TW201922612A - Modified zirconium tungstate phosphate, negative thermal expansion filler, and polymeric composition - Google Patents
Modified zirconium tungstate phosphate, negative thermal expansion filler, and polymeric composition Download PDFInfo
- Publication number
- TW201922612A TW201922612A TW107136439A TW107136439A TW201922612A TW 201922612 A TW201922612 A TW 201922612A TW 107136439 A TW107136439 A TW 107136439A TW 107136439 A TW107136439 A TW 107136439A TW 201922612 A TW201922612 A TW 201922612A
- Authority
- TW
- Taiwan
- Prior art keywords
- tungstate
- phosphate
- zirconium phosphate
- zirconium
- modified zirconium
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
本發明是有關於一種作為負熱膨脹填料有用的改質磷酸鎢酸鋯、使用其的負熱膨脹填料和高分子組成物。The present invention relates to a modified zirconium phosphate tungstate useful as a negative thermal expansion filler, a negative thermal expansion filler using the same, and a polymer composition.
對於大多物質而言，若溫度上升，則因熱膨脹而長度或體積增大。與此相對，亦已知有若加溫則相反地體積變小的顯示負的熱膨脹的材料（以下亦有時稱為「負熱膨脹材」）。關於顯示負的熱膨脹的材料，已知可與其他材料一併使用來抑制由溫度變化引起的材料的熱膨脹的變化。For most substances, as the temperature increases, the length or volume increases due to thermal expansion. On the other hand, there is also known a material that exhibits a negative thermal expansion when the volume is reduced when heated (hereinafter sometimes referred to as a “negative thermal expansion material”). Regarding a material exhibiting negative thermal expansion, it is known that it can be used together with other materials to suppress a change in thermal expansion of the material caused by a temperature change.
作為顯示負的熱膨脹的材料，例如已知有β-鋰霞石（β-eucryptite）、鎢酸鋯（ZrW2 O8 ）、磷酸鎢酸鋯（Zr2 WO4 (PO4 )2 ）、Znx Cd1-x (CN)2 、氮化錳、鉍·鎳·鐵氧化物等。As materials showing negative thermal expansion, for example, β-eucryptite, zirconium tungstate (ZrW 2 O 8 ), zirconium tungstate phosphate (Zr 2 WO 4 (PO 4 ) 2 ), and Zn are known. x Cd 1-x (CN) 2 , manganese nitride, bismuth, nickel, and iron oxide.
磷酸鎢酸鋯的線膨脹係數於0℃～400℃的溫度範圍內為-3.4 ppm/℃～-3.0 ppm/℃，負熱膨脹性大，藉由與顯示正的熱膨脹的材料（以下亦有時稱為「正熱膨脹材」）併用而可製造低熱膨脹的材料（例如參照專利文獻1～專利文獻3）。The linear expansion coefficient of zirconium tungstate phosphate is -3.4 ppm / ° C to -3.0 ppm / ° C in the temperature range of 0 ° C to 400 ° C. The negative thermal expansion is large. (Referred to as a "positive thermal expansion material"), which can be used in combination to produce a material with low thermal expansion (see, for example, Patent Documents 1 to 3).
另外，亦提出有將正熱膨脹材的樹脂等高分子化合物與負熱膨脹材併用（專利文獻4～專利文獻5）。It is also proposed to use a polymer compound such as a resin of a positive thermal expansion material and a negative thermal expansion material in combination (Patent Documents 4 to 5).
然而，關於磷酸鎢酸鋯，若與水接觸，則尤其是結構中的Zr離子或W離子、P離子溶出，存在因此而使作為負熱膨脹材的性能降低的問題，或者因該些溶出金屬離子而使樹脂或其成形品的性能劣化的問題。However, if zirconium tungstate phosphate is in contact with water, especially Zr ions, W ions, and P ions in the structure elute, and therefore there is a problem that the performance as a negative thermal expansion material is reduced, or these metal ions are eluted. In addition, there is a problem that the performance of a resin or a molded article thereof is deteriorated.
另外，除所述問題外，磷酸鎢酸鋯與疏水性樹脂等高分子化合物的親和性存在問題，難以於高分子化合物中均勻地分散，因此，難以獲得含有磷酸鎢酸鋯作為負熱膨脹材的低熱膨脹性材料。In addition, in addition to the problems described above, there is a problem in the affinity of zirconium phosphate tungstate with a polymer compound such as a hydrophobic resin, and it is difficult to uniformly disperse the polymer compound. Therefore, it is difficult to obtain a zirconium phosphate tungstate containing negative thermal expansion material. Low thermal expansion material.
另外，下述非專利文獻1中雖提出有以改良對聚醯亞胺的分散性為目的而利用偶合劑對磷酸鎢酸鋯進行處理，但未揭示具體的偶合劑的種類。
[現有技術文獻]
[專利文獻]In addition, although the following non-patent document 1 proposes treating zirconium phosphate tungstate with a coupling agent for the purpose of improving the dispersibility to polyimide, the specific type of the coupling agent is not disclosed.
[Prior Art Literature]
[Patent Literature]
[專利文獻1]日本專利特開2005-35840號公報
[專利文獻2]日本專利特開2015-10006號公報
[專利文獻3]國際公開第2017/61403號手冊
[專利文獻4]日本專利特開2015-38197號公報
[專利文獻5]日本專利特開2016-113608號公報
[非專利文獻][Patent Document 1] Japanese Patent Laid-Open No. 2005-35840
[Patent Document 2] Japanese Patent Laid-Open No. 2015-10006
[Patent Document 3] International Publication No. 2017/61403
[Patent Document 4] Japanese Patent Laid-Open No. 2015-38197
[Patent Document 5] Japanese Patent Laid-Open No. 2016-113608
[Non-patent literature]
[非專利文獻1]日本化學會講演草稿集第94期No.3 Page.797（2014）[Non-Patent Document 1] Japanese Chemical Society Lecture Draft 94th Issue No.3 Page.797 (2014)
[發明所欲解決之課題]
因此，本發明的目的在於提供一種磷酸鎢酸鋯的Zr離子、W離子及P離子不易溶出，適宜用作高分子化合物所含有的負熱膨脹填料的改質磷酸鎢酸鋯、使用其的負熱膨脹填料和高分子組成物。
[解決課題之手段][Problems to be Solved by the Invention]
Therefore, the object of the present invention is to provide a modified zirconium phosphate tungstate phosphate which is difficult to dissolve out of Zr ions, W ions and P ions of zirconium tungstate phosphate, and is suitable for use as a negative thermal expansion filler contained in a polymer compound, and to use it for negative thermal expansion. Filler and polymer composition.
[Means for solving problems]
本發明者等人鑒於所述實情而反覆進行努力研究，結果發現：藉由利用特定的矽烷偶合劑對磷酸鎢酸鋯的粒子表面進行表面處理而獲得的改質磷酸鎢酸鋯在與水接觸的情況下可有效地抑制Zr離子、W離子及P離子的溶出；並且，該改質磷酸鎢酸鋯均勻地分散於樹脂等高分子化合物中，能夠製造含有負熱膨脹填料的低熱膨脹性材料，從而完成本發明。The inventors of the present invention conducted diligent research in light of the facts, and found that the modified zirconium phosphate tungstate obtained by surface-treating the particle surface of zirconium phosphate tungstate with a specific silane coupling agent is in contact with water. Can effectively suppress the dissolution of Zr ions, W ions, and P ions; and the modified zirconium phosphate tungstate is evenly dispersed in polymer compounds such as resins, and can produce low thermal expansion materials containing negative thermal expansion fillers, Thus, the present invention has been completed.
即，本發明（1）提供一種改質磷酸鎢酸鋯，其特徵在於，其為藉由下述通式（1）：
R1
-Si(OR2
)3
（1）
（式中，R1
表示碳數3以上的烷基。R2
表示碳數1～4的烷基）
所表示的矽烷偶合劑進行處理而得的磷酸鎢酸鋯粒子的表面被覆處理物。That is, the present invention (1) provides a modified zirconium phosphate tungstate, which is characterized by adopting the following general formula (1):
R 1 -Si (OR 2 ) 3 (1)
(In the formula, R 1 represents an alkyl group having 3 or more carbon atoms. R 2 represents an alkyl group having 1 to 4 carbon atoms.)
The surface-coated product of the zirconium phosphate tungstate phosphate particles obtained by treating the indicated silane coupling agent.
另外，本發明（2）提供如（1）所述的改質磷酸鎢酸鋯，其中相對於改質磷酸鎢酸鋯中的磷酸鎢酸鋯，所述通式（1）所表示的矽烷偶合劑的被覆物的被覆量為0.05質量%～30質量%。In addition, the present invention (2) provides the modified zirconium phosphate tungstate as described in (1), wherein the silane couple represented by the general formula (1) is compared to the zirconium tungstate phosphate in the modified zirconium phosphate tungstate. The coating amount of the coating material of the mixture is from 0.05% by mass to 30% by mass.
另外，本發明（3）提供一種改質磷酸鎢酸鋯，其特徵在於，其為利用下述通式（1）：
R1
-Si(OR2
)3
（1）
（式中，R1
表示碳數3以上的烷基。R2
表示碳數1～4的烷基）
所表示的矽烷偶合劑對磷酸鎢酸鋯粒子的表面進行表面被覆處理而得者。In addition, the present invention (3) provides a modified zirconium phosphate tungstate, which is characterized by using the following general formula (1):
R 1 -Si (OR 2 ) 3 (1)
(In the formula, R 1 represents an alkyl group having 3 or more carbon atoms. R 2 represents an alkyl group having 1 to 4 carbon atoms.)
The silane coupling agent shown is obtained by surface-treating the surface of the zirconium phosphate tungstate phosphate particles.
另外，本發明（4）提供如（3）所述的改質磷酸鎢酸鋯，其中相對於所述磷酸鎢酸鋯粒子，所述通式（1）所表示的矽烷偶合劑量為0.05質量%～30質量%。In addition, the present invention (4) provides the modified zirconium phosphate tungstate according to (3), wherein the silane coupling dose represented by the general formula (1) is 0.05% by mass relative to the zirconium phosphate tungstate particles. -30% by mass.
另外，本發明（5）提供如（1）～（4）中任一項所述的改質磷酸鎢酸鋯，其中所述磷酸鎢酸鋯粒子的BET比表面積為0.1 m2 /g～50 m2 /g。In addition, the present invention (5) provides the modified zirconium phosphate tungstate according to any one of (1) to (4), wherein the BET specific surface area of the zirconium phosphate tungstate phosphate is 0.1 m 2 / g to 50 m 2 / g.
另外，本發明（6）提供如（1）～（5）中任一項所述的改質磷酸鎢酸鋯，其中所述磷酸鎢酸鋯粒子的平均粒徑為0.02 μm～50 μm。Further, the present invention (6) provides the modified zirconium phosphate tungstate phosphate according to any one of (1) to (5), wherein the zirconium phosphate tungstate phosphate particles have an average particle diameter of 0.02 μm to 50 μm.
另外，本發明（7）提供如（1）～（6）中任一項所述的改質磷酸鎢酸鋯，其中所述磷酸鎢酸鋯粒子更含有副成分元素。In addition, the present invention (7) provides the modified zirconium phosphate tungstate according to any one of (1) to (6), wherein the zirconium phosphate tungstate phosphate further contains a subcomponent element.
另外，本發明（8）提供如（1）～（7）中任一項所述的改質磷酸鎢酸鋯，其中所述離子溶出試驗中的Zr離子溶出濃度為20 ppm以下，W離子溶出濃度為400 ppm以下，P離子溶出濃度為100 ppm以下。
＜離子溶出試驗＞
於試驗水70 ml中對改質磷酸鎢酸鋯1 g進行1小時沸騰處理，繼而，測定沸騰處理後的試驗水中的Zr離子濃度、W離子濃度及P離子濃度，將該沸騰處理後的試驗水中的各離子濃度設為各離子的溶出濃度。In addition, the present invention (8) provides the modified zirconium phosphate tungstate according to any one of (1) to (7), wherein the Zr ion elution concentration in the ion dissolution test is 20 ppm or less, and the W ion is eluted The concentration is 400 ppm or less, and the P ion elution concentration is 100 ppm or less.
＜ Ion dissolution test ＞
1 g of modified zirconium tungstate phosphate was subjected to boiling treatment in 70 ml of test water for one hour, and then the Zr ion concentration, W ion concentration, and P ion concentration in the test water after the boiling treatment were measured, and the test after the boiling treatment was performed. The concentration of each ion in water was set as the elution concentration of each ion.
另外，本發明（9）提供一種負熱膨脹填料，其特徵在於包含如（1）～（8）中任一項所述的改質磷酸鎢酸鋯。In addition, the present invention (9) provides a negative thermal expansion filler comprising the modified zirconium phosphate tungstate as described in any one of (1) to (8).
另外，本發明（10）提供一種高分子組成物，其特徵在於含有如（9）所述的負熱膨脹填料、及高分子化合物。
[發明的效果]In addition, the present invention (10) provides a polymer composition comprising the negative thermal expansion filler according to (9) and a polymer compound.
[Effect of the invention]
根據本發明，可提供一種磷酸鎢酸鋯的Zr離子、W離子及P離子不易溶出，適宜用作高分子化合物所含有的負熱膨脹填料的改質磷酸鎢酸鋯、使用其的負熱膨脹填料和高分子組成物。According to the present invention, there can be provided a modified zirconium phosphate tungstate phosphate which is not easily dissolved out of Zr ions, W ions and P ions of zirconium tungstate phosphate, and is suitably used as a negative thermal expansion filler contained in a polymer compound, a negative thermal expansion filler using the same, and Polymer composition.
本發明的第一形態的改質磷酸鎢酸鋯的特徵在於，其為藉由下述通式（1）：
R1
-Si(OR2
)3
（1）
（式中，R1
表示碳數3以上的烷基。R2
表示碳數1～4的烷基）
所表示的矽烷偶合劑進行處理而得的磷酸鎢酸鋯粒子的表面被覆處理物。The modified zirconium phosphate tungstate in the first aspect of the present invention is characterized by the following general formula (1):
R 1 -Si (OR 2 ) 3 (1)
(In the formula, R 1 represents an alkyl group having 3 or more carbon atoms. R 2 represents an alkyl group having 1 to 4 carbon atoms.)
The surface-coated product of the zirconium phosphate tungstate phosphate particles obtained by treating the indicated silane coupling agent.
本發明的第二形態的改質磷酸鎢酸鋯的特徵在於，其為利用下述通式（1）：
R1
-Si(OR2
)3
（1）
（式中，R1
表示碳數3以上的烷基。R2
表示碳數1～4的烷基）
所表示的矽烷偶合劑對磷酸鎢酸鋯粒子的表面進行表面被覆處理而得者。The modified zirconium phosphate tungstate in the second aspect of the present invention is characterized by using the following general formula (1):
R 1 -Si (OR 2 ) 3 (1)
(In the formula, R 1 represents an alkyl group having 3 or more carbon atoms. R 2 represents an alkyl group having 1 to 4 carbon atoms.)
The silane coupling agent shown is obtained by surface-treating the surface of the zirconium phosphate tungstate phosphate particles.
本發明的第一形態的改質磷酸鎢酸鋯為藉由使用矽烷偶合劑對磷酸鎢酸鋯粒子的表面進行被覆處理而獲得的「藉由矽烷偶合劑進行處理而得的磷酸鎢酸鋯粒子的表面被覆處理物」。另外，本發明的第二形態的改質磷酸鎢酸鋯為利用矽烷偶合劑對磷酸鎢酸鋯粒子的表面進行表面被覆處理而獲得者。The modified zirconium phosphate tungstate phosphate according to the first aspect of the present invention is a "zirconium tungstate phosphate particle obtained by processing with a silane coupling agent" obtained by coating the surface of the zirconium phosphate tungstate phosphate particles with a silane coupling agent. Surface coatings ". The modified zirconium phosphate tungstate in the second aspect of the present invention is obtained by subjecting the surface of the zirconium phosphate tungstate phosphate particles to a surface coating treatment using a silane coupling agent.
本發明的磷酸鎢酸鋯由下述通式（2）：
Zrx
WOy
(PO4
)z
（2）
（式中，x為1.7≦x≦2.3，較佳為1.8≦x≦2.2，y為0.85≦y≦1.15，較佳為0.90≦y≦1.10，z為1.7≦z≦2.3，較佳為1.8≦z≦2.2）
所表示。The zirconium phosphate tungstate of the present invention has the following general formula (2):
Zr x WO y (PO 4 ) z (2)
(In the formula, x is 1.7 ≦ x ≦ 2.3, preferably 1.8 ≦ x ≦ 2.2, y is 0.85 ≦ y ≦ 1.15, preferably 0.90 ≦ y ≦ 1.10, z is 1.7 ≦ z ≦ 2.3, and preferably 1.8 ≦ z ≦ 2.2)
Indicated.
本發明的磷酸鎢酸鋯粒子為經表面被覆處理之前的粒子。本發明的磷酸鎢酸鋯粒子的製造過程並無特別限制，作為本發明的磷酸鎢酸鋯粒子的製造方法，例如可列舉：1）利用濕式球磨機將磷酸鋯、氧化鎢及MgO等反應促進劑混合，對所得的混合物進行煆燒的方法（例如參照日本專利特開2005-35840號公報）；2）將磷酸銨等磷源、與鎢酸銨等鎢源及氯化鋯等鋯源進行濕式混合後，進行煆燒的方法（例如參照日本專利特開2015-10006號公報）；3）對包含氧化鋯、氧化鎢及磷酸二氫銨的混合物進行煆燒的方法（例如參照「材料研究公報（Materials Research Bulletin）」，44（2009），p2045-2049）；4）將鎢化合物與包含磷及鋯的非晶質化合物的混合物作為反應前驅物，對該反應前驅物進行煆燒的方法（參照國際公開第2017/061402號手冊）等。並且，就本發明的磷酸鎢酸鋯粒子而言，就容易利用工業上有利的方法來控制粒徑或粒子形狀等粉體特性、另外容易獲得負熱特性優異者的觀點而言，較佳為利用所述4）的方法而獲得的磷酸鎢酸鋯粒子。The zirconium phosphate tungstate phosphate particles of the present invention are particles before being subjected to a surface coating treatment. The manufacturing process of the zirconium phosphate tungstate phosphate particles of the present invention is not particularly limited. Examples of the method for manufacturing the zirconium phosphate tungstate phosphate particles of the present invention include: 1) the reaction of zirconium phosphate, tungsten oxide, and MgO is promoted by a wet ball mill; A method of blending an agent and sintering the obtained mixture (for example, refer to Japanese Patent Laid-Open No. 2005-35840); 2) a phosphorus source such as ammonium phosphate, a tungsten source such as ammonium tungstate, and a zirconium source such as zirconium chloride A method of calcining after wet mixing (for example, refer to Japanese Patent Laid-Open No. 2015-10006); 3) A method of calcining a mixture containing zirconia, tungsten oxide, and ammonium dihydrogen phosphate (for example, refer to "Materials Materials Research Bulletin ", 44 (2009), p2045-2049); 4) A mixture of a tungsten compound and an amorphous compound containing phosphorus and zirconium is used as a reaction precursor, and the reaction precursor is subjected to calcination. Method (refer to International Publication No. 2017/061402). In addition, the zirconium tungstate phosphate particles of the present invention are preferred from the viewpoint of easily controlling powder characteristics such as particle size and particle shape by industrially advantageous methods, and easily obtaining excellent negative thermal characteristics. The zirconium phosphate tungstate phosphate particles obtained by the method of 4).
本發明的磷酸鎢酸鋯粒子的BET比表面積並無特別限制，較佳為0.1 m2 /g～50 m2 /g，尤佳為0.1 m2 /g～20 m2 /g。藉由磷酸鎢酸鋯粒子的BET比表面積處於所述範圍，於將改質磷酸鎢酸鋯用作樹脂或玻璃等的填料時，操作變容易。The BET specific surface area of the zirconium phosphate tungstate phosphate particles of the present invention is not particularly limited, but is preferably 0.1 m 2 / g to 50 m 2 / g, and more preferably 0.1 m 2 / g to 20 m 2 / g. When the BET specific surface area of the zirconium tungstate phosphate particles is in the above range, when the modified zirconium phosphate tungstate is used as a filler for a resin, glass, or the like, handling becomes easy.
本發明的磷酸鎢酸鋯粒子的平均粒徑並無特別限制，以藉由掃描型電子顯微鏡觀察法而求出的平均粒徑計，較佳為0.02 μm～50 μm，尤佳為0.5 μm～30 μm。藉由磷酸鎢酸鋯粒子的平均粒徑處於所述範圍，於將改質磷酸鎢酸鋯用作樹脂或玻璃等的填料時，操作變容易。The average particle diameter of the zirconium phosphate tungstate phosphate particles of the present invention is not particularly limited, and it is preferably 0.02 μm to 50 μm, and more preferably 0.5 μm to the average particle diameter determined by a scanning electron microscope observation method. 30 μm. When the average particle diameter of the zirconium tungstate phosphate particles is in the above range, when modified zirconium phosphate tungstate is used as a filler for a resin, glass, or the like, handling becomes easy.
本發明的磷酸鎢酸鋯可以提升對正熱膨脹材的分散性或填充特性為目的而含有副成分元素。作為本發明的磷酸鎢酸鋯的副成分元素，例如可列舉：Mg、V、Zn、Cu、Fe、Cr、Mn、Ni、Li、Al、B、Na、K、F、Cl、Br、I、Ca、Sr、Ba、Ti、Hf、Nb、Ta、Y、Yb、Si、S、Mo、Co、Bi、Te、Pb、Ag、Cd、In、Sn、Sb、Ga、Ge、La、Ce、Nd、Sm、Eu、Tb、Dy及Ho等。該些副成分元素可為一種，亦可為兩種以上。該些副成分元素中，就對正熱膨脹材的分散性或填充特性變高的觀點而言，較佳為Mg及/或V。再者，所謂副成分元素，是指於磷酸鎢酸鋯中含有500 ppm以上的除Zr、W、P及O以外的所有元素。The zirconium phosphate tungstate of the present invention can contain a sub-component element for the purpose of improving dispersibility or filling characteristics to a positive thermal expansion material. Examples of the subcomponent element of the zirconium tungstate phosphate of the present invention include, for example, Mg, V, Zn, Cu, Fe, Cr, Mn, Ni, Li, Al, B, Na, K, F, Cl, Br, I , Ca, Sr, Ba, Ti, Hf, Nb, Ta, Y, Yb, Si, S, Mo, Co, Bi, Te, Pb, Ag, Cd, In, Sn, Sb, Ga, Ge, La, Ce , Nd, Sm, Eu, Tb, Dy and Ho. These secondary component elements may be one kind, or two or more kinds. Among these sub-component elements, Mg and / or V are preferred from the viewpoint that the dispersibility or filling characteristics of the positive thermal expansion material is improved. Note that the term “sub-component element” means that all elements other than Zr, W, P, and O are contained in zirconium phosphate tungstate at 500 ppm or more.
相對於磷酸鎢酸鋯粒子整體，本發明的磷酸鎢酸鋯粒子中的副成分元素的合計含量較佳為0.1質量%～3質量%，尤佳為0.2質量%～2質量%。藉由磷酸鎢酸鋯粒子中的副成分元素的合計含量處於所述範圍，而具有優異的負熱膨脹性，分散性及填充特性優異。再者，於磷酸鎢酸鋯粒子含有僅一種副成分元素的情況下，所述磷酸鎢酸鋯粒子中的副成分元素的合計含量是指該一種副成分元素的含量，另外，於磷酸鎢酸鋯粒子含有兩種以上的副成分元素的情況下，所述磷酸鎢酸鋯粒子中的副成分元素的合計含量是指該些兩種以上的副成分元素的含量的合計。The total content of the sub-component elements in the zirconium phosphate tungstate phosphate particles according to the present invention is preferably 0.1% to 3% by mass, and more preferably 0.2% to 2% by mass, with respect to the entire zirconium phosphate tungstate particles. Since the total content of the sub-component elements in the zirconium tungstate phosphate particles is in the above range, it has excellent negative thermal expansion properties, and excellent dispersibility and filling characteristics. When the zirconium tungstate phosphate particles contain only one kind of sub-component element, the total content of the sub-component elements in the zirconium tungstate phosphate particles refers to the content of the one kind of sub-component element. When the zirconium particles contain two or more kinds of sub-component elements, the total content of the sub-component elements in the zirconium phosphate tungstate particles means the total content of the two or more kinds of sub-component elements.
本發明的磷酸鎢酸鋯粒子的形狀並無特別限制，例如可為球狀、粒狀、板狀、鱗片狀、晶須狀、棒狀、絲（filament）狀、破碎狀。The shape of the zirconium phosphate tungstate phosphate particles of the present invention is not particularly limited, and may be, for example, spherical, granular, plate-like, scale-like, whisker-like, rod-like, filament-like, or broken-like.
本發明的矽烷偶合劑為下述通式（1）：
R1
-Si(OR2
)3
（1）
（式中，R1
表示碳數3以上的烷基。R2
表示碳數1～4的烷基）
所表示的矽烷偶合劑。The silane coupling agent of the present invention has the following general formula (1):
R 1 -Si (OR 2 ) 3 (1)
(In the formula, R 1 represents an alkyl group having 3 or more carbon atoms. R 2 represents an alkyl group having 1 to 4 carbon atoms.)
The indicated silane coupling agent.
關於本發明的第一形態的改質磷酸鎢酸鋯及本發明的第二形態的改質磷酸鎢酸鋯，藉由利用通式（1）所表示的矽烷偶合劑對磷酸鎢酸鋯粒子的表面進行被覆處理，在與水接觸的情況下亦有效地抑制Zr離子、W離子及P離子的溶出，另外均勻地分散於樹脂等高分子化合物中，可獲得含有負熱膨脹填料的低熱膨脹性材料。Regarding the modified zirconium tungstate phosphate in the first aspect of the present invention and the modified zirconium tungstate phosphate in the second aspect of the present invention, the zirconium tungstate phosphate particles were treated with a silane coupling agent represented by the general formula (1). The surface is coated to effectively suppress the dissolution of Zr ions, W ions, and P ions even in contact with water. In addition, it is evenly dispersed in polymer compounds such as resins to obtain low thermal expansion materials containing negative thermal expansion fillers. .
通式（1）中，R1 為碳數3以上、較佳為4～12、尤佳為6～12的烷基，較佳為直鏈狀的烷基。藉由通式（1）中的R1 的碳數為所述範圍，而有效地抑制Zr離子、W離子及P離子的溶出，另外當用作負熱膨脹填料時，對樹脂的分散性良好。通式（1）中的R2 為碳數1～4、較佳為1～2的烷基。In the general formula (1), R 1 is an alkyl group having 3 or more carbon atoms, preferably 4 to 12, particularly preferably 6 to 12, and preferably a linear alkyl group. When the carbon number of R 1 in the general formula (1) is within the above range, the elution of Zr ions, W ions, and P ions is effectively suppressed, and when used as a negative thermal expansion filler, the dispersibility to the resin is good. R 2 in the general formula (1) is an alkyl group having 1 to 4 carbon atoms, and preferably 1 to 2 carbon atoms.
本發明的第一形態的改質磷酸鎢酸鋯中，相對於改質磷酸鎢酸鋯中的磷酸鎢酸鋯，通式（1）所表示的矽烷偶合劑的被覆物的被覆量較佳為0.05質量%～30質量%，尤佳為0.1質量%～10質量%，進而佳為0.2質量%～5.0質量%。藉由通式（1）所表示的矽烷偶合劑的被覆物的被覆量處於所述範圍，而有效地抑制Zr離子、W離子及P離子的溶出，另外抑制由偶合劑引起的粒子彼此的凝聚，進而疏水性亦變良好，當用作負熱膨脹填料時，樹脂分散性變良好。In the modified zirconium phosphate tungstate in the first aspect of the present invention, the coating amount of the coating material of the silane coupling agent represented by the general formula (1) is preferably higher than that of the zirconium tungstate phosphate in the modified zirconium phosphate tungstate. 0.05 to 30% by mass, particularly preferably 0.1 to 10% by mass, and even more preferably 0.2 to 5.0% by mass. When the coating amount of the coating material of the silane coupling agent represented by the general formula (1) is in the above range, the elution of Zr ions, W ions, and P ions is effectively suppressed, and the aggregation of particles caused by the coupling agent is also suppressed. In addition, the hydrophobicity becomes better, and when used as a negative thermal expansion filler, the resin dispersibility becomes good.
本發明的第二形態的改質磷酸鎢酸鋯中，相對於磷酸鎢酸鋯粒子，通式（1）所表示的矽烷偶合劑量較佳為0.05質量%～30質量%，尤佳為0.1質量%～10質量%，進而佳為0.2質量%～5.0質量%。藉由通式（1）所表示的矽烷偶合劑量處於所述範圍，而有效地抑制Zr離子、W離子及P離子的溶出，另外抑制由偶合劑引起的粒子彼此的凝聚，進而疏水性亦變良好，當用作負熱膨脹填料時，樹脂分散性變良好。再者，所謂相對於磷酸鎢酸鋯而言的通式（1）所表示的矽烷偶合劑量，是指表面被覆處理中所使用的通式（1）所表示的矽烷偶合劑相對於進行表面被覆處理之前的磷酸鎢酸鋯粒子的質量的質量比例。In the modified zirconium phosphate tungstate phosphate according to the second aspect of the present invention, the silane coupling dose represented by the general formula (1) is preferably 0.05% by mass to 30% by mass, and more preferably 0.1% by mass, relative to the zirconium phosphate tungstate particles. % To 10% by mass, and more preferably 0.2 to 5.0% by mass. When the silane coupling dose represented by the general formula (1) is in the above range, the dissolution of Zr ions, W ions, and P ions is effectively suppressed, and the aggregation of particles caused by the coupling agent is also suppressed, and the hydrophobicity is also changed. Good, when used as a negative thermal expansion filler, the resin dispersibility becomes good. The silane coupling agent represented by the general formula (1) with respect to zirconium tungstate phosphate refers to the surface coating of the silane coupling agent represented by the general formula (1) used in the surface coating treatment. Mass ratio of mass of zirconium phosphate tungstate phosphate before processing.
藉由通式（1）所表示的偶合劑進行的磷酸鎢酸鋯的粒子的表面處理方法可為濕式或者亦可為乾式。The surface treatment method of the particles of zirconium tungstate phosphate using the coupling agent represented by the general formula (1) may be a wet method or a dry method.
於利用濕式法來實施藉由通式（1）所表示的偶合劑進行的磷酸鎢酸鋯的粒子的表面處理的情況下，作為表面處理方法，可列舉：將磷酸鎢酸鋯粒子浸漬於以所期望的濃度包含通式（1）所表示的偶合劑的溶媒中，對各溶媒進行噴霧乾燥、或於固液分離後進行乾燥，藉此而利用通式（1）所表示的偶合劑對磷酸鎢酸鋯粒子進行表面處理，利用通式（1）所表示的偶合劑被覆磷酸鎢酸鋯粒子的方法。When the surface treatment of the particles of zirconium tungstate phosphate with a coupling agent represented by the general formula (1) is performed by a wet method, examples of the surface treatment method include immersing zirconium phosphate tungstate phosphate particles in In a solvent containing the coupling agent represented by the general formula (1) at a desired concentration, each solvent is spray-dried or dried after solid-liquid separation, thereby using the coupling agent represented by the general formula (1). A method for surface-treating zirconium phosphate tungstate phosphate particles and coating the zirconium phosphate tungstate phosphate particles with a coupling agent represented by the general formula (1).
於利用乾式法來實施藉由通式（1）所表示的偶合劑進行的磷酸鎢酸鋯的粒子的表面處理的情況下，作為表面處理方法，可列舉：利用亨舍爾混合機（Henschel mixer）、氣流式粉碎機等機械構件，以乾式方式將通式（1）所表示的偶合劑與磷酸鎢酸鋯粒子混合的方法；或者，利用溶劑來稀釋通式（1）所表示的偶合劑，將稀釋液與磷酸鎢酸鋯混合，並對所得的混合物進行加熱乾燥的方法。When the surface treatment of the particles of zirconium tungstate phosphate using a coupling agent represented by the general formula (1) is performed by a dry method, the surface treatment method includes a Henschel mixer. ), A method for mixing mechanical components such as a jet mill with a dry method by mixing the coupling agent represented by the general formula (1) with zirconium phosphate tungstate particles; or using a solvent to dilute the coupling agent represented by the general formula (1) A method of mixing the diluent with zirconium phosphate tungstate and heating and drying the resulting mixture.
本發明的第一形態的改質磷酸鎢酸鋯及本發明的第二形態的改質磷酸鎢酸鋯在與水接觸的情況下亦抑制Zr離子及W離子的溶出，故本發明的第一形態的改質磷酸鎢酸鋯及本發明的第二形態的改質磷酸鎢酸鋯於離子溶出試驗中，Zr離子溶出濃度為20 ppm以下，較佳為10 ppm以下，W離子溶出濃度為400 ppm以下，較佳為300 ppm以下，P離子溶出濃度為100 ppm以下，較佳為50 ppm以下。再者，本發明中，離子溶出試驗是藉由於試驗水70 ml中對改質磷酸鎢酸鋯1 g進行1小時沸騰處理，繼而，測定沸騰處理後的試驗水中的Zr離子濃度、W離子濃度及P離子濃度而求出，將沸騰處理後的試驗水中的各離子濃度設為各離子的溶出濃度。The modified zirconium tungstate phosphate in the first aspect of the present invention and the modified zirconium tungstate phosphate in the second aspect of the present invention also suppress the elution of Zr ions and W ions when in contact with water, so the first aspect of the present invention The modified zirconium phosphate tungstate and the modified zirconium phosphate tungstate according to the second aspect of the present invention have a Zr ion dissolution concentration of 20 ppm or less, preferably 10 ppm or less, and a W ion dissolution concentration of 400. ppm or less, preferably 300 ppm or less, and P ion elution concentration is 100 ppm or less, and preferably 50 ppm or less. In addition, in the present invention, the ion dissolution test is performed by subjecting 1 g of modified zirconium tungstate phosphate to boiling treatment in 70 ml of test water for one hour, and then measuring the Zr ion concentration and W ion concentration in the test water after the boiling treatment. And P ion concentration, and each ion concentration in the test water after the boiling treatment was set as the elution concentration of each ion.
本發明的第一形態的改質磷酸鎢酸鋯及本發明的第二形態的改質磷酸鎢酸鋯是以粉末或分散於溶媒中的形態而使用。The modified zirconium tungstate phosphate in the first aspect of the present invention and the modified zirconium tungstate phosphate in the second aspect of the present invention are used in the form of powder or dispersed in a solvent.
本發明的第一形態的改質磷酸鎢酸鋯及本發明的第二形態的改質磷酸鎢酸鋯可與正熱膨脹材併用來提供低熱膨脹的材料。特別是本發明的第一形態的改質磷酸鎢酸鋯及本發明的第二形態的改質磷酸鎢酸鋯可調配於高分子化合物中，而適宜用作用於製造低熱膨脹性材料的負熱膨脹填料。The modified zirconium tungstate phosphate in the first aspect of the present invention and the modified zirconium tungstate phosphate in the second aspect of the present invention can be used together with a positive thermal expansion material to provide a material with low thermal expansion. In particular, the modified zirconium tungstate phosphate tungstate of the first aspect of the present invention and the modified zirconium tungstate phosphate tungstate of the second aspect of the present invention can be blended into a polymer compound, and are suitable for use as a negative thermal expansion for producing a low thermal expansion material. filler.
本發明的負熱膨脹填料的特徵在於包括本發明的第一形態的改質磷酸鎢酸鋯或本發明的第二形態的改質磷酸鎢酸鋯。The negative thermal expansion filler of the present invention includes the modified zirconium phosphate tungstate in the first aspect of the present invention or the modified zirconium tungstate phosphate in the second aspect of the present invention.
本發明的高分子組成物的特徵在於含有本發明的負熱膨脹填料及高分子化合物。即，本發明的高分子組成物中，使用本發明的第一形態的改質磷酸鎢酸鋯或本發明的第二形態的改質磷酸鎢酸鋯作為高分子組成物的負熱膨脹填料。The polymer composition of the present invention is characterized by containing the negative thermal expansion filler of the present invention and a polymer compound. That is, in the polymer composition of the present invention, the modified zirconium phosphate tungstate in the first aspect of the present invention or the modified zirconium tungstate phosphate in the second aspect of the present invention is used as the negative thermal expansion filler of the polymer composition.
本發明的高分子組成物的高分子化合物並無特別限制，例如可列舉：橡膠、聚烯烴、聚環烯烴、聚苯乙烯、丙烯腈-丁二烯-苯乙烯（Acrylonitrile Butadiene Styrene，ABS）、聚丙烯酸酯、聚苯硫醚、酚樹脂、聚醯胺樹脂、聚醯亞胺樹脂、環氧樹脂、矽酮樹脂、聚碳酸酯樹脂、聚乙烯樹脂、聚丙烯樹脂、聚對苯二甲酸乙二酯（polyethylene terephthalate）樹脂（PET樹脂）及聚氯乙烯樹脂等。The polymer compound of the polymer composition of the present invention is not particularly limited, and examples thereof include rubber, polyolefin, polycycloolefin, polystyrene, Acrylonitrile Butadiene Styrene (ABS), Polyacrylate, polyphenylene sulfide, phenol resin, polyamide resin, polyimide resin, epoxy resin, silicone resin, polycarbonate resin, polyethylene resin, polypropylene resin, polyethylene terephthalate Polyethylene terephthalate resin (PET resin) and polyvinyl chloride resin.
本發明的高分子組成物中，可藉由負熱膨脹填料的含量來控制高分子組成物的熱膨脹率。本發明的高分子組成物中，本發明的負熱膨脹填料的含量是根據用途或目的而適當選擇較佳的含量，大多情況下，相對於本發明的高分子組成物總量，本發明的高分子組成物中的本發明的負熱膨脹填料的含量為1體積%～90體積%。In the polymer composition of the present invention, the thermal expansion rate of the polymer composition can be controlled by the content of the negative thermal expansion filler. In the polymer composition of the present invention, the content of the negative thermal expansion filler of the present invention is appropriately selected according to the purpose or purpose. In most cases, the content of the present invention is higher than the total amount of the polymer composition of the present invention. The content of the negative thermal expansion filler of the present invention in the molecular composition is 1 to 90% by volume.
另外，除本發明的負熱膨脹填料以外，本發明的高分子組成物視需要亦可含有抗氧化劑、熱穩定劑、紫外線吸收劑、潤滑劑、剝離劑、包含染料、顏料的著色劑、阻燃劑、交聯劑、軟化劑、分散劑、硬化劑、聚合起始劑、無機填充劑等通常的添加劑作為其他調配物。In addition, in addition to the negative thermal expansion filler of the present invention, the polymer composition of the present invention may contain an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, a release agent, a coloring agent containing a dye and a pigment, and flame retardance, if necessary. Agents, crosslinking agents, softeners, dispersants, hardeners, polymerization initiators, inorganic fillers and other general additives as other formulations.
本發明的高分子組成物是藉由公知的方法而製造。例如，於高分子化合物為硬化性樹脂的情況下，可列舉：將硬化性樹脂（或者預聚物）、本發明的負熱膨脹填料及視需要所調配的其他調配物同時混入的方法；預先將本發明的負熱膨脹填料及視需要所調配的其他調配物與樹脂成分的一種混合，再將其與硬化性樹脂（或者預聚物）混合的方法，另外，於高分子化合物為熱塑性樹脂的情況下，可列舉：利用擠壓機（extruder）將本發明的負熱膨脹填料及視需要所調配的其他調配物熔融混合的方法；或者，將本發明的負熱膨脹填料及視需要所調配的調配物的粒子狀物均勻地機械混合後，利用射出成形機在混合的同時進行成形的方法等。
[實施例]The polymer composition of the present invention is produced by a known method. For example, when the polymer compound is a curable resin, a method of simultaneously mixing the curable resin (or prepolymer), the negative thermal expansion filler of the present invention, and other formulations prepared as necessary may be mentioned; The method for mixing the negative thermal expansion filler of the present invention and other formulations formulated with the resin component as required, and then mixing the same with a hardening resin (or prepolymer), and when the polymer compound is a thermoplastic resin In the following, a method of melt-mixing the negative thermal expansion filler of the present invention and other formulations prepared as required using an extruder may be listed; or the negative thermal expansion filler of the present invention and the formulation prepared as required After uniformly mechanically mixing the particulate matter, a method using an injection molding machine to perform molding while mixing.
[Example]
以下，藉由實施例對本發明進行說明，但本發明並不限定於該些實施例。
＜磷酸鎢酸鋯試樣的製備＞
（製造例1）（ZWP試樣1）
將市售的三氧化鎢（WO3
；平均粒徑1.2 μm）15質量份放入燒杯中，進而添加純水84質量份，並加入1質量份的聚羧酸銨鹽作為分散劑。
於室溫（25℃）下使用三一馬達（three-one motor）攪拌機攪拌120分鐘，製備包含三氧化鎢的15質量%漿料。漿料中的固體成分的平均粒徑為1.2 μm。
繼而，於該漿料中，以漿料中的Zr：W：P的莫耳比成為2.00：1.00：2.00的方式於室溫（25℃）下添加氫氧化鋯、85質量%磷酸水溶液，於2小時攪拌下進行反應。
反應結束後，於200℃、大氣下對漿料的總量進行24小時乾燥，獲得反應前驅物。對所獲得的反應前驅物進行X射線繞射，結果僅觀察到三氧化鎢的繞射峰值。
繼而，於950℃下於大氣中對所獲得的反應前驅物進行2小時煆燒反應，獲得白色的煆燒品。
對所獲得的煆燒品進行X射線繞射分析，結果，煆燒品為單相的Zr2
(WO4
)(PO4
)2
。另外，對所獲得的磷酸鎢酸鋯試樣的平均粒徑、BET比表面積進行測定，將其結果示於表1中。另外，對所獲得的磷酸鎢酸鋯試樣進行掃描型電子顯微鏡觀察，結果其粒子形狀為破碎狀（圖1）。Hereinafter, the present invention will be described by examples, but the present invention is not limited to these examples.
<Preparation of Zirconium Tungstate Phosphate Sample>
(Manufacturing example 1) (ZWP sample 1)
15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle diameter: 1.2 μm) was put into a beaker, 84 parts by mass of pure water was further added, and 1 part by mass of ammonium polycarboxylate was added as a dispersant.
It stirred at room temperature (25 degreeC) using the three-one motor mixer for 120 minutes, and prepared the 15 mass% slurry containing tungsten trioxide. The solid particles in the slurry had an average particle diameter of 1.2 μm.
Then, in this slurry, zirconium hydroxide and an 85% by mass phosphoric acid aqueous solution were added at room temperature (25 ° C.) so that the molar ratio of Zr: W: P in the slurry was 2.00: 1.00: 2.00. The reaction was carried out with stirring for 2 hours.
After completion of the reaction, the total amount of the slurry was dried at 200 ° C. for 24 hours in the air to obtain a reaction precursor. X-ray diffraction was performed on the obtained reaction precursor, and as a result, only a diffraction peak of tungsten trioxide was observed.
Then, the obtained reaction precursor was subjected to a calcination reaction in the air at 950 ° C for 2 hours to obtain a white calcined product.
X-ray diffraction analysis was performed on the obtained burned product, and as a result, the burned product was single-phase Zr 2 (WO 4 ) (PO 4 ) 2 . The average particle diameter and BET specific surface area of the obtained zirconium phosphate tungstate sample were measured, and the results are shown in Table 1. In addition, when the obtained zirconium phosphate tungstate sample was observed by a scanning electron microscope, the particle shape was broken (FIG. 1).
＜平均粒徑的測定方法＞
對測定資料進行掃描型電子顯微鏡觀察，獲得掃描型電子顯微鏡（Scanning Electron Microscope，SEM）圖像，繼而，自該SEM圖像中任意抽取100個粒子，測定各粒子的粒徑，並求出該些的平均值作為平均粒徑。<Method for measuring average particle size>
Scanning electron microscope observation was performed on the measurement data to obtain a Scanning Electron Microscope (SEM) image. Then, 100 particles were arbitrarily extracted from the SEM image, and the particle size of each particle was measured to determine the particle size. These averages are taken as the average particle size.
（製造例2）（ZWP試樣2）
將市售的三氧化鎢（WO3
；平均粒徑1.2 μm）15質量份放入燒杯中，進而添加純水84質量份。
於室溫（25℃）下攪拌120分鐘，製備包含三氧化鎢的15質量%漿料。漿料中的固體成分的平均粒徑為1.2 μm。
繼而，於該漿料中，以漿料中的Zr：W：P的莫耳比成為2.00：1.00：2.00的方式於室溫（25℃）下添加氫氧化鋯、85質量%磷酸水溶液及氫氧化鎂後，升溫至80℃，於4小時攪拌下進行反應。
反應結束後，加入1重量份的聚羧酸銨鹽作為分散劑，一邊攪拌漿料一邊供給至加入有直徑0.5 mm的氧化鋯珠的介質攪拌型珠磨機中，混合15分鐘而進行濕式粉碎。濕式粉碎後的漿料中的固體成分的平均粒徑為0.3 μm。
繼而，於設定為220℃的噴霧乾燥器（spray dryer）中，以2.4 L/h的供給速度供給漿料，獲得反應前驅物。對所獲得的反應前驅物進行X射線繞射，結果僅觀察到三氧化鎢的繞射峰值。
繼而，於960℃下於大氣中對所獲得的反應前驅物進行2小時煆燒反應，獲得白色的煆燒品。
對所獲得的煆燒品進行X射線繞射分析，結果，煆燒品為單相的Zr2
(WO4
)(PO4
)2
。另外，對所獲得的磷酸鎢酸鋯試樣的平均粒徑、BET比表面積進行測定，將其結果示於表1中。對所獲得的磷酸鎢酸鋯試樣進行掃描型電子顯微鏡觀察，結果其粒子形狀為球狀（圖2）。(Manufacture example 2) (ZWP sample 2)
15 parts by mass of commercially available tungsten trioxide (WO 3 ; average particle diameter: 1.2 μm) was placed in a beaker, and 84 parts by mass of pure water was further added.
It stirred at room temperature (25 degreeC) for 120 minutes, and prepared the 15 mass% slurry containing tungsten trioxide. The solid particles in the slurry had an average particle diameter of 1.2 μm.
Then, in this slurry, zirconium hydroxide, an 85% by mass phosphoric acid aqueous solution, and hydrogen were added at a room temperature (25 ° C.) so that the molar ratio of Zr: W: P in the slurry was 2.00: 1.00: 2.00. After magnesium oxide, the temperature was raised to 80 ° C, and the reaction was performed with stirring for 4 hours.
After the reaction was completed, 1 part by weight of a polycarboxylic acid ammonium salt was added as a dispersant, and the slurry was stirred while being fed to a medium stirring type bead mill containing zirconia beads having a diameter of 0.5 mm, and mixed for 15 minutes to perform a wet process. Crush. The average particle diameter of the solid content in the slurry after wet pulverization was 0.3 μm.
Then, the slurry was supplied to a spray dryer set at 220 ° C. at a feed rate of 2.4 L / h to obtain a reaction precursor. X-ray diffraction was performed on the obtained reaction precursor, and as a result, only a diffraction peak of tungsten trioxide was observed.
Then, the obtained reaction precursor was subjected to a calcination reaction in the air at 960 ° C. for 2 hours to obtain a white calcined product.
X-ray diffraction analysis was performed on the obtained burned product, and as a result, the burned product was single-phase Zr 2 (WO 4 ) (PO 4 ) 2 . The average particle diameter and BET specific surface area of the obtained zirconium phosphate tungstate sample were measured, and the results are shown in Table 1. When the obtained zirconium phosphate tungstate sample was observed by a scanning electron microscope, the particle shape was spherical (FIG. 2).
[表1]
（實施例1）
對50 g的ZWP試樣1添加0.25 g（0.5質量%）的矽烷偶合劑（癸基甲氧基矽烷），利用氣流式粉碎機（清新（SEISHIN）企業製造，A-O噴射磨機）進行粉碎混合，獲得對破碎狀的磷酸鎢酸鋯進行了表面被覆處理的改質磷酸鎢酸鋯試樣A。再者，氣流式粉碎機的條件如下所述。
•粉體供給速度：3 g/min
•推進壓力：0.6 MPa
•噴射壓力：0.6 MPa(Example 1)
Add 0.25 g (0.5% by mass) of a silane coupling agent (decylmethoxysilane) to 50 g of ZWP sample 1 and use a jet mill (manufactured by Seishin Corporation, AO jet mill) to pulverize and mix A modified zirconium phosphate tungstate phosphate sample A was obtained by subjecting the broken zirconium phosphate tungstate to a surface coating treatment. The conditions of the air-flow type pulverizer are as follows.
• Powder supply speed: 3 g / min
• Propulsion pressure: 0.6 MPa
• Injection pressure: 0.6 MPa
（實施例2）
對50 g的ZWP試樣2添加0.25 g（0.5質量%）的矽烷偶合劑（癸基甲氧基矽烷），利用混合機（實驗室用混合機：Labo Milser）以2000 rpm混合1分鐘，獲得對球狀的磷酸鎢酸鋯進行了表面被覆處理的球狀的改質磷酸鎢酸鋯試樣B。(Example 2)
To 50 g of ZWP sample 2 was added 0.25 g (0.5% by mass) of a silane coupling agent (decylmethoxysilane), and mixed with a mixer (laboratory mixer: Labo Milser) at 2000 rpm for 1 minute to obtain A spherical modified zirconium phosphate tungstate phosphate sample B having a surface coating treatment on a spherical zirconium phosphate tungstate.
（比較例1～比較例2）
試樣是未實施表面被覆處理的磷酸鎢酸鋯試樣，將ZWP試樣1作為比較例1的試樣，將ZWP試樣2作為比較例2的試樣。(Comparative Example 1 to Comparative Example 2)
The sample was a zirconium tungstate phosphate sample not subjected to a surface coating treatment. A ZWP sample 1 was used as a sample of Comparative Example 1 and a ZWP sample 2 was used as a sample of Comparative Example 2.
（比較例3）環氧偶合劑
對50 g的ZWP試樣1添加0.25 g（0.5質量%）的矽烷偶合劑（3-縮水甘油氧基丙基三甲氧基矽烷），利用氣流式粉碎機（清新（SEISHIN）企業製造，A-O噴射磨機）進行粉碎混合，獲得對破碎狀的磷酸鎢酸鋯進行了表面被覆處理的改質磷酸鎢酸鋯試樣c。再者，氣流式粉碎機的條件如下所述。
•粉體供給速度：3 g/min
•推進壓力：0.6 MPa
•噴射壓力：0.6 MPa(Comparative Example 3) An epoxy coupling agent was added with 0.25 g (0.5% by mass) of a silane coupling agent (3-glycidyloxypropyltrimethoxysilane) to 50 g of ZWP sample 1 and an air jet mill ( Manufactured by SEISHIN company, AO jet mill) was pulverized and mixed to obtain a modified zirconium phosphate tungstate phosphate sample c having a surface coating treatment on the broken zirconium phosphate. The conditions of the air-flow type pulverizer are as follows.
• Powder supply speed: 3 g / min
• Propulsion pressure: 0.6 MPa
• Injection pressure: 0.6 MPa
＜物性的評價＞
（粉體的熱膨脹係數的評價）
對實施例及比較例的磷酸鎢酸鋯或改質磷酸鎢酸鋯試樣，利用帶有升溫功能的X射線繞射（X-Ray Diffraction，XRD）裝置（理學公司的Ultima IV），以升溫速度20℃/min升溫至目標溫度，進而於到達目標溫度後10分鐘後，測定試樣相對於a軸、b軸、c軸的晶格常數，對晶格體積變化（長方體）進行線換算，求出熱膨脹係數（參照材料科學雜誌（J. Mat. Sci.）35（2000）2451-2454）。將其結果示於表2中。＜ Evaluation of physical properties ＞
(Evaluation of powder thermal expansion coefficient)
The samples of zirconium tungstate phosphate or modified zirconium tungstate phosphate of the examples and comparative examples were heated by using an X-Ray Diffraction (XRD) device (Ultima IV of Rigaku) with a temperature rising function. The temperature was raised to the target temperature at a rate of 20 ° C / min, and 10 minutes after the target temperature was reached, the lattice constants of the sample with respect to the a-axis, b-axis, and c-axis were measured, and the lattice volume change (cuboid) was linearly converted. Calculate the thermal expansion coefficient (refer to J. Mat. Sci. 35 (2000) 2451-2454). The results are shown in Table 2.
（溶出試驗）
將試驗試樣1.0 g加入至水70 ml中，於100℃的沸騰水中對試樣進行1小時沸騰處理。
繼而，進行過濾分離，利用感應耦合電漿（Inductively Coupled Plasma，ICP）發光光譜裝置來測定濾液中的Zr離子、W離子、P離子濃度，求出Zr離子濃度及W離子濃度、P離子濃度作為自試樣的溶出濃度。將其結果示於表2中。(Dissolution test)
1.0 g of the test sample was added to 70 ml of water, and the sample was boiled in boiling water at 100 ° C for 1 hour.
Then, filtration and separation were performed, and the concentration of Zr ions, W ions, and P ions in the filtrate was measured using an inductively coupled plasma (ICP) emission spectrometer, and the Zr ion concentration, W ion concentration, and P ion concentration were determined as Dissolution concentration from the sample. The results are shown in Table 2.
[表2]
（實施例3～實施例4）
計量5.8 g的實施例1中獲得的改質磷酸鎢酸鋯試樣A或實施例2中獲得的改質磷酸鎢酸鋯試樣B、及4.2 g的環氧樹脂（三菱化學jER807，環氧當量160～175），利用真空混合機（新基（Thinky）製造的去泡攪拌太郎ARV-310）以旋轉速度2000 rpm進行混合，製作30體積%的糊劑。
繼而，於糊劑中加入100 μL的硬化劑（四國化成製造的固澤爾（Curezol）），利用真空混合機（新基（Thinky）製造的去泡攪拌太郎ARV-310）以旋轉速度1500 rpm進行混合，以150℃歷時1小時使其硬化，獲得高分子組成物試樣。
繼而，將該高分子組成物試樣切成5 mm見方×10 mm，使用熱機械分析裝置（thermomechanical analyzer，TMA）以升溫速度1℃/min測定30℃～120℃的線膨脹係數。將其結果示於表3中。另外，以掃描型電子顯微鏡像觀察所獲得的高分子組成物試樣的剖面，結果，實施例3及實施例4中均可確認到改質磷酸鎢酸鋯均勻地分散於高分子組成物中。(Examples 3 to 4)
5.8 g of modified zirconium tungstate phosphate sample A obtained in Example 1 or modified zirconium tungstate phosphate sample B obtained in Example 2 and 4.2 g of epoxy resin (Mitsubishi Chemical jER807, epoxy The equivalent weight is 160 to 175), and the mixture is mixed with a vacuum mixer (defoaming and stirring Taro ARV-310 manufactured by Thinky) at a rotation speed of 2000 rpm to prepare a 30% by volume paste.
Next, add 100 μL of hardener (Curezol manufactured by Shikoku Chemicals) to the paste, and use a vacuum mixer (defoaming and stirring Taro ARV-310 manufactured by Thinky) at a rotation speed of 1500 Mixing was performed at rpm, and the mixture was hardened at 150 ° C. for 1 hour to obtain a polymer composition sample.
Then, this polymer composition sample was cut into 5 mm square × 10 mm, and a linear expansion coefficient of 30 ° C. to 120 ° C. was measured using a thermomechanical analyzer (TMA) at a temperature rise rate of 1 ° C./min. The results are shown in Table 3. In addition, the cross section of the obtained polymer composition sample was observed with a scanning electron microscope image. As a result, it was confirmed in Examples 3 and 4 that the modified zirconium phosphate tungstate was uniformly dispersed in the polymer composition. .
（參考例1）
計量3.3 g的平均粒徑10 μm的球狀熔融二氧化矽（線膨脹係數5×10-7
/℃）、及4.2 g的環氧樹脂（三菱化學jER807，環氧當量160～175），利用真空混合機（新基（Thinky）製造的去泡攪拌太郎ARV-310）以旋轉速度2000 rpm進行混合，製作30體積%的糊劑。
繼而，於糊劑中加入100 μL的硬化劑（四國化成製造的固澤爾（Curezol）），利用真空混合機（新基（Thinky）製造的去泡攪拌太郎ARV-310）以旋轉速度1500 rpm進行混合，以150℃歷時1小時使其硬化，獲得高分子組成物試樣。將該高分子組成物試樣切成5 mm見方×10 mm，使用熱機械分析裝置（TMA）以升溫速度1℃/min測定30℃～120℃的線膨脹係數。將其結果示於表3中。另外，以掃描型電子顯微鏡像觀察所獲得的高分子組成物試樣的剖面，結果，可確認到球狀熔融二氧化矽粒子均勻地分散於高分子組成物中。(Reference Example 1)
Measure 3.3 g of spherical fused silica with an average particle diameter of 10 μm (linear expansion coefficient 5 × 10 -7 / ℃) and 4.2 g of epoxy resin (Mitsubishi Chemical jER807, epoxy equivalent 160-175), and use A vacuum mixer (defoaming and stirring Taro ARV-310 manufactured by Thinky) was mixed at a rotation speed of 2000 rpm to prepare a 30% by volume paste.
Next, add 100 μL of hardener (Curezol manufactured by Shikoku Chemicals) to the paste, and use a vacuum mixer (defoaming and stirring Taro ARV-310 manufactured by Thinky) at a rotation speed of 1500 Mixing was performed at rpm, and the mixture was hardened at 150 ° C. for 1 hour to obtain a polymer composition sample. This polymer composition sample was cut into 5 mm square × 10 mm, and a linear expansion coefficient of 30 ° C. to 120 ° C. was measured using a thermomechanical analysis device (TMA) at a temperature rise rate of 1 ° C./min. The results are shown in Table 3. In addition, when a cross section of the obtained polymer composition sample was observed with a scanning electron microscope image, it was confirmed that spherical fused silica particles were uniformly dispersed in the polymer composition.
[表3]
無no
圖1是磷酸鎢酸鋯試樣1的掃描型電子顯微鏡照片。FIG. 1 is a scanning electron microscope photograph of a zirconium tungstate phosphate sample 1. FIG.
圖2是磷酸鎢酸鋯試樣2的掃描型電子顯微鏡照片。 FIG. 2 is a scanning electron microscope photograph of a zirconium tungstate phosphate sample 2. FIG.
Claims (10)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017209975 | 2017-10-31 | ||
| JP2017-209975 | 2017-10-31 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW201922612A true TW201922612A (en) | 2019-06-16 |
Family
ID=66332579
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW107136439A TW201922612A (en) | 2017-10-31 | 2018-10-17 | Modified zirconium tungstate phosphate, negative thermal expansion filler, and polymeric composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6553831B1 (en) |
| TW (1) | TW201922612A (en) |
| WO (1) | WO2019087722A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020261976A1 (en) * | 2019-06-24 | 2020-12-30 | 日本化学工業株式会社 | Modified zirconium phosphate tungstate, filler having negative thermal expansion, and polymer composition |
| JP7351477B2 (en) * | 2019-07-23 | 2023-09-27 | 国立大学法人東京工業大学 | Resin composition and resin molding thereof |
| EP4007688A4 (en) * | 2019-08-02 | 2023-08-30 | Airtech International, Inc. | Adjustable cte polymer compositions for extrusion and additive manufacturing processes |
| CN111454574A (en) * | 2020-06-05 | 2020-07-28 | 郑州大学 | Method for improving polyimide performance by coupling agent surface modification treatment negative thermal expansion material |
| WO2023037930A1 (en) * | 2021-09-07 | 2023-03-16 | 日本化学工業株式会社 | Negative thermal expansion material, method for producing same, and paste |
| CN116093333B (en) * | 2023-04-07 | 2023-06-16 | 河南锂动电源有限公司 | Battery anode material, preparation method thereof and semisolid lithium ion battery |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5445442B2 (en) * | 2010-12-24 | 2014-03-19 | 住友ベークライト株式会社 | Resin composition for printed wiring board, prepreg, laminate, resin sheet, printed wiring board, and semiconductor device |
| TWI629306B (en) * | 2013-07-19 | 2018-07-11 | Ajinomoto Co., Inc. | Resin composition |
| JP6710034B2 (en) * | 2014-12-12 | 2020-06-17 | 太陽インキ製造株式会社 | Curable resin composition, dry film, cured product and printed wiring board |
| JP6399989B2 (en) * | 2015-09-25 | 2018-10-03 | 富士フイルム株式会社 | Organic thin film transistor, material for organic thin film transistor, material set for organic thin film transistor, method of manufacturing organic thin film transistor |
| WO2017061403A1 (en) * | 2015-10-07 | 2017-04-13 | 日本化学工業株式会社 | Negative thermal expansion material and composite material including same |
-
2018
- 2018-10-10 JP JP2019507963A patent/JP6553831B1/en active Active
- 2018-10-10 WO PCT/JP2018/037768 patent/WO2019087722A1/en active Application Filing
- 2018-10-17 TW TW107136439A patent/TW201922612A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019087722A1 (en) | 2019-05-09 |
| JPWO2019087722A1 (en) | 2019-11-14 |
| JP6553831B1 (en) | 2019-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW201922612A (en) | Modified zirconium tungstate phosphate, negative thermal expansion filler, and polymeric composition | |
| CN108137325B (en) | Method for preparing zirconium phosphotungstate | |
| TWI755366B (en) | Negative thermal expansion material and composite material and paste containing the same | |
| TWI803653B (en) | Negative thermal expansion material, method of manufacturing the same and composite material | |
| WO2018123571A1 (en) | Hexagonal boron nitride powder and method for producing same | |
| TWI750137B (en) | Method for manufacturing zirconium tungstate phosphate | |
| US20110081548A1 (en) | Zinc oxide particle, method for producing it, exoergic filler, exoergic resin composition, exoergic grease and exoergic coating composition | |
| TWI593629B (en) | Magnesium hydroxide particle and resin composition comprising the same | |
| US11332599B2 (en) | Modified zirconium phosphate tungstate, negative thermal expansion filler and polymer composition | |
| CN113544089A (en) | Modified zirconium phosphotungstate, negative thermal expansion filler and polymer composition | |
| TWI460130B (en) | Process for the production of a storage-stable barium sulphate having good dispersibility | |
| WO2020004072A1 (en) | Negative thermal expansion material, method for manufacturing same, and composite material | |
| JP7239608B2 (en) | Modified zirconium tungstate phosphate, negative thermal expansion filler and polymer composition | |
| JP7472129B2 (en) | Modified zirconium tungstate phosphate, negative thermal expansion filler and polymer composition | |
| JP7364418B2 (en) | Thermal expansion suppressing filler, method for producing the same, and composite material containing the same | |
| WO2023181781A1 (en) | Negative thermal expansion material, method for manufacturing same, and composite material | |
| JP7408721B2 (en) | Negative thermal expansion materials and composite materials | |
| WO2023163057A1 (en) | Negative thermal expansion material and composite material | |
| JP2023143635A (en) | Negative thermal expansion material, production method thereof, and composite material | |
| JP2023123327A (en) | Negative thermal expansion material and composite material |