TW202003724A - Inorganic oxide dispersion having high transparency - Google Patents
Inorganic oxide dispersion having high transparency Download PDFInfo
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
Abstract
Description
本發明是有關於一種具有高透明性的無機氧化物分散體、以及包含所述分散體的油墨、塗料、塗敷液、塗膜、及膜。The present invention relates to an inorganic oxide dispersion having high transparency, and an ink, paint, coating liquid, coating film, and film containing the dispersion.
為了於塗料、膜等用途中達成僅利用樹脂而難以達成的機械特性、及光學特性，自先前以來不斷嘗試將二氧化矽等無機氧化物與樹脂混合的方法。於將無機氧化物與樹脂混合時，以提高機械特性或光學特性為目的而一直利用使用將無機氧化物分散至奈米級的分散體的方法。In order to achieve mechanical properties and optical properties that are difficult to achieve by using resin only in applications such as paints and films, methods of mixing inorganic oxides such as silica and resins have been tried. When mixing an inorganic oxide with a resin, a method of using a dispersion in which the inorganic oxide is dispersed to the nanometer level has been used for the purpose of improving mechanical properties or optical properties.
作為課題可列舉如下情況：若將無機氧化物微細分散至奈米級則需要大量的為使無機氧化物分散穩定化而所需的分散劑，從而導致作為塗料或膜所要求的特性降低。為了解決該課題，提出有藉由於黏合劑中導入具有分散性能的骨架而使特性降低最小化，但可應用的用途有限（專利文獻1）。另外，提出有如下方法：利用低沸點的偶合劑進行處理，且藉由膜加工時的加熱來去除剩餘部分的偶合劑，藉此使對最終物性的影響最小化，所述方法雖然於可處理應用的有限的溶劑體系中可分散氧化鋯及鈦，但根據無機氧化物的種類不同而難以利用（專利文獻2）。另外，提出有藉由併用羥基羧酸與陽離子系界面活性劑而使二氧化鈦溶膠於有機溶劑中穩定化，該方法可適用於二氧化鈦溶膠，但對於例如藉由氣相法而製造的無機氧化物而言，由於分散不足，故難以適用（專利文獻3）。As a problem, the following may be mentioned: When finely dispersing the inorganic oxide to the nanometer level, a large amount of dispersant necessary for stabilizing the dispersion of the inorganic oxide is required, resulting in a decrease in the characteristics required as a coating or a film. In order to solve this problem, it has been proposed to minimize the degradation of characteristics by introducing a skeleton having dispersibility into the adhesive, but the applicable applications are limited (Patent Document 1). In addition, a method has been proposed that uses a low-boiling-point coupling agent for processing and removes the remaining portion of the coupling agent by heating during film processing, thereby minimizing the impact on the final physical properties. Zirconium oxide and titanium can be dispersed in the limited solvent system used, but it is difficult to use depending on the type of inorganic oxide (Patent Document 2). In addition, it has been proposed to stabilize titania sol in an organic solvent by using a hydroxycarboxylic acid and a cationic surfactant in combination. This method can be applied to titania sol, but for inorganic oxides produced by a gas phase method, for example, In other words, due to insufficient dispersion, it is difficult to apply (Patent Document 3).
近年來，作為此種藉由將無機氧化物與樹脂混合來提高機械特性的方法受到關注的領域，可列舉透明聚醯亞胺的機械特性及光學特性控制。然而，存在如下課題：透明聚醯亞胺於製造步驟中，經過250℃～350℃的加熱步驟，故於使用一般的樹脂型分散劑、及陽離子系活性劑的無機氧化物分散體中，伴隨分散劑的分解所致的黃變，聚醯亞胺的透明性及機械物性值受損。 [現有技術文獻] [專利文獻]In recent years, as a method of improving mechanical properties by mixing an inorganic oxide and a resin, attention has been given to the control of mechanical properties and optical properties of transparent polyimide. However, there is a problem that the transparent polyimide undergoes a heating step of 250° C. to 350° C. in the manufacturing step, so it is accompanied by an inorganic oxide dispersion using a general resin-type dispersant and a cationic active agent. The yellowing caused by the decomposition of the dispersant, the transparency and mechanical properties of the polyimide are impaired. [Prior Art Literature] [Patent Literature]
專利文獻1：國際公開第2007/138946號 專利文獻2：日本專利特開2009-143974號公報 專利文獻3：日本專利特開2003-95657號公報Patent Literature 1: International Publication No. 2007/138946 Patent Document 2: Japanese Patent Laid-Open No. 2009-143974 Patent Document 3: Japanese Patent Laid-Open No. 2003-95657
[發明所欲解決之課題] 本發明的一實施形態的目的在於提供一種分散穩定性優異且具有高透明性的無機氧化物分散體、以及包含所述無機氧化物分散體的塗料、塗膜、及膜。 [解決課題之手段][Problems to be solved by the invention] An object of one embodiment of the present invention is to provide an inorganic oxide dispersion having excellent dispersion stability and high transparency, and a paint, coating film, and film containing the inorganic oxide dispersion. [Means to solve the problem]
即，本發明的一實施形態是有關於一種無機氧化物分散體，包含：無機氧化物、下述通式A所表示的胺、分子量為200以下的脂肪族羥基酸、及相對介電常數為18以上的溶媒。
通式A
[化A]
另外，本發明的另一實施形態是有關於一種塗料，包含所述無機氧化物分散體。In addition, another embodiment of the present invention relates to a paint containing the inorganic oxide dispersion.
另外，本發明的又一實施形態是有關於一種塗膜，其是使用所述無機氧化物分散體、或者所述塗料而形成。In addition, another embodiment of the present invention relates to a coating film formed using the inorganic oxide dispersion or the paint.
另外，本發明的又一實施形態是有關於一種膜，其是使用所述無機氧化物分散體、或者所述塗料而形成。 [發明的效果]In addition, another embodiment of the present invention relates to a film formed using the inorganic oxide dispersion or the paint. [Effect of invention]
根據本發明的實施形態，可提供一種分散穩定性優異且具有高透明性的無機氧化物分散體、以及包含所述無機氧化物分散體的塗料、塗膜、及膜。According to the embodiments of the present invention, it is possible to provide an inorganic oxide dispersion having excellent dispersion stability and high transparency, and a paint, coating film, and film containing the inorganic oxide dispersion.
以下，對本發明的實施形態的無機氧化物分散體、塗料、塗膜、及膜進行詳細說明。Hereinafter, the inorganic oxide dispersion, paint, coating film, and film of the embodiment of the present invention will be described in detail.
本發明的實施形態如下。
[1]一種無機氧化物分散體，包含：無機氧化物、下述通式A所表示的胺、分子量為200以下的脂肪族羥基酸、及相對介電常數為18以上的溶媒。
通式A
[化A]
＜無機氧化物分散體＞ 本發明的實施形態的無機氧化物分散體包含：無機氧化物、下述通式A所表示的胺、分子量為200以下的脂肪族羥基酸、及相對介電常數為18以上的溶媒。以下，對本發明的無機氧化物分散體中所使用的材料進行說明。<Inorganic oxide dispersion> The inorganic oxide dispersion of the embodiment of the present invention includes an inorganic oxide, an amine represented by the following general formula A, an aliphatic hydroxy acid having a molecular weight of 200 or less, and a solvent having a relative dielectric constant of 18 or more. Hereinafter, the materials used in the inorganic oxide dispersion of the present invention will be described.
＜無機氧化物＞ 無機氧化物分散體中所使用的無機氧化物可使用選自由金屬、及矽（Si）所組成的群組中的至少任一種元素的氧化物。可根據塗膜、膜等所需的物性值來選定無機氧化物，例如可列舉：氧化鋯（ZrO2 ）、二氧化鈦（TiO2 ）、二氧化矽（SiO2 ）、氧化鋁（Al2 O3 ）、氧化鐵（Fe2 O3 ）、氧化銅（CuO）、氧化鋅（ZnO）、氧化釔（Y2 O3 ）、氧化鈮（Nb2 O5 ）、氧化鉬（MoO3 ）、氧化銦（In2 O3 ）、氧化錫（SnO2 ）、氧化鉭（Ta2 O5 ）、氧化鎢（WO3 ）、氧化鉛（PbO）、氧化鉍（Bi2 O3 ）、氧化鈰（CeO2 ）、氧化銻（Sb2 O5 、Sb2 O3 ）等。所述無機氧化物可單獨使用一種，或者將兩種以上混合使用。<Inorganic oxide> As the inorganic oxide used in the inorganic oxide dispersion, an oxide of at least any one element selected from the group consisting of metal and silicon (Si) can be used. The inorganic oxide can be selected according to the required physical property value of the coating film, film, etc., for example: zirconium oxide (ZrO 2 ), titanium dioxide (TiO 2 ), silicon dioxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), iron oxide (Fe 2 O 3 ), copper oxide (CuO), zinc oxide (ZnO), yttrium oxide (Y 2 O 3 ), niobium oxide (Nb 2 O 5 ), molybdenum oxide (MoO 3 ), indium oxide (In 2 O 3 ), tin oxide (SnO 2 ), tantalum oxide (Ta 2 O 5 ), tungsten oxide (WO 3 ), lead oxide (PbO), bismuth oxide (Bi 2 O 3 ), cerium oxide (CeO 2 ), antimony oxide (Sb 2 O 5 , Sb 2 O 3 ), etc. One type of the inorganic oxide may be used alone, or two or more types may be used in combination.
就透明性的觀點而言，無機氧化物的粒徑較佳為平均粒徑為15 nm～50 nm的範圍。此處，平均粒徑為藉由掃描式電子顯微鏡（scanning electron microscope，SEM）所觀察到的粒徑的算術平均值。詳細而言，為以倍率20000倍觀察塗料用粒子的粉末，並選擇任意100個粒子，將各個粒徑平均而求出的值。於粒子形狀具有長軸、短軸的情況下，將長軸與短軸的長度的平均值設為該粒子的粒徑。From the viewpoint of transparency, the average particle diameter of the inorganic oxide is preferably in the range of 15 nm to 50 nm. Here, the average particle diameter is an arithmetic average value of particle diameters observed with a scanning electron microscope (SEM). Specifically, it is a value obtained by observing the powder of paint particles at a magnification of 20,000 times, selecting 100 arbitrary particles, and averaging the respective particle diameters. When the particle shape has a long axis and a short axis, the average value of the lengths of the long axis and the short axis is the particle size of the particle.
作為無機氧化物的合成方法，大體分為固相法、液相法、氣相法三種。就可獲得微細的無機氧化物而言，較佳為由液相法或氣相法所合成的無機氧化物。尤其是液相法有如下方法等：共沈澱法，藉由pH變化、或添加溶劑等而自溶解有欲合成的物質的構成離子的溶液產生沈澱；水解法，藉由將金屬醇鹽水解而合成粒子；溶劑熱法（solvothermal method），藉由於加壓下的溶媒中進行加熱而進行物質合成或晶體成長；及溶膠凝膠（sol-gel）法，將藉由金屬醇鹽水解而粒子呈膠體狀分散的溶膠製成無流動性的凝膠後，對凝膠進行加熱而獲得粒子。As a method of synthesizing inorganic oxides, it can be roughly divided into three types: solid phase method, liquid phase method, and gas phase method. In terms of obtaining fine inorganic oxides, inorganic oxides synthesized by a liquid phase method or a gas phase method are preferred. In particular, the liquid phase method includes the following methods: co-precipitation method, which generates precipitation from a solution in which the constituent ions of the substance to be synthesized are dissolved by pH change or addition of a solvent, etc.; hydrolysis method, which is obtained by hydrolyzing metal alkoxide Synthetic particles; solvothermal method (solvothermal method), by heating in a solvent under pressure for substance synthesis or crystal growth; and sol-gel (sol-gel) method, the particles will be dissolved by metal alkoxide hydrolysis After the colloidally dispersed sol is made into a fluid-free gel, the gel is heated to obtain particles.
關於無機氧化物，就提高機械物性值的觀點而言，較佳為使用於250℃以上的高溫下進行煅燒，且使無機氧化物的結晶骨架穩定的粒子，更佳為使用於400℃以上的高溫下煅燒的無機氧化物。尤其是當使用聚醯亞胺或聚醯胺酸清漆作為將無機氧化物分散體用作塗料、或膜時的黏合劑時，硬化溫度需要為300℃～400℃，故實施了所述煅燒步驟的無機氧化物的化學性穩定，可抑制膜收縮，且可達成良好的機械物性值的提高而不產生伴隨脫水等的膜內缺陷。因此，藉由使用本發明的實施形態的無機氧化物分散體，即使於300℃以上的高溫下，著色亦少（高耐熱性），可提高塗膜、及膜的機械物性值（熱膨脹性）。Regarding the inorganic oxide, from the viewpoint of improving the mechanical property value, particles that are calcined at a high temperature of 250° C. or higher and stabilize the crystal skeleton of the inorganic oxide are preferred, and those used at 400° C. or higher are more preferred. Inorganic oxide calcined at high temperature. Especially when using polyimide or polyamic acid varnish as the binder when the inorganic oxide dispersion is used as a coating or film, the hardening temperature needs to be 300°C to 400°C, so the calcination step is carried out The chemical stability of the inorganic oxide is stable, the film shrinkage can be suppressed, and a good mechanical property value can be achieved without in-film defects accompanying dehydration. Therefore, by using the inorganic oxide dispersion of the embodiment of the present invention, even at a high temperature of 300° C. or higher, coloring is low (high heat resistance), and the mechanical properties (thermal expansion) of the coating film and the film can be improved .
＜胺＞ 於無機氧化物分散體中，可使用下述通式A所表示的胺。<Amine> In the inorganic oxide dispersion, an amine represented by the following general formula A can be used.
通式A：Formula A:
[化A]
R1 表示碳數2～13的烷基。R2 及R3 分別獨立地表示氫原子、或者碳數2～13的烷基。另外，R1 ～R3 的碳數的合計較佳為6～25，更佳為6～18，進而佳為6～12。藉由使用所述胺，可特異地分散無機氧化物分散體，從而可達成高透明性。另外，不易產生室溫下的胺的揮發，故作為分散體的組成穩定，結果經時穩定性亦優異。R 1 represents an alkyl group having 2 to 13 carbon atoms. R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 2 to 13 carbon atoms. In addition, the total number of carbon numbers of R 1 to R 3 is preferably 6 to 25, more preferably 6 to 18, and still more preferably 6 to 12. By using the amine, the inorganic oxide dispersion can be specifically dispersed, and high transparency can be achieved. In addition, volatilization of amines at room temperature is not likely to occur, so the composition as a dispersion is stable, and as a result, stability over time is also excellent.
＜羥基酸＞ 於無機氧化物分散體中，可使用分子量為80以上且200以下的脂肪族羥基酸，較佳為使用分子量為90以上且200以下的脂肪族羥基酸。尤其是於長時間維持無機氧化物的透明性的方面而言，更佳為羥基酸的分子骨架中的羥基與羧基的個數的比率為羧基/羥基=1～3。另外，當使用聚醯亞胺或聚醯胺酸清漆作為將無機氧化物分散體用作塗料、或膜時的黏合劑時，硬化溫度需要為300℃～400℃。藉由同時使用本發明的實施形態中所使用的胺、及羥基酸，不僅可維持硬化後的透明性，而且不會伴隨分解而產生著色、以及對物性值產生不良影響。<Hydroxy acid> In the inorganic oxide dispersion, an aliphatic hydroxy acid having a molecular weight of 80 or more and 200 or less can be used, and an aliphatic hydroxy acid having a molecular weight of 90 or more and 200 or less is preferably used. In particular, in terms of maintaining the transparency of the inorganic oxide for a long time, it is more preferable that the ratio of the number of hydroxyl groups to the number of carboxyl groups in the molecular skeleton of the hydroxy acid is carboxyl group/hydroxyl group=1 to 3. In addition, when polyimide or polyamic acid varnish is used as a binder when the inorganic oxide dispersion is used as a paint or a film, the curing temperature needs to be 300°C to 400°C. By using the amine and the hydroxy acid used in the embodiment of the present invention together, not only can the transparency after curing be maintained, but also coloring due to decomposition and adverse effects on physical property values are not caused.
相對於無機氧化物100質量份，胺及羥基酸的添加量分別較佳為1質量份～50質量份，更佳為5質量份～30質量份的範圍。若胺與羥基酸的添加量處於所述範圍，則可長時間維持無機氧化物粒子的透明性，且不會對製成塗膜、或膜時的物性值產生不良影響。藉由將胺與羥基酸組合來使用，即使與添加相對於無機氧化物100質量份而為50質量份左右的現有方法相比分散劑量為低添加量，亦可確保透明性。The addition amount of amine and hydroxy acid is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass relative to 100 parts by mass of the inorganic oxide. If the addition amount of the amine and the hydroxy acid is within the above range, the transparency of the inorganic oxide particles can be maintained for a long time without adversely affecting the physical properties of the coating film or the film. By using an amine in combination with a hydroxy acid, even if the amount of dispersion is lower than the conventional method of adding about 50 parts by mass relative to 100 parts by mass of the inorganic oxide, transparency can be ensured.
＜溶媒＞ 於無機氧化物分散體中，可使用相對介電常數為18以上的溶媒。此處，所謂相對介電常數為介質的介電常數與真空的介電常數的比。<Solvent> In the inorganic oxide dispersion, a solvent having a relative dielectric constant of 18 or more can be used. Here, the relative dielectric constant is the ratio of the dielectric constant of the medium to the dielectric constant of vacuum.
就無機氧化物分散體的經時的分散穩定性的保持、以及分散粒徑的微細分散更好的方面而言，所述溶媒較佳為水、醇、γ-丁內酯、或含氮的有機溶劑，進而佳為γ-丁內酯、或含氮的有機溶劑。此處，所謂含氮的有機溶劑是於分子內具有氮的溶劑的總稱，例如可列舉：N-甲基-2-吡咯啶酮、二甲基乙醯胺、二甲基亞碸、二甲基甲醯胺、及乙腈等。In terms of maintaining the dispersion stability of the inorganic oxide dispersion over time and the fine dispersion of the dispersed particle size, the solvent is preferably water, alcohol, γ-butyrolactone, or nitrogen-containing The organic solvent is further preferably γ-butyrolactone or a nitrogen-containing organic solvent. Here, the nitrogen-containing organic solvent is a general term for a solvent having nitrogen in the molecule, and examples include: N-methyl-2-pyrrolidone, dimethylacetamide, dimethylsulfoxide, and dimethyl Carboxamide, acetonitrile, etc.
γ-丁內酯、以及含氮的有機溶劑易於溶解各種聚合物，故可廣泛地用作溶解各種聚合物的溶媒。另外，如後述般，當黏合劑為通常廣泛使用的聚醯亞胺、或聚醯胺酸清漆時，為了製作無機氧化物分散體，較佳為使用γ-丁內酯、或含氮的有機溶劑。γ-Butyrolactone and nitrogen-containing organic solvents are easy to dissolve various polymers, so they can be widely used as solvents for dissolving various polymers. In addition, as described later, when the binder is generally widely used polyimide or polyamic acid varnish, in order to produce an inorganic oxide dispersion, it is preferable to use γ-butyrolactone or a nitrogen-containing organic Solvent.
＜分散方法＞ 當製作無機氧化物分散體時，出於達成高透明性的目的，可使用通常使用的分散機，例如可列舉：分散器（disper）、均質混合機（homomixer）、行星式攪拌機（planetary mixer）、M技術（M technique）公司製造的「科利爾密克斯（CLEARMIX）」、譜萊密克斯（PRIMIX）公司的「費魯密克斯（Filmix）」、塗料調和器（paint conditioner）（紅魔（RED DEVIL）公司製造）、球磨機、砂磨機（新丸企業（SHINMARU ENTERPRISES）公司製造的「戴諾磨機（Dyno Mill）」等）、磨碎機、珠磨機（pearl mill）（愛立許（Eirich）公司製造的「DCP磨機（DCP Mill）」等）、環隙球磨機（CoBall Mill）、濕式噴射式磨機（基納斯（Genus）公司製造的「基納斯PY（Genus PY）」、杉野機械（SUGINO machine）公司製造的「思達巴斯特（Starburst）」、納麥澤（Nanomizer）公司製造的「納麥澤（Nanomizer）」等）、M技術（M technique）公司製造的「科利爾SS-5（CLEAR SS-5）」、奈良機械製作所公司製造的「麥庫洛斯（Micros）」、輥磨機等分散機。分散機可僅單獨使用一種，亦可併用多種。<Dispersion method> When preparing an inorganic oxide dispersion, for the purpose of achieving high transparency, a commonly used disperser can be used, and examples include a disper, a homomixer, and a planetary mixer. , "CLEARMIX" made by M technique company, "Filmix" by PRIMIX company, paint conditioner (Manufactured by RED DEVIL), ball mill, sand mill ("Dyno Mill" manufactured by SHINMARU ENTERPRISES, etc.), attritor, bead mill ("DCP Mill" manufactured by Eirich, etc.), CoBall Mill, and wet jet mill ("Genus" manufactured by Genus) PY (Genus PY), "Starburst" manufactured by SUGINO machine, "Nanomizer" manufactured by Nanomizer, etc.), M technology ( M technique) "Clear SS-5" manufactured by the company, "Micros" manufactured by Nara Machinery Co., Ltd., roller mills and other dispersers. Only one kind of disperser can be used alone, or multiple kinds can be used in combination.
＜分散粒徑＞ 關於無機氧化物分散體的分散粒徑，就塗料、或膜時的透明性的觀點而言，分散粒徑越小則可見光區域下的光散射越減少，故較佳，當出於抑制聚醯亞胺等的熱膨脹的目的而添加無機氧化物時，若考慮到與透明性的並存，則較佳為15 nm～150 nm的範圍，更佳為30 nm～100 nm的範圍。再者，所謂分散粒徑，為使用動態光散射方式的粒度分佈計，於體積粒度分佈中，於自粒徑小者累積該粒子的體積比例時，成為50%的粒徑。<dispersed particle size> Regarding the dispersion particle diameter of the inorganic oxide dispersion, from the viewpoint of transparency in coatings or films, the smaller the dispersion particle diameter, the smaller the light scattering in the visible light region. Therefore, it is preferable to suppress the polymerization When an inorganic oxide is added for the purpose of thermal expansion such as imine, in consideration of the coexistence with transparency, it is preferably in the range of 15 nm to 150 nm, and more preferably in the range of 30 nm to 100 nm. In addition, the dispersion particle size is a particle size distribution meter using a dynamic light scattering method, and in the volume particle size distribution, when the volume ratio of the particles is accumulated from the person with a small particle size, it becomes a particle size of 50%.
＜無機氧化物塗料＞ 本發明的實施形態的無機氧化物分散體視需要可添加黏合劑、硬化劑、乾燥防止劑、螯合劑、流變控制（rheological control）劑、或矽烷偶合劑等，而用作能夠塗佈於各種基材上的無機氧化物塗料。<Inorganic oxide coating> The inorganic oxide dispersion according to the embodiment of the present invention may be added as a coating agent by adding a binder, a hardener, an anti-drying agent, a chelating agent, a rheological control agent, a silane coupling agent, or the like. Inorganic oxide coatings on various substrates.
＜黏合劑＞ 黏合劑可根據塗膜、或膜等所需要的物性來選定，例如可列舉：將聚丙烯酸、聚碳酸酯、聚酯、聚醯胺、聚烯烴、聚胺基甲酸酯、聚醚、及聚偏二氟乙烯等樹脂溶解於溶媒中而成的清漆、或分散而成的乳膠（emulsion）。本發明的實施形態的無機氧化物分散體尤其較佳為使用聚醯亞胺、或聚醯胺酸清漆作為黏合劑，尤其是藉由使用聚醯亞胺、或聚醯胺酸清漆作為黏合劑，於聚醯亞胺、或聚醯胺酸清漆的通常的硬化溫度即300℃～400℃下脂肪族羥基酸、及胺揮發，不僅維持透明性而且機械物性值提高，故進而佳。<Adhesive> The adhesive can be selected according to the required physical properties of the coating film, film, etc., for example, polyacrylic acid, polycarbonate, polyester, polyamide, polyolefin, polyurethane, polyether, and A varnish made by dissolving resin such as polyvinylidene fluoride in a solvent, or an emulsion made by dispersion. In the inorganic oxide dispersion of the embodiment of the present invention, it is particularly preferable to use polyimide or polyamic acid varnish as a binder, especially by using polyimide or polyamic acid varnish as a binder The aliphatic hydroxy acid and amine are volatilized at the normal curing temperature of polyimide or polyamic acid varnish, that is, 300°C to 400°C, which not only maintains transparency, but also improves mechanical property values, which is better.
＜無機氧化物塗膜＞ 將無機氧化物塗料塗佈於各種基材上，藉由進行加熱而使溶媒乾燥，且視需要進行硬化，藉此可用作無機氧化物塗膜。基材可根據所需要的物性來選定，例如可列舉包含聚丙烯酸、聚碳酸酯、聚酯、聚醯胺、聚烯烴、聚胺基甲酸酯、聚醚、聚偏二氟乙烯或聚對苯二甲酸乙二酯等樹脂；鐵、不鏽鋼、銅或鋁等金屬；或者玻璃等無機氧化物的膜、板或成形物等。<Inorganic oxide coating film> The inorganic oxide coating is applied to various substrates, the solvent is dried by heating, and hardened as necessary, thereby being used as an inorganic oxide coating film. The base material can be selected according to the required physical properties, and examples include polyacrylic acid, polycarbonate, polyester, polyamide, polyolefin, polyurethane, polyether, polyvinylidene fluoride, or polyparaethylene. Resins such as ethylene terephthalate; metals such as iron, stainless steel, copper, or aluminum; or films, plates, or molded products of inorganic oxides such as glass.
＜無機氧化物膜＞ 將無機氧化物塗料塗佈於各種具有剝離性的基材上，藉由進行加熱而使溶媒乾燥，且視需要進行硬化，藉此獲得無機氧化物塗膜，藉由將所述無機氧化物塗膜自基材剝離而可獲得無機氧化物膜。所獲得的無機氧化物膜可視需要而接著、黏接於聚丙烯酸、聚碳酸酯、聚酯、聚醯胺、聚烯烴、聚胺基甲酸酯、聚醚、聚偏二氟乙烯或聚對苯二甲酸乙二酯等樹脂；鐵、不鏽鋼、銅或鋁等金屬；或者玻璃等無機氧化物等的膜等上而用作積層膜。<Inorganic oxide film> The inorganic oxide coating is applied to various substrates with releasability, the solvent is dried by heating, and if necessary, hardened, thereby obtaining an inorganic oxide coating film, by coating the inorganic oxide The film is peeled from the substrate to obtain an inorganic oxide film. The obtained inorganic oxide film can be adhered to polyacrylic acid, polycarbonate, polyester, polyamide, polyolefin, polyurethane, polyether, polyvinylidene fluoride, or parylene if necessary. Resins such as ethylene terephthalate; metals such as iron, stainless steel, copper, or aluminum; or films such as inorganic oxides such as glass are used as laminated films.
＜透明性＞ 透明性越高越佳，當以於乾燥時成為相同膜厚的方式將清漆塗佈於基材，以所得的塗板為基準算出將無機氧化物塗料塗佈於基材而得的塗板的總光線透過率時，透明性較佳為95%～100%，更佳為97%～100%。<Transparency> The higher the transparency, the better. When the varnish is applied to the substrate so that the film thickness is the same when drying, the total light of the coated plate obtained by applying the inorganic oxide coating to the substrate is calculated based on the obtained coated plate. In the case of transmittance, the transparency is preferably 95% to 100%, and more preferably 97% to 100%.
＜耐熱性＞ 尤其是將聚醯亞胺用作黏合劑的塗膜、以及膜，較佳為於硬化溫度300℃～400℃附近伴隨著色等而透明性的降低少，若將無機氧化物塗料塗佈於基材而得的塗板中，自加熱前的總光線透過率的值減去加熱後的總光線透過率的值而得的值的絕對值未滿1%，則較佳，若未滿0.5%則更佳。<heat resistance> In particular, the coating film and the film using polyimide as a binder are preferably reduced in transparency near the curing temperature of 300° C. to 400° C. with coloring or the like. If an inorganic oxide coating is applied to the base In the coated board made of wood, the absolute value of the value obtained by subtracting the value of the total light transmittance after heating from the value of the total light transmittance before heating is less than 1%, preferably, if less than 0.5% Better.
＜熱膨脹性＞ 尤其是對於將聚醯亞胺用作黏合劑的膜，藉由將無機氧化物均勻地分散於膜中，相較於黏合劑單獨的情況，能夠降低表示加熱時的尺寸變化的線膨脹係數。尤其是使用氧化鋁作為無機氧化物時，線膨脹係數更低而較佳。線膨脹係數可藉由如下方式而求出：按照所調節的程式使物質的溫度變化，同時施加非振動負荷，將該物質的變形作為溫度的函數來進行測定。若膜的厚度為50 μm左右，則較佳為根據施加拉伸應力時的變形而求出。<Thermal expansion> In particular, for a film using polyimide as a binder, by uniformly dispersing the inorganic oxide in the film, it is possible to reduce the linear expansion coefficient indicating the dimensional change during heating compared to the case of the binder alone. In particular, when alumina is used as the inorganic oxide, the coefficient of linear expansion is lower and preferably. The coefficient of linear expansion can be obtained by changing the temperature of the substance according to the adjusted formula while applying a non-vibrating load, and measuring the deformation of the substance as a function of temperature. If the thickness of the film is about 50 μm, it is preferably determined based on the deformation when tensile stress is applied.
本發明與2018年5月28日申請的日本專利申請編號2018-101435號的主題相關，並藉由參照而將其揭示內容全部併入至本說明書中。 [實施例]The present invention is related to the subject of Japanese Patent Application No. 2018-101435 filed on May 28, 2018, and the disclosure content thereof is fully incorporated into this specification by reference. [Example]
以下，藉由實施例來更具體地說明本發明的實施形態，但本發明的實施形態只要不超出其要旨，則並不限定於以下的實施例。再者，實施例及比較例中，只要無特別說明，則「份」、「%」分別是指質量份、質量%。Hereinafter, the embodiments of the present invention will be described more specifically by way of examples, but the embodiments of the present invention are not limited to the following examples as long as the gist of the invention is not exceeded. In addition, in the Examples and Comparative Examples, unless otherwise specified, "parts" and "%" refer to parts by mass and% by mass, respectively.
＜無機氧化物＞ 以下，列舉實施例及比較例中所使用的無機氧化物。 阿洛西德（AEROXIDE）Alu C（氧化鋁、贏創德固賽（Evonik Degussa）公司製造） 阿洛斯（AEROSIL）200（二氧化矽、贏創德固賽（Evonik Degussa）公司製造） PCS-60（氧化鋯、新日本電工股份有限公司製造） TTO-V-3（氧化鈦、石原產業股份有限公司製造） 納諾發（NANOFINE）50A（氧化鋅、堺化學工業股份有限公司製造） 貝萊爾（Biral）Al-L40P（氧化鋁溶膠、多木化學股份有限公司製造）<Inorganic oxide> The inorganic oxides used in Examples and Comparative Examples are listed below. AEROXIDE Alu C (alumina, Evonik Degussa (made by Evonik Degussa)) AEROSIL 200 (silica, made by Evonik Degussa) PCS-60 (Zirconium oxide, manufactured by New Nippon Electric Co., Ltd.) TTO-V-3 (Titanium oxide, manufactured by Ishihara Industries Co., Ltd.) NANOFINE 50A (zinc oxide, manufactured by Sakai Chemical Industry Co., Ltd.) Belair (Biral) Al-L40P (alumina sol, manufactured by Tamu Chemical Co., Ltd.)
＜胺＞ 以下，列舉實施例及比較例中所使用的胺。 三乙胺（三級胺、富士軟片和光純藥股份有限公司製造） 三丙胺（三級胺、富士軟片和光純藥股份有限公司製造） 二丁胺（二級胺、富士軟片和光純藥股份有限公司製造） 二己胺（二級胺、富士軟片和光純藥股份有限公司製造） 二辛胺（二級胺、富士軟片和光純藥股份有限公司製造） 雙十二胺（二級胺、富士軟片和光純藥股份有限公司製造） 辛胺（一級胺、富士軟片和光純藥股份有限公司製造） 十二胺（一級胺、東京化成工業股份有限公司製造） 硬脂胺（一級胺） 日產卡其歐（Nissan Cation）2-DB-800E（四級胺、不揮發成分80%、日油股份有限公司製造） 日產卡其歐（Nissan Cation）MA（一級胺乙酸鹽、不揮發成分100%、日油股份有限公司製造）<Amine> The amines used in Examples and Comparative Examples are listed below. Triethylamine (tertiary amine, Fuji film and Wako Pure Chemicals Co., Ltd.) Tripropylamine (tertiary amine, Fuji film and Wako Pure Chemicals Co., Ltd.) Dibutylamine (secondary amine, Fuji Film and Wako Pure Chemicals Co., Ltd.) Dihexylamine (secondary amine, Fuji film Wako Pure Chemicals Co., Ltd.) Dioctylamine (secondary amine, Fuji film and Wako Pure Chemicals Co., Ltd.) Didodecylamine (secondary amine, Fuji film and Wako Pure Chemicals Co., Ltd.) Octylamine (first grade amine, Fuji film Wako Pure Chemicals Co., Ltd.) Dodecylamine (primary amine, manufactured by Tokyo Chemical Industry Co., Ltd.) Stearylamine (primary amine) Nissan Cation (Nissan Cation) 2-DB-800E (quaternary amine, non-volatile content 80%, manufactured by NOF Corporation) Nissan Cation (Nissan Cation) MA (first grade amine acetate, non-volatile content 100%, manufactured by NOF Corporation)
＜脂肪族羥基酸＞ 以下，列舉實施例及比較例中所使用的脂肪族羥基酸。 乳酸（富士軟片和光純藥股份有限公司製造、分子量90.08） DL-蘋果酸（富士軟片和光純藥股份有限公司製造、分子量134.09） 檸檬酸（富士軟片和光純藥股份有限公司製造、分子量192.12） 酒石酸（富士軟片和光純藥股份有限公司製造、分子量150.09） 奎尼酸（quinic acid）（富士軟片和光純藥股份有限公司製造、分子量192.17） 12-羥基硬脂酸（伊藤製油股份有限公司製造、分子量300.48）<aliphatic hydroxy acid> The aliphatic hydroxy acids used in Examples and Comparative Examples are listed below. Lactic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight 90.08) DL-malic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight 134.09) Citric acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight 192.12) Tartaric acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight 150.09) Quinic acid (made by Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight 192.17) 12-Hydroxystearic acid (made by Ito Oil Co., Ltd., molecular weight 300.48)
＜芳香族羥基酸＞ 以下，列舉比較例中所使用的芳香族羥基酸。 水楊酸（富士軟片和光純藥股份有限公司製造、分子量138.12） 3,4,5-三羥基苯甲酸（富士軟片和光純藥股份有限公司製造、分子量170.12）<Aromatic Hydroxy Acid> The aromatic hydroxy acids used in the comparative examples are listed below. Salicylic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight 138.12) 3,4,5-Trihydroxybenzoic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., molecular weight 170.12)
＜脂肪族羥基酸銨鹽＞ 以下，列舉比較例中所使用的脂肪族羥基酸銨鹽。 乳酸銨（不揮發成分40%、富士軟片和光純藥股份有限公司製造） 檸檬酸三銨（富士軟片和光純藥股份有限公司製造）＜aliphatic hydroxy acid ammonium salt＞ The aliphatic hydroxy acid ammonium salt used in the comparative example is listed below. Ammonium lactate (40% non-volatile content, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) Triammonium citrate (manufactured by Fuji Film Wako Pure Chemical Co., Ltd.)
＜溶媒＞ 以下，列舉實施例及比較例中所使用溶媒。 精製水（相對介電常數為80.1） N,N-二甲基亞碸（相對介電常數為48.9、三菱氣體化學股份有限公司製造） N,N-二甲基乙醯胺（相對介電常數為38.9、三菱氣體化學股份有限公司製造） N-甲基-2-吡咯啶酮（相對介電常數為32.0、三菱化學股份有限公司製造） γ-丁內酯（相對介電常數為18.3、三菱化學股份有限公司製造） 甲醇（相對介電常數為33.1、富士軟片和光純藥股份有限公司製造） 乙醇（相對介電常數為23.8、富士軟片和光純藥股份有限公司製造） 2-丙醇（相對介電常數為18.3、富士軟片和光純藥股份有限公司製造） 甲基異丁基酮（相對介電常數為13.1、富士軟片和光純藥股份有限公司製造） 乳酸乙酯（相對介電常數為13.1、富士軟片和光純藥股份有限公司製造） PGMEA（丙二醇單甲醚乙酸酯（Propylene Glycol Monomethyl Ether Acetate）、相對介電常數為8.0、富士軟片和光純藥股份有限公司製造） 乙酸乙酯（相對介電常數為6.0、富士軟片和光純藥股份有限公司製造）<Solvent> The solvents used in Examples and Comparative Examples are listed below. Refined water (relative dielectric constant is 80.1) N,N-dimethyl sulfoxide (relative dielectric constant is 48.9, manufactured by Mitsubishi Gas Chemical Co., Ltd.) N,N-dimethylacetamide (relative dielectric constant is 38.9, manufactured by Mitsubishi Gas Chemical Co., Ltd.) N-methyl-2-pyrrolidone (relative dielectric constant is 32.0, manufactured by Mitsubishi Chemical Corporation) γ-butyrolactone (relative dielectric constant 18.3, manufactured by Mitsubishi Chemical Corporation) Methanol (relative dielectric constant is 33.1, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) Ethanol (relative dielectric constant is 23.8, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) 2-Propanol (relative dielectric constant 18.3, Fuji Film Wako Pure Chemical Co., Ltd.) Methyl isobutyl ketone (relative dielectric constant is 13.1, manufactured by Fuji Film and Wako Pure Chemical Industries, Ltd.) Ethyl lactate (relative dielectric constant is 13.1, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) PGMEA (Propylene Glycol Monomethyl Ether Acetate), a relative dielectric constant of 8.0, manufactured by Fuji Film Wako Pure Chemicals Co., Ltd. Ethyl acetate (relative dielectric constant 6.0, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)
＜樹脂型分散劑＞ 以下列舉比較例中所使用的樹脂型分散劑。 迪斯帕畢克（DisperBYK）-102（酸性分散劑、日本畢克化學（BYK Chemie Japan）股份有限公司製造）<Resin type dispersant> The resin-type dispersants used in the comparative examples are listed below. DisperBYK-102 (Acid dispersant, manufactured by BYK Chemie Japan Co., Ltd.)
＜黏合劑＞ 以下列舉實施例及比較例中所使用的黏合劑。 斯皮薩瑞（SPIXAREA）TP001（聚醯亞胺、桑瑪（Somar）股份有限公司製造、不揮發成分25w%）<Adhesive> The binders used in Examples and Comparative Examples are listed below. SPIXAREA TP001 (polyimide, manufactured by Somar Co., Ltd., non-volatile content 25w%)
＜無機氧化物分散體的製備＞ 按照表1所示的調配組成，以變得均勻的方式進行攪拌混合後，進而使用直徑0.1 mm的氧化鋯珠且利用砂磨機分散5小時後，利用孔徑1 μm的過濾器進行過濾，分別製作無機氧化物分散體。再者，表1中，未記載單位的數字表示份，空欄表示未調配。<Preparation of inorganic oxide dispersion> According to the formulation composition shown in Table 1, after stirring and mixing in such a manner as to become uniform, and then using zirconia beads with a diameter of 0.1 mm and dispersing with a sand mill for 5 hours, filtration was performed using a filter with a pore size of 1 μm, respectively Preparation of inorganic oxide dispersion. In addition, in Table 1, the number of unrecorded units indicates the share, and the blank column indicates that it is not allocated.
[表1]
表1-1
＜無機氧化物塗料的製備＞ 按照表2所示的調配組成，以變得均勻的方式進行攪拌混合，分別製作無機氧化物塗料。再者，表2中，未記載單位的數字表示份，空欄表示未調配。<Preparation of inorganic oxide coatings> According to the formulation composition shown in Table 2, stirring and mixing were performed so as to be uniform, and inorganic oxide paints were produced separately. In addition, in Table 2, the number of unrecorded units indicates the share, and the blank column indicates that it is not allocated.
[表2]
表2
[評價] 利用下述方法對所獲得的無機氧化物分散體的黏度、及分散性、經時穩定性進行評價。將結果示於表3中。利用下述方法對使用該無機氧化物分散體而調整的無機氧化物塗料、及膜的透明性、耐熱性進行評價。將結果示於表4中。[Evaluation] The viscosity, the dispersibility, and the stability over time of the obtained inorganic oxide dispersion were evaluated by the following methods. Table 3 shows the results. The transparency and heat resistance of the inorganic oxide paint and the film adjusted using this inorganic oxide dispersion were evaluated by the following method. Table 4 shows the results.
（黏度） 關於無機氧化物分散體的黏度，使用B型黏度計（東機產業公司製造、BII）測定25℃、60 rpm時的黏度。就處理性的觀點而言，黏度較佳為低，按照下述的基準進行評價。 A：15 mPa·s以下（極其良好） B：超過15 mPa·s且50 mPa·s以下（良好） C：超過50 mPa·s（不良）(Viscosity) Regarding the viscosity of the inorganic oxide dispersion, a B-type viscometer (manufactured by Toki Industries, Ltd., BII) was used to measure the viscosity at 25°C and 60 rpm. From the viewpoint of handleability, the viscosity is preferably low, and evaluation is performed according to the following criteria. A: 15 mPa·s or less (extremely good) B: More than 15 mPa·s and 50 mPa·s or less (good) C: More than 50 mPa·s (bad)
（分散粒徑） 無機氧化物分散體的分散粒徑是使用動態光散射方式的粒度分佈計（日機裝公司製造、麥克羅特雷克（Microtrac）UPA），於體積粒度分佈中，於自粒徑小者累積該粒子的體積比例時，測定成為50%的粒徑。再者，關於測定中使用的試樣，實施例1、實施例3～實施例28、比較例1～比較例15是於分散體製作時所使用的溶劑中添加能夠測定的任意的量的分散體，且利用浴式超音波裝置進行分散、調整。實施例2是於乙醇中添加能夠測定的任意的量的分散體，且利用浴式超音波裝置進行分散、調整。就透明性的觀點而言，分散粒徑越小越佳，按照下述的基準進行評價。 A：100 nm以下（極其良好） B：超過100 nm且150 nm以下（良好） C：超過150 nm（不良）(Dispersed particle size) The dispersion particle size of the inorganic oxide dispersion is a particle size distribution meter (manufactured by Nikkiso Co., Ltd., Microtrac UPA) using a dynamic light scattering method. In the volume particle size distribution, it is accumulated from the smaller particle size When the volume ratio of the particles is measured, the particle diameter becomes 50%. In addition, regarding the samples used in the measurement, Example 1, Example 3 to Example 28, and Comparative Example 1 to Comparative Example 15 were added to the solvent used at the time of dispersion preparation to add an arbitrary amount of dispersion that can be measured It is dispersed and adjusted using a bath ultrasonic device. In Example 2, an arbitrary amount of dispersion that can be measured was added to ethanol, and dispersion and adjustment were performed using a bath-type ultrasonic device. From the viewpoint of transparency, the smaller the dispersed particle diameter, the better, and evaluation is performed according to the following criteria. A: Below 100 nm (extremely good) B: More than 100 nm and below 150 nm (good) C: Over 150 nm (bad)
（經時穩定性） 關於無機氧化物的經時穩定性，測定將無機氧化物分散體於50℃下靜置7天的試樣的黏度，將自靜置前的黏度的值減去靜置後的黏度的值所得的值的絕對值作為黏度的變化率進行評價。黏度的變化率越小越佳，按照下述的基準進行評價。 A：5 mPa·s以下（極其良好） B：超過5 mPa·s且10 mPa·s（良好） C：超過10 mPa·s（不良）(Stability over time) Regarding the stability over time of the inorganic oxide, the viscosity of the sample with the inorganic oxide dispersion standing at 50°C for 7 days was measured, and the value of the viscosity before standing was subtracted from the value of the viscosity after standing The absolute value of the value is evaluated as the rate of change of viscosity. The smaller the change rate of viscosity, the better, and the evaluation is performed according to the following criteria. A: 5 mPa·s or less (extremely good) B: More than 5 mPa·s and 10 mPa·s (good) C: More than 10 mPa·s (bad)
（透明性） 使用刮刀將無機氧化物塗料以乾燥後的膜厚成為2 μm的方式塗佈於10 cm×10 cm的玻璃基板，利用烘箱於140℃下乾燥30分鐘，從而形成塗膜。黏合劑亦藉由相同的方法進行塗佈、乾燥，而形成塗膜。使用霧度計（haze meter）（日本電色工業公司製造、NDH-2000），以塗佈有黏合劑的玻璃板的值為基準，測定無機氧化物塗膜的總光線透過率的值。總光線透過率的值越接近100越佳，按照下述的基準進行評價。 A：97%以上且100%以下（極其良好） B：95%以上且未滿97%（良好） C：未滿95%（不良）(Transparency) The inorganic oxide paint was applied to a glass substrate of 10 cm×10 cm so that the film thickness after drying was 2 μm using a doctor blade, and dried at 140° C. for 30 minutes in an oven to form a coating film. The adhesive is also coated and dried by the same method to form a coating film. Using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH-2000), the value of the total light transmittance of the inorganic oxide coating film was measured based on the value of the glass plate coated with the adhesive. The closer the value of the total light transmittance is to 100, the better, and evaluation is performed according to the following criteria. A: 97% or more and 100% or less (extremely good) B: More than 95% and less than 97% (good) C: Less than 95% (bad)
（耐熱性） 將透明性評價中使用的塗膜利用烘箱於氮氣環境下、且300℃下加熱1小時後，進行透明性評價，根據自加熱前的總光線透過率的值減去加熱後的總光線透過率的值所得的值的絕對值進行評價。加熱前後的總光線透過率的變化越小耐熱性越高，故較佳，按照下述的基準進行評價。 A：未滿0.5%（極其良好） B：0.5%以上且未滿1%（良好） C：1%以上（不良）(Heat resistance) After the coating film used for the transparency evaluation was heated in a nitrogen atmosphere at 300°C for 1 hour in an oven, the transparency evaluation was performed, and the total light transmittance after heating was subtracted from the value of the total light transmittance before self-heating The absolute value of the value obtained is evaluated. The smaller the change in total light transmittance before and after heating is, the higher the heat resistance is, so it is preferable, and evaluation is performed according to the following criteria. A: Less than 0.5% (extremely good) B: 0.5% or more and less than 1% (good) C: 1% or more (bad)
（熱膨脹性） 使用刮刀將無機氧化物塗料以乾燥後的膜厚成為50 μm的方式塗佈於250 μm厚的聚對苯二甲酸乙二酯（polyethylene terephthalate，PET）膜，利用烘箱於105℃下乾燥1小時，從而形成塗膜。將該塗膜自基材剝離，製作無機氧化物膜。將無機氧化物膜利用烘箱於250℃下加熱1小時後，加工成4.5 mm×3.0 cm的試驗片，使用Q400EM（TA儀器（TA Instrument）公司製造），根據施加拉伸負荷時的溫度與試驗片的應變的關係來測定線膨脹係數。黏合劑亦藉由相同的方法進行塗佈、乾燥，而形成膜，並測定線膨脹係數。根據自僅有黏合劑的膜的線膨脹係數的值減去無機氧化物膜的線膨脹係數所得的值，按照下述的基準進行評價。 A：10 ppm/℃以上（極其良好） B：未滿10 ppm/℃且5 ppm以上（良好） C：未滿5 ppm/℃（不良）(Thermal expansion) The inorganic oxide coating was applied to a 250 μm thick polyethylene terephthalate (PET) film with a doctor blade so that the film thickness after drying became 50 μm, and dried at 105°C for 1 hour in an oven. To form a coating film. The coating film was peeled off from the substrate to produce an inorganic oxide film. After heating the inorganic oxide film in an oven at 250°C for 1 hour, it was processed into a test piece of 4.5 mm×3.0 cm, using Q400EM (manufactured by TA Instrument), according to the temperature and test when a tensile load was applied The coefficient of linear expansion is determined based on the strain of the sheet. The adhesive is also coated and dried by the same method to form a film, and the linear expansion coefficient is measured. Based on the value obtained by subtracting the linear expansion coefficient of the inorganic oxide film from the value of the linear expansion coefficient of the adhesive-only film, the evaluation was performed according to the following criteria. A: 10 ppm/℃ or more (extremely good) B: Less than 10 ppm/℃ and more than 5 ppm (good) C: Less than 5 ppm/℃ (bad)
[表3]
表3
[表4]
表4
如表3所示般，實施例1～實施例28的無機氧化物分散體的黏度、分散粒徑、及經時穩定性均良好。尤其是實施例1～實施例8、實施例10～實施例20、及實施例25～實施例28的無機氧化物分散體的經時穩定性的結果更良好。另外，如表4所示般，實施例29～實施例52的無機氧化物塗料、及膜的透明性、耐熱性均良好，尤其是實施例29～實施例36、及實施例38～實施例52的無機氧化物塗料、及膜更良好。 [產業上之可利用性]As shown in Table 3, the inorganic oxide dispersions of Examples 1 to 28 have good viscosity, dispersion particle size, and stability over time. In particular, the results of the stability over time of the inorganic oxide dispersions of Examples 1 to 8, 8, 10 to 20, and 25 to 28 were even better. In addition, as shown in Table 4, the inorganic oxide coatings of Examples 29 to 52, and the films have good transparency and heat resistance, and in particular, Examples 29 to 36, and Examples 38 to Examples 52 inorganic oxide coatings, and membranes are better. [Industry availability]
本發明的實施形態的無機氧化物分散體可廣泛地應用於出於調整機械特性（機械強度等）、光學特性、電特性等目的而添加的無機氧化物中，因此能夠用於需要表面硬度調整、折射率調整、紅外線截止、抗靜電性調整、熱膨脹性調整等的塗膜、膜等的廣泛的用途中。The inorganic oxide dispersion of the embodiment of the present invention can be widely applied to inorganic oxides added for the purpose of adjusting mechanical properties (mechanical strength, etc.), optical properties, electrical properties, etc., and therefore can be used for surface hardness adjustment. It is used in a wide range of applications such as coating films and films such as refractive index adjustment, infrared cutoff, antistatic adjustment, and thermal expansion adjustment.
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| US20080286583A1 (en) * | 2004-10-08 | 2008-11-20 | Tokuyama Corporation | Coating Composition and Production Process Thereof |
| JP2006131899A (en) * | 2004-10-08 | 2006-05-25 | Tokuyama Corp | Composition for coating agent and method for producing the same |
| JP4692630B2 (en) | 2006-05-29 | 2011-06-01 | 東洋インキ製造株式会社 | Method for producing metal oxide dispersion, laminate and dispersant |
| JP5082814B2 (en) | 2007-12-11 | 2012-11-28 | 住友大阪セメント株式会社 | Inorganic oxide-containing transparent composite and method for producing the same |
| US7820724B2 (en) * | 2008-02-14 | 2010-10-26 | Millennium Inorganic Chemicals, Inc. | Colloidal titanium dioxide sols |
| JP5728816B2 (en) * | 2010-03-26 | 2015-06-03 | 東洋インキＳｃホールディングス株式会社 | Vinyl polymer for inorganic oxide dispersion and conductive inorganic oxide dispersion comprising the same |
| JP6520063B2 (en) * | 2013-12-05 | 2019-05-29 | 東洋インキＳｃホールディングス株式会社 | Pigment composition, method for producing the same, and pigment composition for color filter |
| KR102628748B1 (en) * | 2015-04-30 | 2024-01-24 | 닛산 가가쿠 가부시키가이샤 | Coating composition and optical member |
-
2018
- 2018-05-28 JP JP2018101435A patent/JP6631656B2/en active Active
-
2019
- 2019-05-27 CN CN201980035581.3A patent/CN112424297A/en active Pending
- 2019-05-27 WO PCT/JP2019/020836 patent/WO2019230629A1/en active Application Filing
- 2019-05-27 KR KR1020207035123A patent/KR20210013705A/en active Search and Examination
- 2019-05-28 TW TW108118422A patent/TW202003724A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JP6631656B2 (en) | 2020-01-15 |
| JP2019206611A (en) | 2019-12-05 |
| CN112424297A (en) | 2021-02-26 |
| WO2019230629A1 (en) | 2019-12-05 |
| KR20210013705A (en) | 2021-02-05 |
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