e)中，將0.5-30重量%的表面處理聚合物引入矽石懸浮液中，在步驟b)中將pH調整至7-2。此加入期間宜介於1至30分鐘之間，尤其是5至15分鐘之間，且宜在步驟a)中沉澱之反應溫度進行，即尤其是在50至90℃，較佳為50-65℃。接著如記述於步驟c)與d)中，經由過濾而分離此經表面處理之矽石，且乾燥。In step e) of the process according to the invention, from 0.5 to 30% by weight of the surface-treated polymer is introduced into the vermiculite suspension, and in step b) the pH is adjusted to 7-2. This period of addition is preferably between 1 and 30 minutes, in particular between 5 and 15 minutes, and preferably carried out at the reaction temperature of the precipitation in step a), i.e. especially at 50 to 90 ° C, preferably 50-65. °C. Next, as described in steps c) and d), the surface-treated vermiculite is separated by filtration and dried.

在具體實施例2)之中In the specific embodiment 2)

採用如記述於步驟c)中的過濾的方法，分離依據步驟a)及b)所沉澱得到的本發明的矽石，視需要使用去離子水淸洗，然後使用水或硫酸或使用水與硫酸之混合物將其再懸浮，且然後執行步驟e)，將0.5-30重量%的表面處理聚合物引入此懸浮液中，且在噴霧乾燥器之中將生成的懸浮液噴霧，而使得在乾燥操作期間發生表面處理。此外，也可考慮經由噴嘴而同時引入矽石懸浮液與矽氧烷。在200-500℃噴霧乾燥，使產物的殘餘濕氣含量少於10%。作噴霧的矽石懸浮液的固含量可至高達25重量%。The vermiculite of the present invention precipitated according to steps a) and b) is separated by filtration as described in step c), optionally washed with deionized water, then with water or sulfuric acid or with water and sulfuric acid. The mixture is resuspended, and then step e) is performed, 0.5-30% by weight of the table The surface treatment polymer is introduced into the suspension, and the resulting suspension is sprayed in a spray dryer so that surface treatment occurs during the drying operation. In addition, it is also conceivable to simultaneously introduce a vermiculite suspension and a decane via a nozzle. Spray drying at 200-500 ° C gives the product a residual moisture content of less than 10%. The vermiculite suspension as a spray can have a solids content of up to 25% by weight.

在具體實施例3)之中In the specific embodiment 3)

如敘述於本發明方法的步驟a)-d)中，製備且乾燥矽石。接著在步驟e)中，將此乾燥沉澱矽石混合以0.5-30重量%的表面處理聚合物，且將二者完全地混合。於0至120分鐘內，較佳於0至60分鐘內，更佳於0至30分鐘內將聚合物加入。進一步於20-150℃將混合物混合0-2小時。宜在20-100℃進行混合，更佳在20-80℃。混合操作宜進行0-1 h，且更佳進行0-30分鐘。As described in steps a)-d) of the process of the invention, vermiculite is prepared and dried. Next in step e), the dry precipitated vermiculite is mixed with 0.5-30% by weight of the surface treated polymer and the two are thoroughly mixed. The polymer is added in 0 to 120 minutes, preferably in 0 to 60 minutes, more preferably in 0 to 30 minutes. The mixture was further mixed at 0 to 150 ° C for 0 to 2 hours. It is preferred to carry out the mixing at 20 to 100 ° C, more preferably at 20 to 80 ° C. The mixing operation should be carried out for 0-1 h, and more preferably for 0-30 minutes.

在本發明製備方法中，於反應期間，加入的聚合物宜使聚合物對矽石的比例為0.5g：100g至30g：100g，尤其是2g：100g至20 8：100g，特別在3g：100g至13g：100g。In the preparation process of the invention, during the reaction, the polymer is preferably added in a ratio of polymer to vermiculite of 0.5 g: 100 g to 30 g: 100 g, especially 2 g: 100 g to 20 8: 100 g, especially at 3 g: 100 g. To 13g: 100g.

作為表面處理聚合物，有可能在本發明方法中使用聚有機矽氧烷或改良的聚有機矽氧烷。此改良的聚有機矽氧烷尤其是聚醚-改良的及丙烯酸酯-及/或聚丙烯酸酯-改良的聚有機矽氧烷。亦可使用聚烷氧基矽氧烷。As a surface treatment polymer, it is possible to use polyorganosiloxane or modified polyorganosiloxane in the process of the invention. The modified polyorganosiloxane is especially a polyether-modified and acrylate- and/or polyacrylate-modified polyorganosiloxane. Polyalkoxy oxiranes can also be used.

一項本發明較佳的具體實施例中，使用聚有機矽氧烷其具有以下的一般結構：其中Y=-OH、-OR或Y=H₅ C₂ -O-(C₂ H₄ O)_m -，H₇ C₃ -O-(C₃ H₆ O)_m -或 R=烷基，尤其是甲基或乙基，R₂ =烷基，R₃ =烷基，a=0-100，b=0-100，c=0-100，d=0-100，m=0-100且k=0-100。In a preferred embodiment of the invention, a polyorganosiloxane is used which has the following general structure: Wherein Y=-OH, -OR or Y=H ₅ C ₂ -O-(C ₂ H ₄ O) _m -, H ₇ C ₃ -O-(C ₃ H ₆ O) _m - or R = alkyl, especially methyl or ethyl, R ₂ = alkyl, R ₃ = alkyl, a = 0-100, b = 0-100, c = 0-100, d = 0-100, m =0-100 and k=0-100.

本發明另一項較佳的具體實施例，係使用具有以下通用結構的聚有機矽氧烷：其中R₁ 為甲基基團或 Another preferred embodiment of the invention employs a polyorganosiloxane having the following general structure: Wherein R ₁ is a methyl group or

及/或且單元a之總和=0至100，單元b之總和=0至15，在基團R₁ 中甲基對烷氧基基團之比例少於50：1，且若a=0時b≧1，且若b=0時a≧5。更詳細地，尤其是關於製備此類聚矽氧烷，可見於DE 36 27 782 A1。DE 3 627 782 A1之全文在此加入作為參考文獻。And/or And the sum of the units a = 0 to 100, the sum of the units b = 0 to 15, the ratio of the methyl group to the alkoxy group in the group R ₁ is less than 50:1, and if a = 0, b≧1 And if b=0, a≧5. In more detail, in particular with regard to the preparation of such polyoxyalkylenes, it can be found in DE 36 27 782 A1. The entire text of DE 3 627 782 A1 is incorporated herein by reference.

視需要在具體實施例1)及2)中也可加入乳化輔助劑，例如LA-S 687(TEGOgmbH)。此將特別地適合不具水溶性的機矽化合物。Emulsifying adjuvants such as LA-S 687 (TEGOgmbH) may also be added in specific examples 1) and 2) as needed. This will be particularly suitable for machine compounds which are not water soluble.

為達成所需要之顆粒分佈，須要在步驟f)中將已乾燥的經表面處理之矽石碾磨且同時分類。此研磨可用商購的一般的互流式磨機(例如購自Alpine或Netzsch-Condux)進行。In order to achieve the desired particle distribution, the dried surface treated vermiculite needs to be milled and simultaneously classified in step f). This grinding can be carried out using a commercially available general interflow mill (for example from Alpine or Netzsch-Condux).

為了避免超大尺寸或小塊，於經表面處理之沉澱矽石已乾燥之後或於研磨步驟f)之後或於研磨步驟f)期間，可有利地分離除去直徑50μm以上的微粒，較佳者大於30μm的微粒，尤其是大於20μm的微粒。取決於減光劑的細微度，此項分離可經由各種方式完成，例如對應的篩子或分粒機裝置，亦可將其整合在磨機中。In order to avoid oversize or small pieces, it may be advantageous to separate and remove particles having a diameter of 50 μm or more, preferably more than 30 μm, after the surface-treated precipitated vermiculite has been dried or after the grinding step f) or during the grinding step f). Particles, especially those larger than 20 μm. Depending on the subtlety of the lightening agent, this separation can be accomplished in a variety of ways, such as a corresponding screen or classifier device, or it can be integrated into the mill.

本發明沉澱矽石的物理化學數據係由以下方法測定：The physicochemical data of the precipitated vermiculite of the present invention is determined by the following method:

測定塗層材料的透光度Determination of the transmittance of the coating material

透光度的測量，係使用UV/Vis分光光度計Specord 200，產自Analytik JenagmbH，在1 cm石英小室中，於在室溫下，以空氣作為參考。狹縫寬度與進階長度為2 nm。The transmittance was measured using a UV/Vis spectrophotometer Specord 200 from Analytik JenagmbH in a 1 cm quartz chamber at room temperature with air as a reference. The slit width and the advanced length are 2 nm.

為達此目的，引入折射率n_D 20=1.4492的酸硬化(AC)淸漆，其具有與以下一的般組成物作為起始用料： 30.2重量%的二甲苯15.1重量%的乙氧基丙醇15.1重量%的乙醇39.6重量%的普拉斯多(Plastopal)BT，60%強度(尿素-甲醛樹脂，內含有胺基甲酸酯基團且經過短鏈醇類醚化，產自BASF AG，Ludwigshafen)For this purpose, an acid hardening (AC) enamel having a refractive index n _D 20 = 1.4492 was introduced, which had the following composition as a starting material: 30.2% by weight of xylene 15.1% by weight of ethoxylate Propyl alcohol 15.1% by weight ethanol 39.6% by weight Plasto BT, 60% strength (urea-formaldehyde resin containing urethane groups and etherified by short-chain alcohols, produced by BASF AG, Ludwigshafen)

且加入2.5g的相應的減光劑(經表面處理之矽石)。在室溫下使用槳式攪拌器以2000轉/分鐘的轉速攪拌10分鐘，將此減光劑分散在50g的AC淸漆之中。在190毫升PE混合燒杯之中，於室溫下執行分散。攪拌器的槳直徑為43mm。接著將此新鮮製備的分散液置於1 cm石英小室中且用UV/Vis光譜紀錄其介於190與1100 nm之間的透光度。And 2.5 g of the corresponding light reducing agent (surface treated vermiculite) was added. The light-reducing agent was dispersed in a 50 g AC lacquer by stirring at room temperature for 10 minutes at 2000 rpm using a paddle stirrer. Dispersion was carried out at room temperature in a 190 ml PE mixing beaker. The paddle diameter of the agitator is 43 mm. This freshly prepared dispersion was then placed in a 1 cm quartz cell and its transmittance between 190 and 1100 nm was recorded using a UV/Vis spectrum.

測定矽石的改良西爾斯數(Sears number)Determination of the modified Sears number of meteorites (Sears number)

在pH 6至pH 9之範圍中，使用氫氧化鉀溶液，經由滴定法測量矽石，有可能測定改良的西爾斯數(如下稱為西爾斯數V₂ )，而測量自由羥基基團之數目。In the range of pH 6 to pH 9, using a potassium hydroxide solution, the vermiculite is measured by titration, and it is possible to measure the modified Sears number (hereinafter referred to as Sears number V ₂ ), and measure the free hydroxyl group. The number.

測定方法係基於以下化學反應，其中"Si"-OH代表矽醇基團："Si"-OH+NaCl → "Si"-ONa+HCl HCl+KOH → KCl+H₂ O。The measurement method is based on the following chemical reaction, wherein "Si"-OH represents a sterol group: "Si"-OH + NaCl → "Si"-ONa + HCl HCl + KOH → KCl + H ₂ O.

步驟step

在IKA萬用磨機M 20(550 W；20 000 rpm)之中，將10.00g的濕氣含量在5±1%之粉末、圓珠或顆粒形式的矽石碾磨60秒。可能必須經由在乾燥箱之中於105℃乾燥，或經由均勻潮濕化而而調整濕氣含量。於室溫下稱重2.50g的如此處理之矽石置入250毫升的滴定容器中，且加入60.0毫升的甲醇(分析用)(p.a.,pro analysis)。試樣已完全溼潤，加入40.0毫升的去離子水，且使用Ultra Turrax T 25(攪拌器軸KV-18G，18mm直徑)將混合物分散30秒，採用18 000 rpm的旋轉速度。使用100毫升的去離子水將黏附至容器邊緣與攪拌器上的微粒試樣沖洗入懸浮液中，且在恆溫水浴中將懸浮液調整至25℃。10.00 g of vermiculite in the form of powder, beads or granules having a moisture content of 5 ± 1% was milled for 60 seconds in an IKA universal mill M 20 (550 W; 20 000 rpm). It may be necessary to adjust the moisture content by drying at 105 ° C in a dry box or by uniform humidification. Weigh at room temperature The 2.00 g of this treated vermiculite was placed in a 250 ml titration vessel and 60.0 ml of methanol (for analysis) (p.a., pro analysis) was added. The sample was completely wetted, 40.0 ml of deionized water was added, and the mixture was dispersed for 30 seconds using an Ultra Turrax T 25 (Agitator Shaft KV-18G, 18 mm diameter) with a rotational speed of 18 000 rpm. The microparticle sample adhered to the edge of the container and the stirrer was rinsed into the suspension using 100 ml of deionized water, and the suspension was adjusted to 25 ° C in a constant temperature water bath.

pH計(購自Krick，模式：766 pH計Calimatic，附有溫度而感應器)及pH電極(合併購自Schott，型號N7680的電極)，在室溫下使用緩衝溶液溶液(pH 7.00及9.00)校正。首先於25℃使用pH計測量起始懸浮液的pH，且然後取決於結果而使用氫氧化鉀溶液(0.1mol/l)或氫鹽酸溶液(0.1mol/l)將pH值調至6.0。達到pH6.00所消耗的以毫升計之KOH或HCl溶液用量記為V₁ '。pH meter (purchased from Krick, mode: 766 pH meter Calimatic, with temperature sensor) and pH electrode (combined from Schott, model N7680 electrode), using buffer solution at room temperature (pH 7.00 and 9.00) Correction. The pH of the starting suspension was first measured using a pH meter at 25 ° C, and then the pH was adjusted to 6.0 using a potassium hydroxide solution (0.1 mol/l) or a hydrochloric acid solution (0.1 mol/l) depending on the result. The amount of KOH or HCl solution in milliliters consumed to reach pH 6.00 is recorded as V ₁ '.

之後計量加入20.0毫升的氯化鈉溶液(250.00g的NaCl(分析用)(p.a.)，用去離子水加到1公升)。使用0.1莫耳/公升KOH，然後繼續滴定使pH為9.00。達到pH 9.00所消耗的以毫升計之KOH溶液記為V₂ '。Then 20.0 ml of sodium chloride solution (250.00 g of NaCl (for analysis) (pa) was added, and 1 liter of deionized water was added). 0.1 mol/liter KOH was used and then the titration was continued to bring the pH to 9.00. The KOH solution in milliliters consumed to reach pH 9.00 is designated as V ₂ '.

接著首先將體積V₁ ’與V₂ '標準化而得到1g理論試樣重量，且用因子5擴大，得到V₁ 與以ml/5g單位計的西爾斯數V₂ 。在各案例中重複進行此項測定。Next, the volumes V ₁ ' and V ₂ ' are first normalized to obtain 1 g of the theoretical sample weight, and expanded by a factor of 5 to obtain V ₁ and a Sears number V _{2 in} units of ml/5 g. This measurement was repeated in each case.

DBP吸收DBP absorption

如下依據標準DIN 53601測定DBP吸收(DBP數目)為沉澱矽石吸收度之測量值：The DBP absorption (number of DBP) is determined as follows based on the standard DIN 53601 as a measure of the precipitation of precipitated vermiculite:

步驟step

將12.50g的呈粉末或圓珠形式的，濕氣含量在0-10%(可合適地經由在乾燥箱之中於105℃乾燥而調整濕氣含量)之矽石，引入柏班得吸收計"E"(物件編號279 061)的捏合機腔室中。針對顆粒形式，使用的3.15至1mm篩子分層(不銹鋼篩子係購自Retsch)(使用塑膠壓舌板，經由3.15-mm孔隙尺寸篩子將顆粒溫和加壓)。在室溫下，經由柏班得T 90/50 Dosimat，採用4ml/min之速率，使用連續混合(捏合機葉片的周邊速度：125 rpm)將酞酸二丁酯逐滴加入混合物中。其混合加入僅須要小量的力，且可經由數位顯示器監測。接進測定結束時，混合物變得糊狀，可由所需要的力有陡急的增加而看出。當顯示讀出的600數字(扭矩為0.6 Nm)，將關閉捏合機與DBP進料兩者的電氣接觸。針對DBP進料的同步運動係聯接至數位計數器，而使得可讀取以毫升計的消耗DBP。Introducing 12.50 g of vermiculite in the form of powder or beads, having a moisture content of 0-10% (which can be suitably adjusted by drying in a drying oven at 105 ° C to adjust the moisture content), into a Paipan absorption meter "E" (object number 279 061) in the kneading machine chamber. For the pellet form, the 3.15 to 1 mm sieve used was layered (stainless steel screen was purchased from Retsch) (using a plastic tongue depressor, the pellets were gently pressurized via a 3.15-mm pore size sieve). Dibutyl phthalate was added dropwise to the mixture via Celite T 90/50 Dosimat at a rate of 4 ml/min using continuous mixing (peripheral speed of the kneader blades: 125 rpm). The mixing requires only a small amount of force and can be monitored via a digital display. At the end of the measurement, the mixture becomes mushy and can be seen by a sharp increase in the required force. When the read 600 number (torque is 0.6 Nm) is displayed, the electrical contact between the kneader and the DBP feed will be turned off. The synchronized motion for the DBP feed is coupled to the digital counter so that the consumed DBP in milliliters can be read.

評估Evaluation

DBP吸收係以g/100g報導，且用DBP的消耗測量由下式計算。DBP於20℃的密度典型為1.047g/ml。The DBP absorption is reported in g/100g and is calculated by the following equation using the DBP consumption measurement. The density of DBP at 20 ° C is typically 1.047 g/ml.

以g/100g計的DBP吸收=以毫升計之DBP消耗*以 g/ml計的DBP密度* 100/12.5gDBP absorption in g/100g = DBP consumption in milliliters* DBP density in g/ml* 100/12.5g

此DBP吸收係針對無水、乾燥的矽石而定義。當使用潮濕的沉澱矽石，此特性必須經由如下的校正表作校正。This DBP absorption is defined for anhydrous, dry vermiculite. When using wet precipitated vermiculite, this property must be corrected via the calibration table below.

將對應於水含量的校正值加入實驗的DBP值中；例如水含量在5.8%，意指針對DBP吸收將加入33g/100g。A correction value corresponding to the water content is added to the DBP value of the experiment; for example, the water content is 5.8%, and the meaning pointer to the DBP absorption will be added 33 g/100 g.

針對酞酸二丁酯吸收的校正表Correction table for the absorption of dibutyl phthalate -無水-- waterless -

測定矽石的濕氣含量Determination of moisture content of vermiculite

依據此ISO 787-2線上方法及工作，於105℃乾燥2小時之後，測定矽石的揮發性分層(如下為簡單化稱為"濕氣含量")。此乾燥損失一般主要包含水濕氣。According to this ISO 787-2 online method and work, after drying at 105 ° C for 2 hours, the volatile stratification of vermiculite was determined (hereinafter referred to as "moisture content" as simplification). This drying loss generally consists primarily of moisture.

步驟step

稱取10g的呈粉末、圓珠或顆粒形式之矽石，準確到0.1毫克(試樣重量E)，置入帶有磨砂玻璃蓋的乾燥玻璃稱重舟皿(直徑8 cm，高3 cm)中。將蓋子打開，在乾燥箱之中於105±2℃將試樣乾燥2小時。之後在一附有矽石凝膠作為乾燥劑的乾燥器之中將此稱重舟皿密封且冷卻至室溫。測定最終重量A。Weigh 10g of vermiculite in the form of powder, beads or granules to the nearest 0.1 mg (sample weight E) and place the dry glass weighing boat with a frosted glass cover (8 cm in diameter and 3 cm high) in. The lid was opened and the sample was dried at 105 ± 2 ° C for 2 hours in a dry box. The weighing boat was then sealed in a desiccator with a vermiculite gel as a desiccant and cooled to room temperature. The final weight A was determined.

以%計的濕氣含量測定為(以g計的E-以g計的A)^＊ 100%/以g計的E。The moisture content in % is determined as (E in g - A in g) ^* 100% / E in g.

重複進行測量。Repeat the measurement.

測定燃燒損失：Determination of combustion loss:

於1000℃乾燥2小時之後，採用DIN 55 921/3.4，ISO 3262After drying at 1000 ° C for 2 hours, use DIN 55 921/3.4, ISO 3262

測定d50Determination d50

經由雷射繞射儀(Coulter)測定聚集尺寸分佈Determination of aggregate size distribution via a laser diffractometer (Coulter)

裝置：Device:

雷射繞射儀器LS 230，CoulterLaser diffraction instrument LS 230, Coulter

德國班得利公司(Bandelin)超音波桿，類型HD 2200，帶有DH 13g角Bandelin Ultrasonic Rod, type HD 2200, with DH 13g angle

冷卻浴80毫升Cooling bath 80 ml

艾班多(Eppendorf)公司移液管5毫升Eppendorf pipette 5 ml

離心玻璃，高7 cm，3 cmCentrifugal glass, 7 cm high, 3 cm

培養皿，高度4 cm，7 cmPetri dish, height 4 cm, 7 cm

戴瓦(Dewar)真空絕熱容器，高21 cm，4 cmDewar vacuum insulated container, 21 cm high, 4 cm

數位溫度計，準確度±0.1 KDigital thermometer with an accuracy of ±0.1 K

試劑：Reagents:

乙醇，(分析用)(p.a.)，默克公司Ethanol, (for analysis) (p.a.), Merck

崔頓(Triton)x-100，默克公司Triton x-100, Merck

六偏磷酸鈉，貝克公司(Baker)Sodium hexametaphosphate, Baker

試樣製備：Sample preparation:

將顆粒放置在研缽之中且將粗糙顆粒塊壓碎，不研磨。The granules were placed in a mortar and the coarse granules were crushed without grinding.

稱取1g未老化的矽石(製作後不超過10天)，置入帶有滾邊的30毫升玻璃容器，且加入20毫升的分散溶液(取20g的六偏磷酸鈉，用去礦物質水加到1000毫升)。接著將試樣放置在冷卻浴中，其可防止懸浮液快速升溫，且使用超音波處理1分鐘(20 W功率，80%脈衝)。Weigh 1 g of unaged vermiculite (not more than 10 days after preparation), place in a 30 ml glass container with piping, and add 20 ml of a dispersion solution (take 20 g of sodium hexametaphosphate, add demineralized water) To 1000 ml). The sample was then placed in a cooling bath which prevented the suspension from heating up quickly and was treated with ultrasonic for 1 minute (20 W power, 80% pulse).

針對各矽石連續地製備三份分散溶液試樣。Three samples of the dispersion solution were continuously prepared for each vermiculite.

將懸浮液放置在附有磁性攪拌器培養皿之中，直到試樣注入液體模組中，以預防任何沈降。Place the suspension in a petri dish with a magnetic stirrer until the test Sample into the liquid module to prevent any settling.

步驟：step:

在開始測量之前，將儀器與液體模組加熱至少30分鐘，且將模組自動輕洗10分鐘(功能選單條"控制/沖洗")。Before starting the measurement, heat the instrument and the liquid module for at least 30 minutes, and automatically lightly wash the module for 10 minutes (function menu "Control/Flush").

在Coulter軟體的對控制條上，經由功能選單項目"測定"選擇檔案窗"計算操作模式"，且定義折射率(液體折射率實數=1.332；材料折射率實數=1.46，虛數=0.1)。On the control strip of the Coulter software, select the file window "Calculation Operation Mode" via the function menu item "Measurement" and define the refractive index (liquid refractive index real number = 1.332; material refractive index real number = 1.46, imaginary number = 0.1).

在檔案窗"測量循環"中，將泵速度之水準設定在26%且將超音波功率設定在3%。超音波的啟動項目為"於試樣加入期間"，"在各次測量之前"，及"於測量期間"。In the file window "measurement cycle", the pump speed level is set at 26% and the ultrasonic power is set at 3%. The starting items for the ultrasonic wave are "during the sample addition period", "before each measurement", and "during the measurement period".

額外地在檔案窗中選擇以下項目：補償測量(1×每日)調整背景測量設定測量濃度鍵入試樣訊息鍵入測量訊息開始2個測定自動漂洗使用PIDS數據Additionally select the following items in the file window: Compensation measurement (1 × daily) adjustment background measurement setting measurement concentration type sample message type measurement information start 2 measurements automatic rinsing using PIDS data

當校正完成，將試樣加入。加入分散的矽石直到光吸收達到約45%，且儀器報告OK。使用Fraunhofer模式進行測量，使用雷射繞射儀器LS 230的標準軟體，其係產自Coulter公司。When the calibration is complete, the sample is added. The dispersed vermiculite was added until the light absorption reached approximately 45% and the instrument reported OK. Use the Fraunhofer mode For line measurement, the standard software for the laser diffraction instrument LS 230 was used, which was produced by Coulter.

針對加入的各試樣進行三次60秒的重複測定。Repeated measurements were performed three times for each of the added samples for 60 seconds.

由原始數據，使用繪圖軟體基於體積分佈而計算粒徑分佈。From the raw data, the particle size distribution was calculated based on the volume distribution using the drawing software.

測定C含量Determination of C content

裝置：Device:

C-mat 500，產自Strohlein Instruments公司分析天平帶有蓋子的瓷舟皿鑷子測量匙C-mat 500, manufactured by Strohlein Instruments, analytical balance, porcelain boat with lid, measuring spoon

試劑：Reagents:

Euro分析對照組試樣077-2(Strohlein Instruments公司)氧Euro analysis control sample 077-2 (Strohlein Instruments) oxygen

步驟step

對照組試樣之測量Measurement of control sample

首先就對照組試樣進行測量。為達此目的，在分析天平上，於在完全烘烤且冷卻的瓷舟皿中稱取0.14-0.18g的試樣。因為天平與C-mat耦合，當啟動開始鍵，將留下重量。必須在30秒之中將此舟皿推入燃燒管中央。當燃燒完成，測量圖將轉化成脈衝，且經由電腦評估。可進行二或更多個測定。若須要，儀器因子必須重新設定。此因子係依據以下公式計算： First, the measurement was performed on the control sample. To this end, 0.14-0.18 g of the sample was weighed in a fully baked and cooled porcelain boat on an analytical balance. Because the balance is coupled to the C-mat, the weight will be left when the start button is activated. The boat must be pushed into the center of the combustion tube in 30 seconds. When the combustion is complete, the measurement map will be converted to a pulse and evaluated via a computer. Two or more measurements can be made. The instrument factor must be reset if necessary. This factor is calculated according to the following formula:

矽石試樣之測量Measurement of vermiculite samples

於測定因子之後，測量矽石試樣。為達此目的，在瓷舟皿中稱取0.04-0.05g的各種矽石，且用瓷蓋將舟皿覆蓋。接著採用如針對對照組試樣的相同方式測試矽石試樣。當誤差>0.005%，作第三次測量，且若須要，進行其它的測且計算平均值。After the factor was measured, the vermiculite sample was measured. To this end, 0.04-0.05 g of various vermiculite was weighed in a porcelain boat, and the boat was covered with a porcelain cover. The vermiculite samples were then tested in the same manner as for the control samples. For the third measurement when the error is >0.005%, and if necessary, perform other measurements and calculate the average.

評估Evaluation

依據以下公式計算碳含量： Calculate the carbon content according to the following formula:

其中：P=脈衝F=因子E=以克計的起始重量Where: P = pulse F = factor E = starting weight in grams

結果報告Result report

結果呈現為%C，到小數兩位。The result is presented as %C, to two decimal places.

附註Note

可依據Strohlein Instruments公司的操作用法說明而操作C-m於500。The C-m can be operated at 500 according to the operating instructions of Strohlein Instruments.

以下實施例係用以闡明本發明且並非用以限制在其保護範圍，如在本專利市申請專利範圍中所敘明的保護範圍。The following examples are intended to clarify the invention and are not intended to limit the scope of the invention, as set forth in the scope of the patent application.

實施例Example 實施例1-3Examples 1-3

經由DE 1767332之方法製備矽石：Preparation of vermiculite by the method of DE 1767332:

在可加熱的具有攪拌單元的120公升沉澱容器中，注入80公升的水，且用5.5公升的水玻璃(密度=1.346g/l，SiO₂ 含量=27.3%，Na₂ 0含量=7.9%)將鹼數目調至20。將此起始用料加熱至85℃。在此溫度進行全部沉澱。之後，同時平行地計量加入下列二者，使用計量速率為207ml/min的水玻璃，與計量速率為45ml/min的硫酸(50%)，所採取的方式係使其中鹼數目不改變。於30分鐘之後，連接剪切單位，且於後續的沉澱期間剪切沉澱懸浮液，所採用的強度係使沉澱結束時可獲得微粒分佈d50=7μm。於45分鐘之後，計量加入水玻璃與硫酸中斷30分鐘。然後重新開始計量加入水玻璃與硫酸，且採用如上述相同速率。於再45分鐘之後，關閉計量加入水玻璃，且計量加入硫酸直到達到3.5的pH值。然後結束沉澱。In a heatable 120 liter sedimentation vessel with a stirring unit, 80 liters of water was injected, and with 5.5 liters of water glass (density = 1.346 g/l, SiO ₂ content = 27.3%, Na ₂ 0 content = 7.9%) Adjust the number of bases to 20. This starting material was heated to 85 °C. All precipitation was carried out at this temperature. Thereafter, the following two were metered in simultaneously, using water glass having a metering rate of 207 ml/min and sulfuric acid (50%) having a metering rate of 45 ml/min, in such a manner that the number of bases therein did not change. After 30 minutes, the shearing unit was attached and the precipitation suspension was sheared during the subsequent precipitation, using a strength such that a particle distribution d50 = 7 μm was obtained at the end of the precipitation. After 45 minutes, the metered addition of water glass and sulfuric acid was interrupted for 30 minutes. The metering of water glass and sulfuric acid was then restarted and at the same rate as described above. After a further 45 minutes, the metered water glass was switched off and the sulphuric acid was metered in until a pH of 3.5 was reached. The precipitation is then ended.

接著一次將列於下表中所有聚有機矽氧烷乳液之用量(TEGO Foamex 1435，TEGOgmbH)加入矽石懸浮液中，且在高溫下繼續攪拌30分鐘。之後由過濾而分離如此經塗覆的矽石，淸洗、乾燥、碾磨、且經由DE 17 67 332之方法分類。The amount of all polyorganoprenee emulsions (TEGO Foamex 1435, TEGOgmbH) listed in the table below was then added to the vermiculite suspension and stirring was continued for 30 minutes at elevated temperature. The thus coated vermiculite is then separated by filtration, rinsed, dried, milled and classified according to the method of DE 17 67 332.

表1顯示經由上述方法製備的三種經表面處理之矽石，與有未處理矽石ACEMATT HK 400(可公開自由得到的Degussa公司的商業產品)的比較結果。實施例1-3為換用不同用量聚有機矽氧烷處理之矽石。Table 1 shows the results of comparison of three surface-treated vermiculite prepared by the above method with untreated vermiculite ACEMATT HK 400 (a commercially available product of Degussa, which is publicly available). Examples 1-3 were replaced with vermiculite treated with different amounts of polyorganosiloxane.

實施例4Example 4

經由塗層材料的透光度測定，可比較本發明減光劑與先前技藝中的減光劑。為達此目的，製備三種塗層混合物，將2.5g的各種減光劑加入50g的下列一般組成的酸硬化(AC)淸漆(折射率n_D 20=1.4492)中： 30.2重量%的二甲苯15.1重量%的乙氧基丙醇15.1重量%的乙醇39.6重量%的普拉斯多(Plastopal)BT，60%強度(尿素-甲醛樹脂，其中含有胺基甲酸酯基團且經短鏈醇類作醚化，BASF AG，Ludwigshafen)The light reducing agent of the present invention can be compared to the light reducing agent of the prior art by the transmittance measurement of the coating material. For this purpose, three coating mixtures were prepared, 2.5 g of various light reducing agents were added to 50 g of the following general composition of acid hardening (AC) enamel paint (refractive index n _D 20 = 1.4492): 30.2% by weight of xylene 15.1% by weight of ethoxypropanol 15.1% by weight of ethanol 39.6% by weight of Plasto BT, 60% strength (urea-formaldehyde resin containing urethane groups and short chain alcohols Etherification, BASF AG, Ludwigshafen)

試樣製備：Sample preparation:

進行測量，在室溫下使用槳式攪拌器以2000轉/分鐘，將2.5g的減光劑分散在50g的AC淸漆之中10分鐘。於室溫下在180毫升PE混合燒杯之中進行分散。攪拌器槳的直徑為43mm。Measurements were carried out, and 2.5 g of the light-reducing agent was dispersed in 50 g of the AC paint for 10 minutes at room temperature using a paddle stirrer at 2000 rpm. Dispersion was carried out in a 180 ml PE mixing beaker at room temperature. The agitator paddle has a diameter of 43 mm.

測量：measuring:

紀錄新鮮製備的分散液的UV/Vis光譜，介於190與1100nm之間的透光度。採用Specord 200 UV/Vis分光光度計作測定，其係購自Analytik JenagmbH，在1 cm石英小室中，於在室溫下測定，以空氣作為參考。狹縫寬度及步驟長度為2 nm。The UV/Vis spectrum of the freshly prepared dispersion was recorded, with a transmission between 190 and 1100 nm. A Specord 200 UV/Vis spectrophotometer was used for the measurement, which was purchased from Analytik JenagmbH in a 1 cm quartz chamber at room temperature with air as a reference. Slit width and The step length is 2 nm.

依據以上的說明，測量依據實施例2或3的內含減光劑之塗層材料或PE-蠟塗覆的減光劑ACEMATT OK 412的透光度值。ACEMATT OK 412為可開自由地得到的商業產物，產自Degussa AG公司，對應於12/02的產品資訊傳單。此外，也測量未加減光劑的未攙雜淸漆透光度值。According to the above description, the transmittance value of the coating material containing the light-reducing agent according to Example 2 or 3 or the PE-wax-coated light-reducing agent ACEMAT OK 412 was measured. ACEMATT OK 412 is a freely available commercial product from Degussa AG, corresponding to the product newsletter for 12/02. In addition, the transmittance of the unfilled enamel paint without the addition of a light reducing agent was also measured.

得到的透光度值如下： The obtained transmittance values are as follows:

如顯見於以上表中，內含由實施例2或3的本發明減光劑之塗層材料的透光度值，非常接近於那些未攙雜，未減光的淸漆。據此，此類塗層材料非常澄淸且透明。As is apparent from the above table, the transmittance of the coating material containing the light-reducing agent of the present invention of Example 2 or 3 is very close to those of the undoped, undiluted enamel. Accordingly, such coating materials are very clear and transparent.

內含一般的、普遍用的減光劑ACEMATT OK 412之塗層材料，所顯示的透光度較差，至少差35%，此顯示塗層材料有嚴重的霧狀。The coating material of ACEMAT OK 412, which contains the general and commonly used light-reducing agent, exhibits poor transmittance, at least 35%, which indicates that the coating material has a severe haze.

如下圖1與2顯示內含依據實施例2或3減光劑的酸硬化(AC)淸漆，在各案例中相較於內含ACEMATT OK 412的相同AC淸漆。可非常淸楚看出，內含本發明減光劑的塗層材料實質上較淸晰。Figures 1 and 2 below show an acid hardening (AC) lacquer containing the lightening agent according to Example 2 or 3, in each case compared to the same AC lacquer containing ACEMATT OK 412. It can be seen very clearly that the dimming of the invention is included The coating material of the agent is substantially clear.

接著將參照圖示詳細說明本發明，其中圖1為比較內含ACEMATT OK 412的酸硬化(AC)淸漆，與內含實施例2減光劑的AC淸漆兩者之霧化現象；圖2為比較內含ACEMATT OK 412的酸硬化(AC)淸漆，與內含實施例3減光劑的AC淸漆兩者之霧化現象。The invention will now be described in detail with reference to the accompanying drawings in which FIG. 1 is a comparison of the atomization phenomenon of an acid hardening (AC) enamel containing ACEMATT OK 412 and an AC enamel containing the light absorbing agent of Example 2; 2 is a comparison of the atomization phenomenon of both the acid hardening (AC) enamel containing ACEMATT OK 412 and the AC enamel containing the light absorbing agent of Example 3.

Claims

一種表面經聚合物處理之沉澱矽石，其使得內含5重量%的此類經處理之沉澱矽石的澄清塗層材料，相較於內含5重量%經以聚乙烯蠟處理的沉澱矽石之相同澄清塗層材料而言，至少可使透光度改進20%，該澄清塗層材料的折射率n_D 20=1.4492，其中該聚合物為聚有機矽氧烷或改良的聚有機矽氧烷；以及該聚有機矽氧烷具有以下通用結構其中Y=-OH、-OR或Y=H₅ C₂ -O-(C₂ H₄ O)_m -,H₇ C₃ -O-(C₃ H₆ O)_m -或 R=烷基，R₂ =烷基， R₃ =烷基，a=0-100，b=0-100，c=0-100，d=0-100，m=0-100且k=0-100。A polymer-treated precipitated vermiculite having a clear coating material containing 5% by weight of such treated precipitated vermiculite compared to 5% by weight of precipitated tantalum treated with polyethylene wax For the same clear coating material of stone, at least the transmittance can be improved by 20%, and the refractive index of the clear coating material is n _D 20 = 1.4492, wherein the polymer is a polyorganosiloxane or a modified polyorganoquinone. Oxytomane; and the polyorganosiloxane has the following general structure Wherein Y=-OH, -OR or Y=H ₅ C ₂ -O-(C ₂ H ₄ O) _m -, H ₇ C ₃ -O-(C ₃ H ₆ O) _m - or R = alkyl, R ₂ = alkyl, R ₃ = alkyl, a = 0-100, b = 0-100, c = 0-100, d = 0-100, m = 0-100 and k = 0 -100.

如申請專利範圍第1項之沉澱矽石，其中R為甲基或乙基。 A precipitated vermiculite according to claim 1 wherein R is a methyl group or an ethyl group.

如申請專利範圍第1項之沉澱矽石，其中該聚有機矽氧烷具有以下通用結構其中R₁ 為甲基基團或及/或且單元a之總和=0至100，單元b之總和=0至15，在基團R₁ 中甲基對烷氧基基團之比例少於50：1，且若a=0時b≧1，且若b=0時a≧5。The precipitated vermiculite according to claim 1, wherein the polyorganosiloxane has the following general structure Wherein R ₁ is a methyl group or And/or And the sum of the units a = 0 to 100, the sum of the units b = 0 to 15, the ratio of the methyl group to the alkoxy group in the group R ₁ is less than 50:1, and if a = 0, b≧1 And if b=0, a≧5.

如申請專利範圍第1項之沉澱矽石，其以下列物理化學數據為特徵：d50：1-50μm DBP：100-600g/100g C含量：1-20%。 The precipitated vermiculite of claim 1 is characterized by the following physicochemical data: d50: 1-50 μm DBP: 100-600 g/100 g C content: 1-20%.

如申請專利範圍第1至4項中任一項之沉澱矽石，其西爾斯數V₂ <25ml/5g。The precipitated vermiculite according to any one of claims 1 to 4, which has a Sears number V ₂ <25 ml/5 g.

如申請專利範圍第4項之沉澱矽石，其中顆粒分佈d50為1-40μm。 The precipitated vermiculite according to item 4 of the patent application, wherein the particle distribution d50 is 1-40 μm.

如申請專利範圍第4項之沉澱矽石，其中油吸收DBP為200-500g/100g。 The precipitated vermiculite according to item 4 of the patent application, wherein the oil absorption DBP is 200-500 g/100 g.

如申請專利範圍第4項之沉澱矽石，其中C含量為1-10%。 For example, the precipitated vermiculite of claim 4, wherein the C content is 1-10%.

如申請專利範圍第1至4項中任一項之沉澱矽石，當相較於內含5重量%經以聚乙烯蠟處理的沉澱矽石之相同塗層材料時，內含5重量%的此類經處理之沉澱矽石的澄清塗層材料至少可使透光度改進25%，該澄清塗層材料的折射率n_D 20=1.4492。The precipitated vermiculite according to any one of claims 1 to 4, which contains 5% by weight when compared with the same coating material containing 5% by weight of precipitated vermiculite treated with polyethylene wax. The clear coating material of such treated precipitated vermiculite can at least improve the transmittance by 25%, and the refractive index material of the clear coating material has a refractive index n _D 20 = 1.4492.

如申請專利範圍第1至4項中任一項之沉澱矽石，內含5重量%的此類經處理之沉澱矽石的澄清塗層材料，相較於內含5重量%經以聚乙烯蠟處理的沉澱矽石之相同塗層材料而言，至少可使透光度改進30%，該澄清塗層材料的折射率n_D 20=1.4492。The precipitated vermiculite according to any one of claims 1 to 4, which contains 5% by weight of a clear coating material of such treated precipitated vermiculite, compared to 5% by weight of the polyethylene For the same coating material of the wax-treated precipitated vermiculite, at least the transmittance can be improved by 30%, and the refractive index of the clear coating material is n _D 20 = 1.4492.

如申請專利範圍第1至4項中任一項之沉澱矽石，相對於以ACEMATT^® OK 412作為參考的沉澱矽石，係具有改良的透光度。The precipitated vermiculite according to any one of claims 1 to 4 has improved transmittance compared to precipitated vermiculite with ACEMATT ^® OK 412 as a reference.

如申請專利範圍第1至4項中任一項之沉澱矽石，相對於含有相同未處理沉澱矽石但經塗覆聚乙烯蠟者以作為參考沉澱矽石，係具有改良透光度。 The precipitated vermiculite according to any one of claims 1 to 4 has improved light transmittance relative to the precipitated vermiculite containing the same untreated precipitated vermiculite but coated with polyethylene wax as a reference.

一種製備經表面處理的疏水化沉澱矽石之方法，其包括a)於弱酸至鹼性的條件之下使用酸化劑沉澱鹼金屬矽酸鹽溶液，b)進一步加入酸化劑將pH設定在7至2，以生成矽石懸浮液，c)經由過濾而分離此沉澱固體，及d)經由緩慢乾燥或經由快速乾燥而乾燥此固體，使此產物的殘餘濕氣含量少於10%，其中包括在步驟e)中使用聚合物處理此沉澱矽石，選擇聚合物的用量及性質而使經處理之沉澱矽石，使內含有5重量%此類經處理之沉澱矽石的澄清塗層材料相較於內含5重量%經以聚乙蠟處理的沉澱矽石之相同塗層材料而言，至少可使透光度改進20%，該澄清塗層材料的折射率n_D 20=1.4492，其中該聚合物為聚有機矽氧烷或改良的聚有機矽氧烷；以及該聚有機矽氧烷具有以下通用結構其中Y=-OH、-OR或Y=H₅ C₂ -O-(C₂ H₄ O)_m -，H₇ C₃ -O-(C₃ H₆ O)_m -或 R=烷基，R₂ =烷基，R₃ =烷基，a=0-100，b=0-100，c=0-100，d=0-100，m=0-100且k=0-100。A method for preparing a surface-treated hydrophobized precipitated vermiculite comprising: a) precipitating an alkali metal citrate solution with an acidifying agent under mild acid to alkaline conditions, b) further adding an acidifying agent to set the pH to 7 2, to form a vermiculite suspension, c) to separate the precipitated solid by filtration, and d) to dry the solid via slow drying or by rapid drying, so that the product has a residual moisture content of less than 10%, including In step e), the precipitated vermiculite is treated with a polymer, and the amount and nature of the polymer are selected to treat the precipitated vermiculite to a clear coating material containing 5% by weight of such treated precipitated vermiculite. For the same coating material containing 5% by weight of the precipitated vermiculite treated with polyethene wax, at least the transmittance can be improved by 20%, and the refractive index of the clear coating material is n _D 20=1.4492, wherein The polymer is a polyorganosiloxane or a modified polyorganosiloxane; and the polyorganosiloxane has the following general structure Wherein Y=-OH, -OR or Y=H ₅ C ₂ -O-(C ₂ H ₄ O) _m -, H ₇ C ₃ -O-(C ₃ H ₆ O) _m - or R = alkyl, R ₂ = alkyl, R ₃ = alkyl, a = 0-100, b = 0-100, c = 0-100, d = 0-100, m = 0-100 and k = 0 -100.

如申請專利範圍第13項之方法，其中R為甲基或乙基。 The method of claim 13, wherein R is methyl or ethyl.

如申請專利範圍第13項之方法，其中該聚有機矽氧烷具有以下通用結構其中R₁ 為甲基基團或及/或且單元a之總和=0至100，單元b之總和=0至15，在基團R₁ 中甲基對烷氧基基團之比例少於50：1，且若a=0時b≧1，且若b=0時a≧5。The method of claim 13, wherein the polyorganosiloxane has the following general structure Wherein R ₁ is a methyl group or And/or And the sum of the units a = 0 to 100, the sum of the units b = 0 to 15, the ratio of the methyl group to the alkoxy group in the group R ₁ is less than 50:1, and if a = 0, b≧1 And if b=0, a≧5.

如申請專利範圍第13項之方法，其中該緩慢乾燥係採用旋轉管乾燥器或板乾燥器進行，且該快速乾燥係採用噴霧乾燥器、旋轉快速乾燥器進行。 The method of claim 13, wherein the slow drying is carried out using a rotary tube dryer or a plate dryer, and the rapid drying is carried out using a spray dryer or a rotary quick dryer.

如申請專利範圍第13項之方法，其中在步驟e)中將0.5-30重量%的具有以下通用結構的聚有機矽氧烷：其中Y=-OH、-OR或Y=H₅ C₂ -O-(C₂ H₄ O)_m -，H₇ C₃ -O-(C₃ H₆ O)_m -或 R=烷基，R₂ =烷基，R₃ =烷基，a=0-100，b=0-100，c=0-100，d=0-100，m=0-100且k=0-100，加入步驟b)中pH調整至7-2的矽石懸浮液。The method of claim 13, wherein in step e), from 0.5 to 30% by weight of the polyorganosiloxane having the following general structure: Wherein Y=-OH, -OR or Y=H ₅ C ₂ -O-(C ₂ H ₄ O) _m -, H ₇ C ₃ -O-(C ₃ H ₆ O) _m - or R = alkyl, R ₂ = alkyl, R ₃ = alkyl, a = 0-100, b = 0-100, c = 0-100, d = 0-100, m = 0-100 and k = 0 -100, adding the vermiculite suspension adjusted to pH 7-2 in step b).

如申請專利範圍第17項之方法，其中R為甲基或乙基。 The method of claim 17, wherein R is methyl or ethyl.

如申請專利範圍第13項之方法，其中在步驟e)中將0.5-30重量%的具有以下通用結構的聚有機矽氧烷：其中R₁ 為甲基基團或及/或且單元a之總和=0至100，單元b之總和=0至15，在基團R₁ 中甲基對烷氧基基團之比例少於50：1，且若a=0時b≧1，且若b=0時a≧5，加入步驟b)中pH調整至7-2的矽石懸浮液。The method of claim 13, wherein in step e), from 0.5 to 30% by weight of the polyorganosiloxane having the following general structure: Wherein R ₁ is a methyl group or And/or And the sum of the units a = 0 to 100, the sum of the units b = 0 to 15, the ratio of the methyl group to the alkoxy group in the group R ₁ is less than 50:1, and if a = 0, b≧1 And if b = 0 a a, add the vermiculite suspension adjusted to pH 7-2 in step b).

如申請專利範圍第13-19項中任何一項之方法，其中步驟e)中之加入是在1至30分鐘期間且在攪拌下進行。 The method of any one of claims 13 to 19, wherein the addition in step e) is carried out during 1 to 30 minutes with stirring.

如申請專利範圍第13-19項中任何一項之方法，其中在步驟e)中矽石懸浮液之溫度為20-100℃。 The method of any one of claims 13-19, Wherein the temperature of the vermiculite suspension in step e) is from 20 to 100 °C.

如申請專利範圍第13項之方法，其中根據步驟c)中經由過濾而分離且任意地使用去離子水作清洗的矽石，係使用水或硫酸或使用水與硫酸之混合物將其再懸浮，且接著在步驟e)中，將0.5-30重量%的聚有機矽氧烷或改良的聚有機矽氧烷加入此懸浮液中，且將生成的懸浮液乾燥。 The method of claim 13, wherein the vermiculite separated according to the step c) by filtration and optionally using deionized water is resuspended by using water or sulfuric acid or using a mixture of water and sulfuric acid. And then in step e), 0.5 to 30% by weight of polyorganosiloxane or modified polyorganosiloxane is added to the suspension and the resulting suspension is dried.

如申請專利範圍第22項之方法，其中採用噴霧乾燥法來乾燥該生成的懸浮液。 The method of claim 22, wherein the sprayed suspension is used to dry the resulting suspension.

如申請專利範圍第13項之方法，其中根據步驟c)中經由過濾而分離且任意地使用去離子水作清洗的矽石，係使用水或硫酸或使用水與硫酸之混合物將其再懸浮，且接著在步驟e)中，將0.5-30重量%的具有以下通用結構的聚有機矽氧烷：其中Y=-OH、-OR或Y=H₅ C₂ -O-(C₂ H₄ O)_m -，H₇ C₃ -O-(C₃ H₆ O)_m -或 R=烷基，R₂ =烷基，R₃ =烷基，a=0-100，b=0-100，c=0-100，d=0-100，m=0-100且k=0-100加入此懸浮液中，且將生成的懸浮液乾燥。The method of claim 13, wherein the vermiculite separated according to the step c) by filtration and optionally using deionized water is resuspended by using water or sulfuric acid or using a mixture of water and sulfuric acid. And then in step e), 0.5 to 30% by weight of polyorganosiloxane having the following general structure: Wherein Y=-OH, -OR or Y=H ₅ C ₂ -O-(C ₂ H ₄ O) _m -, H ₇ C ₃ -O-(C ₃ H ₆ O) _m - or R = alkyl, R ₂ = alkyl, R ₃ = alkyl, a = 0-100, b = 0-100, c = 0-100, d = 0-100, m = 0-100 and k = 0 -100 was added to this suspension and the resulting suspension was dried.

如申請專利範圍第24項之方法，其中R為甲基或乙基。 The method of claim 24, wherein R is methyl or ethyl.

如申請專利範圍第24項之方法，其中採用噴霧乾燥法來乾燥該生成的懸浮液。 The method of claim 24, wherein the sprayed suspension is used to dry the resulting suspension.

如申請專利範圍第13項之方法，其中根據步驟c)中經由過濾而分離且任意地使用去離子水作清洗的矽石，係使用水或硫酸或使用水與硫酸之混合物將其再懸浮，且接著在步驟e)中，將0.5-30重量%的具有以下通用結構的聚有機矽氧烷：其中R₁ 為甲基基團或及/或且單元a之總和=0至100，單元b之總和=0至15，在基團R₁ 中甲基對烷氧基基團之比例少於50：1，且若a=0時b≧1，且若b=0時a≧5加入此懸浮液中，且將生成的懸浮液乾燥。The method of claim 13, wherein the vermiculite separated according to the step c) by filtration and optionally using deionized water is resuspended by using water or sulfuric acid or using a mixture of water and sulfuric acid. And then in step e), 0.5 to 30% by weight of polyorganosiloxane having the following general structure: Wherein R ₁ is a methyl group or And/or And the sum of the units a = 0 to 100, the sum of the units b = 0 to 15, the ratio of the methyl group to the alkoxy group in the group R ₁ is less than 50:1, and if a = 0, b≧1 And if b = 0, a ≧ 5 is added to the suspension, and the resulting suspension is dried.

如申請專利範圍第27項之方法，其中採用噴霧乾燥法來乾燥該生成的懸浮液。 The method of claim 27, wherein the resulting suspension is dried by spray drying.

如申請專利範圍第22-28項中任何一項之方法，其中於步驟e)之後所進行乾燥係使得產物的殘餘濕氣含量少於10%。 The method of any one of claims 22-28, wherein the drying system after step e) is such that the residual moisture of the product is contained The amount is less than 10%.

如申請專利範圍第29之方法，其中在步驟e)中矽石懸浮液之溫度為20-100℃。 The method of claim 29, wherein the temperature of the vermiculite suspension in step e) is from 20 to 100 °C.

如申請專利範圍第13項之方法，其中於步驟d)之後，將0.5-30重量%的聚有機矽氧烷或改良的聚有機矽氧烷在步驟e)中加入矽石，且使二者充份地混合。 The method of claim 13, wherein after step d), 0.5-30% by weight of the polyorganosiloxane or the modified polyorganosiloxane is added to the vermiculite in step e), and the two are Mix well.

如申請專利範圍第13項之方法，其中於步驟d)之後，將0.5-30重量%的具有以下通用結構的聚有機矽氧烷：其中Y=-OH、-OR或Y=H₅ C₂ -O-(C₂ H₄ O)_m -，H₇ C₃ -O-(C₃ H₆ O)_m -或 R=烷基，R₂ =烷基，R₃ =烷基， a=0-100，b=0-100，c=0-100，d=0-100，m=0-100且k=0-100在步驟e)中加入矽石，且使二者充份地混合。The method of claim 13, wherein after step d), from 0.5 to 30% by weight of the polyorganosiloxane having the following general structure: Wherein Y=-OH, -OR or Y=H ₅ C ₂ -O-(C ₂ H ₄ O) _m -, H ₇ C ₃ -O-(C ₃ H ₆ O) _m - or R = alkyl, R ₂ = alkyl, R ₃ = alkyl, a = 0-100, b = 0-100, c = 0-100, d = 0-100, m = 0-100 and k = 0 -100 Add vermiculite in step e) and mix the two thoroughly.

如申請專利範圍第32項之方法，其中R為甲基或乙基。 The method of claim 32, wherein R is methyl or ethyl.

如申請專利範圍第13項之方法，其中於步驟d)之後，將0.5-30重量%的具有以下通用結構的聚有機矽氧烷：其中R₁ 為甲基基團或及/或且單元a之總和=0至100，單元b之總和=0至15，在基團R₁ 中甲基對烷氧基基團之比例少於50：1，且若a=0時b≧1，且若b=0時a≧5在步驟e)中加入矽石，且使二者充份地混合。The method of claim 13, wherein after step d), from 0.5 to 30% by weight of the polyorganosiloxane having the following general structure: Wherein R ₁ is a methyl group or And/or And the sum of the units a = 0 to 100, the sum of the units b = 0 to 15, the ratio of the methyl group to the alkoxy group in the group R ₁ is less than 50:1, and if a = 0, b≧1 And if b=0, a≧5 is added to the vermiculite in step e), and the two are thoroughly mixed.

如申請專利範圍第31-34項中任何一項之方法，其中在步驟e)中進行加入的期間為0至120分鐘，且伴隨著混合進行。 The method of any one of claims 31 to 34, wherein the period of addition in step e) is from 0 to 120 minutes, with mixing.

如申請專利範圍第35項之方法，其中將矽石與聚合物再混合0-2小時。 The method of claim 35, wherein the vermiculite is mixed with the polymer for another 0 to 2 hours.

如申請專利範圍第36項之方法，其中在步驟e)中混合物溫度為20-150℃。 The method of claim 36, wherein the temperature of the mixture in step e) is from 20 to 150 °C.

如申請專利範圍第13-19項中任何一項之方法，其中於經表面處理之矽石已乾燥之後，於步驟f)中進行研磨。 The method of any one of claims 13 to 19, wherein after the surface-treated vermiculite has been dried, the grinding is carried out in step f).

如申請專利範圍第13-19項中任何一項之方法，其中於經表面處理之矽石已乾燥之後，或於步驟f)研磨之後或於步驟f)研磨期間，分離出直徑大於50μm的微粒。 The method of any one of claims 13 to 19, wherein after the surface-treated vermiculite has been dried, or after the step f) grinding or during the step f) grinding, the particles having a diameter larger than 50 μm are separated. .

一種如申請專利範圍第1-12項中任何一項的沉澱矽石之應用，其係用於減光劑。 An application of precipitated vermiculite according to any one of claims 1 to 12 for use as a light reducing agent.

一種如申請專利範圍第13-39項中任何一項之方法所製備的沉澱矽石之應用，其係用於減光劑。Use of precipitated vermiculite prepared by the method of any one of claims 13-39, which is used for a light reducing agent.