CN117098622A - 烧结成型体用组合物和烧结成型体 - Google Patents
烧结成型体用组合物和烧结成型体 Download PDFInfo
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- CN117098622A CN117098622A CN202280024838.7A CN202280024838A CN117098622A CN 117098622 A CN117098622 A CN 117098622A CN 202280024838 A CN202280024838 A CN 202280024838A CN 117098622 A CN117098622 A CN 117098622A
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- polyacetal resin
- sintered compact
- organic binder
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Classifications
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
- B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/105—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing inorganic lubricating or binding agents, e.g. metal salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/447—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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Abstract
本发明的目的在于提供一种不损害基于聚缩醛树脂所具备的刚性的生坯成型体的形状保持性、具有高流动性并且在脱脂时不发生龟裂和鼓起的烧结成型体用组合物。本发明的烧结成型体用组合物的特征在于，所述烧结成型体用组合物包含可烧结的无机粉末和有机粘结剂，所述有机粘结剂至少包含聚缩醛树脂和聚烯烃树脂，并且所述聚缩醛树脂的熔体流动指数为70g/10分钟～200g/10分钟。
Description
技术领域
本发明涉及在制造烧结成型体时使用的成型用原料。
背景技术
利用金属、陶瓷、金属陶瓷等可烧结的粉体的特别是精密的烧结成型体、复杂形状的烧结成型体通过如下方法成型：将含有可烧结的粉体和粘结剂的烧结成型体制造用组合物进行加热、混炼而得到烧结成型体用原料，通过将该烧结成型体用原料进行注射成型而成型出生坯成型体，然后对该生坯成型体进行脱脂工序，接着对其进行烧结。
在利用上述方法的烧结成型体的成型中，用于获得没有龟裂、鼓起、变形等缺陷的品质良好的成型体的最重要的工序是脱脂工序。该脱脂工序是从包含注射成型体的生坯成型体中除去粘结剂的工序，该脱脂工序利用如下方法：通过对生坯成型体进行加热，从而使粘结剂加热分解而气化的方法；或者通过对生坯成型体进行溶剂处理而将生坯成型体中的可溶性粘结剂成分溶出、除去，然后使剩余的粘结剂加热分解而气化的方法。顺便说一下，在对生坯成型体进行加热而脱脂的加热脱脂方法中，当生坯成型体中的粘结剂的热分解和气化短时间集中地发生时，有时在脱脂工序中的成型体中产生龟裂或鼓起，因此必须通过长时间的加热而进行脱脂。
已经知道通过将作为解聚型聚合物的聚缩醛树脂单独或与其他聚合物一起作为粘结剂使用，能够取得如下等效果：基于聚缩醛树脂所具备的刚性的生坯成型体的形状保持性和利用加热的脱脂工序中的成型体的形状保持性优异，而且在利用加热的脱脂后不残留残渣，利用加热的脱脂工序快，因此能够提高生产效率(例如，日本特开平4-247802号公报、日本特开平5-98306号公报等)。
发明内容
发明所要解决的问题
然而，在日本特开平4-247802号公报、日本特开平5-98306号公报等中记载的方法中，关于市售的高流动性聚缩醛树脂的流动性，熔体流动指数为约45g/10分钟，当使用包含大量聚缩醛树脂的粘结剂时，存在给料的流动性变低，特别是对具有薄的部分的制品而言成型性变差的问题。另外，在想要提高使用了聚缩醛树脂的粘结剂的流动性的情况下，可以考虑加入大量的蜡等流动助剂，但加入大量的一种成分会导致脱脂时的急剧的挥发，存在产生龟裂或鼓起的问题。
另外，例如在日本专利第5249213号中记载的使用硝酸等酸对生坯成型体进行脱脂的酸脱脂方法中，提出了包含含有2摩尔％的1,3-二氧杂环庚烷的聚缩醛树脂、聚乙烯、聚-1,3-二氧杂环庚烷的改进了流动性的粘结剂组合物，但没有关于聚缩醛树脂的流动性的记载，设想在实施例中记载的上述聚缩醛树脂的流动性低，在制成与金属粉末的复合物时难以得到厚度为1mm～2mm的薄的成型体。
另外，当为了提高上述聚缩醛树脂的流动性而提高1,3-二氧杂环庚烷的浓度时，存在如下问题：聚缩醛树脂所具有的强度变低，通过制备与金属粉末的复合物并进行注射成型而得到的成型体的强度下降。
因此，本发明的目的在于提供一种不损害基于聚缩醛树脂所具备的刚性的生坯成型体的形状保持性、具有高流动性并且在脱脂时不发生龟裂和鼓起的烧结成型体用组合物。
用于解决问题的手段
本发明人为了解决上述问题而进行了深入研究，结果发现：包含含有具有规定的熔体流动指数的聚缩醛树脂和聚烯烃树脂的有机粘结剂的烧结成型体用组合物能够解决上述问题，从而完成了本发明。
即，本发明如下所示。
[1]一种烧结成型体用组合物，其特征在于，所述烧结成型体用组合物包含可烧结的无机粉末和有机粘结剂，
所述有机粘结剂至少包含聚缩醛树脂和聚烯烃树脂，
所述聚缩醛树脂的熔体流动指数为70g/10分钟～200g/10分钟。
[2]根据权利要求1所述的烧结成型体用组合物，其中，所述聚烯烃树脂的熔体流动指数(190℃、2.16kg)为40g/10分钟以上。
[3]根据[1]或[2]所述的烧结成型体用组合物，其中，以所述有机粘结剂的质量为基准，在所述有机粘结剂中包含5质量％～95质量％的所述聚缩醛树脂和5质量％～95质量％的所述聚烯烃树脂。
[4]根据[1]～[3]中任一项所述的烧结成型体用组合物，其中，当将所述烧结成型体用组合物设为100质量份时，所述烧结成型体用组合物包含70质量份～95质量份的所述可烧结的无机粉末。
[5]根据[1]～[4]中任一项所述的烧结成型体用组合物，其中，以所述有机粘结剂的质量为基准，在所述有机粘结剂中包含5质量％～60质量％的流动性赋予剂。
[6]根据[1]～[5]中任一项所述的烧结成型体用组合物，其中，所述聚缩醛树脂包含氧亚甲基单元和氧亚乙基单元。
[7]根据[1]～[6]中任一项所述的烧结成型体用组合物，其中，以所述有机粘结剂的质量为基准，所述有机粘结剂包含5质量％～50质量％的所述聚缩醛树脂。
[8]根据[1]～[7]中任一项所述的烧结成型体用组合物，其中，所述有机粘结剂包含含氮化合物和脂肪酸金属盐。
[9]一种生坯成型体，其中，所述生坯成型体通过将[1]～[8]中任一项所述的烧结成型体用组合物成型而得到。
[10]根据[9]所述的生坯成型体，其中，在所述生坯成型体中存在100mm2以上的厚度为1mm以下的部位。
发明效果
根据本发明，能够提供一种不损害基于聚缩醛树脂所具备的刚性的生坯成型体的形状保持性、具有高流动性并且在脱脂时不发生龟裂和鼓起的烧结成型体用组合物。
另外，通过使用本发明的烧结成型体用组合物，能够容易地成型出薄的成型体，并且脱脂性也良好，因此能够以良好的成品率得到烧结成型体。
具体实施方式
以下，对用于实施本发明的方式详细地进行说明。需要说明的是，本发明并不限定于以下的记载，能够在其主旨的范围内进行各种变形而实施。
[烧结成型体用组合物]
在本实施方式中，烧结成型体用组合物包含可烧结的无机粉末和有机粘结剂，优选由上述无机粉末和上述有机粘结剂构成。
上述烧结成型体用组合物可以除了包含上述无机粉末、上述有机粘结剂以外还包含其他添加物。
<有机粘结剂>
上述有机粘结剂包含聚缩醛树脂和聚烯烃树脂。
聚缩醛树脂和聚烯烃树脂各自具有不同的热分解起始温度，因此能够在加热脱脂时的升温过程中从生坯成型体中逐渐除去有机粘结剂。另外，在酸脱脂中，聚缩醛树脂被硝酸等酸分解并从生坯成型体中除去，但通过配合不被酸分解的聚烯烃树脂，能够保持除去了聚缩醛树脂后的生坯成型体的形状。
在上述有机粘结剂中所含的树脂成分优选仅为上述聚缩醛树脂、上述聚烯烃树脂、后述的流动性赋予剂、后述的含氮化合物(例如，聚酰胺树脂)。
作为上述烧结成型体用组合物中的上述有机粘结剂的质量比例，从良好地保持注射成型中的成型性、能够进一步抑制在脱脂工序时的龟裂和鼓起的观点出发，相对于100质量份的烧结成型体用组合物，上述有机粘结剂优选为5质量份～30质量份，更优选为5质量份～20质量份，进一步优选为5质量份～15质量份。
(聚缩醛树脂)
作为上述聚缩醛树脂，可举出：聚缩醛均聚物、聚缩醛共聚物或其混合物。其中，从热稳定性的观点出发，上述聚缩醛树脂优选为聚缩醛共聚物。
上述聚缩醛树脂可以单独使用一种，也可以组合使用多种。
作为上述聚缩醛均聚物，可举出在主链中具有氧亚甲基单元的聚合物，并且能够利用酯基或醚基封闭聚合物的两末端。聚缩醛均聚物能够以甲醛和公知的分子量调节剂作为原料得到，能够使用公知的盐类聚合催化剂并以烃等作为溶剂通过公知的淤浆法例如在日本特公昭47-6420号公报或日本特公昭47-10059号公报中记载的聚合方法从这些原料得到。
需要说明的是，聚缩醛均聚物优选除两末端以外的主链的99.8摩尔％以上由氧亚甲基单元构成，更优选为除两末端以外的主链仅由氧亚甲基单元构成的聚缩醛均聚物。
作为聚缩醛共聚物，可举出在主链中具有氧亚甲基单元和氧亚乙基单元的聚合物，例如能够通过在聚合催化剂的存在下使三聚甲醛与环状醚和/或环状缩甲醛共聚而得到。三聚甲醛是甲醛的环状三聚物，一般通过在酸性催化剂的存在下使甲醛水溶液反应而得到。
上述三聚甲醛有时含有水、甲醇、甲酸、甲酸甲酯等使其发生链转移的杂质，因此优选例如通过蒸馏等方法除去这些杂质而进行纯化。在该情况下，相对于1摩尔的三聚甲醛，优选将使其发生链转移的杂质的合计量调节为1×10-3摩尔以下，更优选调节为0.5×10-3摩尔以下。通过将杂质的量减少至像上述数值一样，在实用上能够充分提高聚合反应速度，并且生成的聚合物能够获得优异的热稳定性。
环状醚和/或环状缩甲醛是能够与上述三聚甲醛共聚的成分，例如可举出：环氧乙烷、环氧丙烷、环氧丁烷、环氧氯丙烷、环氧溴丙烷、氧化苯乙烯、氧杂环丁烷、1,3-二氧杂环戊烷、乙二醇缩甲醛、丙二醇缩甲醛、二乙二醇缩甲醛、三乙二醇缩甲醛、1,4-丁二醇缩甲醛、1,5-戊二醇缩甲醛、1,6-己二醇缩甲醛等。特别优选环氧乙烷、1,3-二氧杂环戊烷。这些物质可以单独仅使用一种，也可以并用两种以上。
相对于1摩尔的上述三聚甲醛，环状醚和环状缩甲醛的添加量优选为1.0摩尔％以上，更优选为3.0摩尔％以上，进一步优选为3.5摩尔％以上。另外，相对于1摩尔的上述三聚甲醛，环状醚和环状缩甲醛的添加量优选为8.0摩尔％以下，更优选为7.0摩尔％以下，进一步优选为5.0摩尔％以下。
作为聚合催化剂，可举出以路易斯酸为代表的硼、锡、钛、磷、砷和锑的化合物，特别优选三氟化硼、三氟化硼类水合物、以及含氧原子或硫原子的有机化合物与三氟化硼的配位络合物。作为优选例，例如可举出：三氟化硼、三氟化硼乙醚络合物、三氟化硼二正丁醚络合物。这些物质可以单独仅使用一种，也可以并用两种以上。
相对于1摩尔的上述三聚甲醛，聚合催化剂的添加量优选在0.1×10-5摩尔～0.1×10-3摩尔的范围内，更优选在0.3×10-5摩尔～0.5×10-4摩尔的范围内，进一步优选在0.5×10-5摩尔～0.4×10-4摩尔的范围内。当聚合催化剂的添加量在上述范围内时，能够稳定地实施长时间的聚合反应。
在聚缩醛共聚物的制造中，聚合催化剂的失活通过如下方式进行：将通过聚合反应而得到的聚缩醛树脂投入到包含氨、三乙胺、三正丁胺等胺类或者碱金属或碱土金属的氢氧化物、无机酸盐、有机酸盐等催化剂中和失活剂中的至少一种的水溶液或有机溶剂溶液中，在浆液状态下一般搅拌几分钟～几小时。催化剂中和失活后的浆液通过过滤、清洗而除去未反应单体和催化剂中和失活剂、催化剂中和盐，然后进行干燥。
另外，作为聚合催化剂的失活，也能够使用如下方法：通过使氨、三乙胺等的蒸气与聚缩醛共聚物接触而使聚合催化剂失活的方法；利用混合机使受阻胺类、三苯基膦和氢氧化钙等中的至少一种与聚缩醛树脂接触而使催化剂失活的方法。
另外，也可以不进行聚合催化剂的失活，而是使用通过在聚缩醛共聚物的熔点以下的温度下并且在非活性气体气氛下加热而使聚合催化剂挥发减少后的聚缩醛共聚物进行后述的末端稳定化处理。以上的聚合催化剂的失活操作和聚合催化剂的挥发减少操作也可以根据需要在将通过聚合反应而得到的聚缩醛树脂粉碎后进行。
所得到的聚缩醛树脂的末端稳定化处理中，通过下述方法分解除去不稳定末端部分。作为不稳定末端部的分解除去方法，例如能够使用带排气口的单螺杆式挤出机或带排气口的双螺杆式挤出机，在作为去除剂的氨或三乙胺、三丁胺等脂肪酸胺、以氢氧化钙为代表的碱金属或碱土金属的氢氧化物、无机弱酸盐、有机弱酸盐等公知的能够分解不稳定末端部的碱性物质的存在下，将聚缩醛树脂熔融，并分解除去不稳定末端部。
相对于100质量％的有机粘结剂，上述有机粘结剂中的上述聚缩醛树脂的质量比率优选为5质量％～95质量％，更优选为5质量％～70质量％，特别优选为5质量％～60质量％。
在通过加热而从生坯成型体中除去有机粘结剂的情况下，相对于100质量％的有机粘结剂，聚缩醛树脂的质量比率优选为5质量％～50质量％，更优选为5质量％～45质量％，特别优选为10质量％～40质量％。
通过将有机粘结剂中的聚缩醛树脂的比率设定在上述范围内，具有能够良好地保持生坯成型体的形状的倾向。
上述聚缩醛树脂的熔体流动指数根据ASTM-D-1238-57T在190℃、2.16kg的条件下测定，优选为70g/10分钟以上且200g/10分钟以下，更优选大于等于90g/10分钟且小于200g/10分钟，进一步优选大于等于90g/10分钟且小于140g/10分钟。通过将熔体流动指数调节为70g/10分钟以上，烧结成型体用组合物的流动性提高，通过将熔体流动指数调节为200g/10分钟以下，能够提高生坯成型体的强度。
需要说明的是，聚缩醛树脂的熔体流动指数能够以通过增加在聚合时添加的分子量调节剂(例如，甲缩醛、甲醇、甲酸、甲酸甲酯等)的量而使得熔体流动指数变大的方式操作。
作为上述聚缩醛树脂的熔点，优选为100℃～200℃，更优选为140℃～180℃。上述熔点是通过JIS K7121测定的熔化峰温度，在存在多个熔化温度的情况下为高温侧的熔点。
(聚烯烃树脂)
上述聚烯烃树脂是具有衍生自具有2个～8个碳原子、优选2个～4个碳原子的烯烃的结构单元的均聚物或共聚物。
从聚缩醛树脂与可烧结的无机粉末的混炼性、注射成型性的观点出发，在190℃、2.16kg的条件下测定的上述聚烯烃树脂的熔体流动指数优选为40g/10分钟以上。更优选为50g/10分钟以上，进一步优选为70g/10分钟以上，特别优选为80g/10分钟以上。当聚烯烃树脂的熔体流动指数大于上述下限值时，具有薄件成型性优异、并且加热脱脂的脱脂性更优异的倾向。从使成型体的强度良好的观点出发，聚烯烃树脂的熔体流动指数优选为200g/10分钟以下，更优选为150g/10分钟以下。
作为上述聚烯烃树脂，具体可举出：聚乙烯、聚丙烯、乙烯-丙烯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-乙烯醇共聚物、聚异戊二烯、聚丁二烯等。优选聚乙烯、聚丙烯和它们的混合物，从脱脂工序中的形状保持性、抑制在脱脂工序中的龟裂和鼓起的观点出发，更优选聚乙烯或聚丙烯。作为聚乙烯市售的商品之中能够适合使用的商品，例如可举出：SUNTECHD系列(旭化成株式会社制造)、SUNTEC LD系列(旭化成株式会社制造)、SUNTEC EVA系列(旭化成株式会社制造)、NEO-ZEX、ULTZEX、Evolue(以上为普瑞曼聚合物株式会社制造)等，作为聚丙烯，可举出：住友NOBLEN(住友化学株式会社制造)、NOVATEC PP(日本聚丙烯株式会社制造)、SunAllomer PM系列(SunAllomer株式会社制造)、Prime Polypro(普瑞曼聚合物株式会社制造)等。
从酸脱脂后的成型体的形状保持性的观点出发，上述聚烯烃树脂优选不易被酸分解。从酸脱脂后的成型体的形状保持性的观点出发，上述聚烯烃树脂在JIS K 7114中记载的方法中在23℃(室温)、70℃的条件下在30％的硝酸水溶液中浸渍24小时后的重量优选为浸渍前的10％以下，更优选为浸渍前的5％以下，特别优选为浸渍前的1％以下。
从生坯成型体的形状保持以及能够良好地保持酸脱脂后的成型体的形状的观点出发，相对于100质量％的有机粘结剂，上述有机粘结剂中的上述聚烯烃树脂的质量比率优选为5质量％～95质量％，更优选为5质量％～70质量％，特别优选为5质量％～60质量％。
相对于100质量份的上述聚缩醛树脂，上述聚烯烃树脂的质量比例优选为1质量份～200质量份，更优选为5质量份～150质量份，进一步优选为10质量份～120质量份。
作为在上述有机粘结剂100质量％中的上述聚缩醛树脂和上述聚烯烃树脂的合计质量的比率，优选为45质量％以上。另外，作为在上述有机粘结剂100质量％中的上述聚缩醛树脂、上述聚烯烃树脂和后述的流动性赋予剂的合计质量的比率，优选为90质量％以上，更优选为95质量％以上，进一步优选为98质量％以上。
从进一步减少脱脂工序时的龟裂、鼓起的观点出发，上述聚缩醛树脂的热分解起始温度(℃)与上述聚烯烃树脂的热分解起始温度(℃)之差优选为30℃以上，更优选为30℃～100℃。上述热分解起始温度是使用热重差示热分析装置测定的温度。
(流动性赋予剂)
本实施方式的烧结成型体用组合物优选还包含流动性赋予剂。通过包含上述流动性赋予剂，烧结成型体用组合物的流动性进一步提高。
上述流动性赋予剂是除了上述的聚缩醛树脂、聚烯烃树脂以外的化合物，例如可举出蜡类。作为上述蜡类，例如可举出：石蜡、聚乙烯蜡、聚丙烯蜡、巴西棕榈蜡、聚乙二醇、聚四亚甲基二醇、聚四亚乙基二醇、聚异丁烯、微晶蜡、褐煤蜡、蜂蜡、木蜡、合成蜡、聚-1,3-二氧杂环戊烷、聚-1,3-二氧杂环庚烷等。其中，从注射成型中的烧结成型体用组合物的流动性更优异的观点出发，优选石蜡、聚乙二醇、聚四亚甲基二醇。
从注射成型中的烧结成型体用组合物的流动性更优异的观点出发，相对于100质量％的上述有机粘结剂，上述流动性赋予剂的质量比率优选为5质量％～60质量％，更优选为5质量％～50质量％，特别优选为10质量％～50质量％。
(含氮化合物、脂肪酸金属盐)
上述聚缩醛树脂优选还包含含氮化合物和/或脂肪酸金属盐，更优选还包含含氮化合物和脂肪酸金属盐。
通过包含上述含氮化合物和上述脂肪酸金属盐，能够使在制造聚缩醛树脂时的挤出性、热稳定性、异物的抑制性优异。另外，具有同时改善通过与金属粉末混炼而得到的烧结成型体用组合物的流动性和生坯成型体的强度的倾向。通过包含上述含氮化合物和上述脂肪酸金属盐，烧结成型体用组合物的热稳定性提高。
作为上述含氮化合物，没有特别限制，例如可举出：聚酰胺树脂、酰胺化合物、脲衍生物、三嗪衍生物等，其中，从烧结成型体用组合物的热稳定性更优异、生坯成型体的强度也更优异的观点出发，优选聚酰胺树脂。这些含氮化合物可以单独使用一种，也可以组合使用两种以上。
作为上述聚酰胺树脂，没有特别限制，例如可举出：通过二元胺与二元羧酸的缩合、氨基酸的缩合、内酰胺的开环聚合等而得到的尼龙6、尼龙11、尼龙12、尼龙66、尼龙6·10、尼龙6/6·10、尼龙6/6·6、尼龙6·6/6·10、尼龙6/6·6/6·10、聚-β-丙氨酸等。
作为上述酰胺化合物，没有特别限制，例如可举出：由脂肪族一元羧酸、脂肪族二元羧酸、芳香族一元羧酸或芳香族二元羧酸与脂肪族一元胺、脂肪族二元胺、芳香族一元胺或芳香族二元胺生成的硬脂酰硬脂胺、油酰硬脂胺、芥酰硬脂胺、二硬脂酰乙二胺、二山嵛酰乙二胺、二硬脂酰六亚甲基二胺、二芥酰乙二胺、二芥酰苯二甲胺、二硬脂酰苯二甲胺、癸二酰胺等。
作为上述脲衍生物，没有特别限制，例如可举出：N-苯基脲、N,N’-二苯基脲、N-苯基硫脲、N,N’-二苯基硫脲等。
作为上述三嗪衍生物，没有特别限制，例如可举出：三聚氰胺、苯基胍胺、N-苯基三聚氰胺、蜜勒胺、N,N’-二苯基三聚氰胺、N-羟甲基三聚氰胺、N,N’,N”-三羟甲基三聚氰胺、2,4-二氨基-6-环己基三嗪、蜜白胺等。
相对于100质量份的聚缩醛树脂，上述含氮化合物的质量比例优选为0.005质量份～0.2质量份，特别优选为0.005质量份～0.1质量份。当上述含氮化合物的质量比例在上述范围内时，从在将可烧结的无机粉末与有机粘结剂进行混炼时聚缩醛树脂的热稳定性提高的观点考虑是优选的。
作为上述脂肪酸金属盐，没有特别限制，例如可举出：由碳原子数10～35的饱和或不饱和的脂肪酸或被羟基取代的脂肪酸与碱金属或碱土金属的氢氧化物、氧化物或氯化物得到的脂肪酸金属盐。
作为上述脂肪酸金属盐的脂肪酸，可举出：癸酸、十一烷酸、月桂酸、十三烷酸、肉豆蔻酸、十五烷酸、棕榈酸、十七烷酸、硬脂酸、十九烷酸、花生酸、山嵛酸、木蜡酸、蜡酸、二十七烷酸、褐煤酸、十一碳烯酸、油酸、反油酸、鲸蜡烯酸、芥酸、巴西烯酸、山梨酸、亚油酸、亚麻酸、花生四烯酸、丙炔酸、硬脂炔酸、12-羟基十二烷酸、3-羟基癸酸、16-羟基十六烷酸、10-羟基十六烷酸、12-羟基十八烷酸、10-羟基-8-十八烷酸等。另外，金属化合物为锂、钠、钾等碱金属；镁、钙、锶、钡等碱土金属；锌或铝的氢氧化物或氯化物。其中，优选脂肪酸为肉豆蔻酸、棕榈酸、硬脂酸，金属化合物为钙的氢氧化物、氧化物和氯化物，更优选为肉豆蔻酸钙、棕榈酸钙、硬脂酸钙。
在上述烧结成型体用组合物中添加上述含氮化合物和上述脂肪酸金属盐的情况下，上述脂肪酸金属盐的质量相对于上述含氮化合物的质量的比例(脂肪酸金属盐的质量/含氮化合物的质量)优选在特定的范围内，具体地，该比例为1～15，优选为1～10。通过将该比例设定为1～15，在能够提高有机粘结剂中的聚缩醛树脂的热稳定性的方面是优选的。
<可烧结的无机粉末>
在本实施方式中，“可烧结的无机粉末”能够从所有公知的适当的可烧结的无机粉末中选择。优选从金属粉末、合金粉末、羰基金属粉末和这些粉末的混合物中选择。其中，为了赋予功能性，特别优选金属粉末、陶瓷粉末。
可烧结的上述无机粉末可以单独使用一种，也可以组合使用多种。
作为上述金属粉末，具体的例子可举出：铝、镁、钡、钙、钴、锌、铜、镍、铁、硅、钛、钨以及基于这些金属的金属化合物和金属合金的粉末。在此，不仅能够使用已经制成的合金，还能够使用各个合金成分的混合物。
作为陶瓷粉末，可举出：氧化锌、氧化铝、氧化锆等氧化物；羟基磷灰石等氢氧化物；碳化硅等碳化物；氮化硅、氮化硼等氮化物；萤石等卤化物；块滑石等硅酸盐；钛酸钡、锆钛酸铅等钛酸盐；碳酸盐；磷酸盐；铁素体；高温超导物质等。
上述无机粉末可以单独使用一种，也可以组合使用各种金属、金属合金或陶瓷等几种无机物质。作为特别优选的金属、合金金属，可举出：钛合金、SUS316L等不锈钢，作为陶瓷，可举出：Al2O3、ZrO2。
作为上述无机粉末的平均粒径，优选为30μm以下，更优选为20μm以下。上述平均粒径例如能够通过采用激光衍射法的粒度分布测定装置测定。
相对于100质量份的上述烧结成型体用组合物，可烧结的上述无机粉末的质量比例优选为70质量份～95质量份，更优选为75质量份～95质量份，特别优选为80质量份～95质量份。通过可烧结的无机粉末的质量比例在上述范围内，能够得到具有适合于注射成型的熔融粘度的烧结成型体用组合物，而且能够得到强度高的生坯成型体。
<其他添加物>
作为能够添加在上述烧结成型体用组合物中的除了上述成分以外的其他添加剂，只要不损害本发明的效果就没有限制，但作为优选的添加剂，可举出抗氧化剂。
作为上述抗氧化剂，例如可举出：3-(3’,5’-二叔丁基-4’-羟基苯基)丙酸正十八烷基酯、3-(3’-甲基-5’-叔丁基-4’-羟基苯基)丙酸正十八烷基酯、3-(3’,5’-二叔丁基-4’-羟基苯基)丙酸正十四烷基酯、1,6-己二醇-双(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)、1,4-丁二醇-双(3-(3,5-二叔丁基-4-羟基苯基)丙酸酯)、3-(3,5-二叔丁基-4-羟基苯基)丙酸十八烷基酯、三乙二醇-双(3-(3-叔丁基-5-甲基-4-羟基苯基)丙酸酯)、四(亚甲基-3-(3’-叔丁基-4-羟基苯基)丙酸酯)甲烷、N,N’-双(3-(3,5-二叔丁基-4-羟基苯酚)丙酰基)肼、N,N’-双(3-(3’-甲基-5’-叔丁基-4-羟基苯酚)丙酰基)四亚甲基二胺、N,N’-双(3-(3’,5’-二叔丁基-4-羟基苯酚)丙酰基)六亚甲基二胺、3-(N-水杨酰基)氨基-1,2,4-三唑、N,N’-双(2-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基氧基)乙基)草酰胺、N,N’-六亚甲基-双(3-(3,5-二叔丁基-4-羟基苯基)丙酰胺)等。这些抗氧化剂可以使用一种，也可以组合使用两种以上。
相对于100质量份的聚缩醛树脂，抗氧化剂的含量为0.01质量份～1.0质量份，优选为0.05质量份～0.5质量份。通过抗氧化剂的含量在上述范围内，热稳定性提高。
本实施方式的烧结成型体用组合物的熔体流动指数根据ASTM-D-1238-57T在190℃、2.16kg的条件下测定，优选大于等于80g/10分钟且小于200g/10分钟，更优选大于等于90g/10分钟且小于180g/10分钟，进一步优选大于等于90g/10分钟且小于140g/10分钟。通过将熔体流动指数调节为80g/10分钟以上，烧结成型体用组合物的流动性提高，通过将熔体流动指数调节为小于200g/10分钟，能够提高生坯成型体的强度。
需要说明的是，烧结成型体用组合物的熔体流动指数例如能够通过使用的聚缩醛树脂的种类或质量比例而控制在上述范围内，聚缩醛树脂的熔体流动指数越大，具有烧结成型体用组合物的熔体流动指数也越大的倾向。
[烧结成型体用组合物的制造方法]
上述烧结成型体用组合物的制造方法没有特别限制，能够通过公知的方法制造。具体地，能够通过如下方式制造：将上述的可烧结的无机粉末和有机粘结剂例如利用亨舍尔混合机、滚筒、V型掺和机等混合，然后使用单螺杆挤出机或双螺杆挤出机、加热辊、捏合机、班伯里密炼机等混炼机在半熔融状态下进行熔融混炼，并且能够以线状、颗粒状等各种形态的制品的形式获得。
[生坯成型体]
本实施方式的烧结成型体用组合物能够用作在通过注射成型而成型出作为烧结成型体的预成型体的生坯成型体时的成型用原料。能够通过使用螺杆式和活塞式注射成型机由该烧结成型体用组合物得到生坯成型体。
本实施方式的生坯成型体优选至少具有厚度为1mm以下的部分，更优选具有厚度为1mm以下且表面积为1mm2以上的部位。上述成型方法能够得到存在表面积为1mm2以上的厚度为1mm以下的部位的生坯成型体。
(生坯成型体的强度)
进行通过上述成型方法得到的上述生坯成型体的三点弯曲试验，最大抗弯强度(MPa)的值与应变为0.05％～0.1％时的弹性模量(MPa)的值的乘积优选为50,000以上，更优选为100,000以上。上述最大抗弯强度和弹性模量能够通过在后述的实施例中记载的方法测定。
当最大抗弯强度的值与应变为0.05％～0.1％时的弹性模量的上述乘积小于50,000时，在搬运通过注射成型而得到的生坯成型体时，生坯成型体容易产生变形或产生破损。
(生坯成型体的脱脂/烧结)
将生坯成型体收容在密闭的脱脂/烧结炉中，并在所期望的条件下进行脱脂/烧结，从而能够得到烧结成型体。
在通过加热进行脱脂的方法的情况下，通过在氮气气氛下从常温升温到500℃至600℃而进行脱脂。也可以在加热前在溶剂中使流动性赋予剂溶出。
接下来，通过升温到可烧结的无机粉末的烧结温度而能够得到烧结成型体。
在通过酸进行脱脂的方法的情况下，通过在氮气气氛下使硝酸气体流通并从常温升温到110℃至120℃而进行脱脂。
接下来，通过升温到可烧结的无机粉末的烧结温度而能够得到烧结成型体。
实施例
以下，列举具体的实施例和比较例对本发明详细地进行说明，但本发明并不限定于以下的实施例。
需要说明的是，实施例和比较例中的术语和特性的测定方法如下所述。
[原料]
(A聚缩醛树脂)
(A-1)
将带有能够使热介质通过的夹套的双轴桨叶型连续聚合反应器(栗本铁工所株式会社制造，直径2B、L/D＝14.8)调节到温度80℃。将利用环己烷将作为聚合催化剂的三氟化硼-二正丁醚络合物稀释到0.26质量％的催化剂调配液以69g/小时、将三聚甲醛以3500g/小时、将1,3-二氧杂环戊烷以121g/小时、将作为分子量调节剂的甲缩醛以7.1g/小时连续地供给到聚合反应器中并进行聚合。
将从聚合反应器排出的物质投入到0.5质量％的三乙胺水溶液中而进行聚合催化剂的失活，然后进行过滤、清洗、干燥。
接着，供给到设定为200℃的带排气口的双螺杆挤出机(L/D＝40)中，在末端稳定化区域中以换算成氮量为20ppm的方式添加0.8质量％三乙胺水溶液，在90kPa下减压脱气的同时进行稳定化，并利用造粒机制成颗粒。然后，在100℃下干燥2小时，从而得到了(A-1)聚缩醛树脂。
所得到的(A-1)聚缩醛树脂的熔点为164℃，熔体流动指数为70g/10分钟。
(A-2)
除了将作为分子量调节剂的甲缩醛的流量调节为7.9g/小时以外，与(A-1)聚缩醛树脂的制造方法同样地制造了(A-2)聚缩醛树脂。所得到的(A-2)聚缩醛树脂的熔点为164℃，熔体流动指数为90g/10分钟。
(A-3)
除了将作为分子量调节剂的甲缩醛的流量调节为9.4g/小时以外，与(A-1)聚缩醛树脂的制造方法同样地制造了(A-3)聚缩醛树脂。所得到的(A-3)聚缩醛树脂的熔点为164℃，熔体流动指数为121g/10分钟。
(A-4)
除了将作为分子量调节剂的甲缩醛的流量调节为10.6g/小时以外，与(A-1)聚缩醛树脂的制造方法同样地制造了(A-4)聚缩醛树脂。所得到的(A-4)聚缩醛树脂的熔点为164℃，熔体流动指数为180g/10分钟。
(A-5)
除了将作为分子量调节剂的甲缩醛的流量调节为11.6g/小时以外，与(A-1)聚缩醛树脂的制造方法同样地制造了(A-5)聚缩醛树脂。所得到的(A-5)聚缩醛树脂的熔点为164℃，熔体流动指数为213g/10分钟。
(A-6)
除了将作为分子量调节剂的甲缩醛的流量调节为6.9g/小时以外，与(A-1)聚缩醛树脂的制造方法同样地制造了(A-6)聚缩醛树脂。所得到的(A-6)聚缩醛树脂的熔点为164℃，熔体流动指数为60g/10分钟。
(A-7)
除了使用121g/小时的1,4-丁二醇缩甲醛替代1,3-二氧杂环戊烷并将作为分子量调节剂的甲缩醛的流量调节为7.1g/小时以外，与(A-1)聚缩醛树脂的制造方法同样地制造了(A-7)聚缩醛树脂。所得到的(A-7)聚缩醛树脂的熔点为164℃，熔体流动指数为64g/10分钟。
(B聚烯烃树脂)
B-1：聚丙烯(住友化学株式会社制造，住友NOBLEN UH501E1，MFR 100g/10分钟)
B-2：聚乙烯(旭化成株式会社制造，SUNTEC TM LDPE M6555，MFR 55g/10分钟)
B-3：聚丙烯(日本聚丙烯株式会社制造，NOVATEC PP BC08C，MFR 60g/10分钟)
B-4：聚乙烯(试制品，MFR 100g/10分钟)
B-4的聚乙烯通过以下的步骤进行聚合。
1)固体催化剂A
利用干燥氮气除去高压釜内部的氧气和水分，然后加入三氯硅烷0.5mol/L的己烷溶液1.6L和己烷1.2L，并升温到70℃。接着，在70℃下用1小时引入Al0.15Mg(n-Bu)1.75(O-nBu)0.7(金属浓度为0.8mol/L的辛烷溶液)45L和己烷0.35L。进一步引入包含TiO4 0.7g的己烷0.6L，并在70℃下反应1小时。对反应混合物进行过滤，并利用己烷清洗。将其作为固体催化剂A。
2)固体催化剂B
将(C2H5)(n-C4H9)Mg与粘度为15厘沲的氢甲基聚硅氧烷的Si/Mg＝1.0/1.0的反应产物3.0摩尔和四氯化钛3.0摩尔与己烷6L一起加入到高压釜中，并在-10℃下反应3小时。与固体催化剂A的情况同样地对反应混合物进行后处理，从而得到了固体催化剂B。
3)MFR为100g/10分钟的聚乙烯的聚合
将容量100L的两个反应器串联连接，向第一个反应器中连续地供给固体催化剂A0.20g/小时、三异丁基铝(Al(i-C4H9)3)2.5毫摩尔/小时、环己烷溶剂100L/小时、乙烯8kg/小时、1-丁烯5kg/小时、氢气1.0L/小时，从第一个反应器中连续地取出聚合溶液，并供给到第二个反应器中，同时向第二个反应器中连续地供给固体催化剂B 0.10g/小时、三异丁基铝(Al(i-C4H9)3)1.5毫摩尔/小时、环己烷50L/小时、乙烯4kg/小时、氢气0.03L/小时，并进行聚合。在第一个反应器的温度为140℃、第二个反应器的温度为180℃的条件下进行聚合。所得到的乙烯-1-丁烯共聚物的MFR为100g/10分钟。
(C含氮化合物)
尼龙66(分子量10000)
(D脂肪酸金属盐〕
硬脂酸钙
(E流动性赋予剂)
E-1：石蜡(日本精蜡株式会社制造，Paraffin wax-145)
E-2：聚乙二醇(西格玛-奥德里奇公司制造)
E-3：聚四亚甲基二醇(三菱化学株式会社制造)
[烧结成型体用组合物的制造]
向100质量份的(A-1)～(A-7)的聚缩醛树脂中均匀添加并混合0.05质量份的(C)尼龙66、0.3质量份的(D)硬脂酸钙，供给到设定为200℃的带排气口的双螺杆挤出机(L/D＝40)中，并在90kPa下减压脱气的同时制成颗粒。然后，在100℃下干燥2小时。
使用SUS316L(平均粒径10μm)作为可烧结的无机粉末，将上述聚缩醛树脂组合物、(B)聚烯烃树脂、(E)流动性赋予剂以表1、表2所示的比例配合，从而制备了烧结成型体用组合物。
[评价]
(熔体流动指数(MI))
根据ASTM-D-1238使用东洋精机株式会社制造的MELT INDEXER在190℃、2160g的条件下测定了MI(熔体流动指数：g/10分钟)。
(生坯成型体的成型)
将实施例1～18和比较例1～11的烧结成型体用组合物利用加压捏合机在170℃下混炼1小时，然后使用注射成型机(发那科株式会社制造，ROBOSHOTα-50iA)将通过对该混炼物进行冷却、粉碎而得到的注射成型用原料在成型温度175℃～200℃下成型，从而得到了根据ISO 10724-1的哑铃形状的生坯成型体试验片。另外，能够将该试验片的厚度变为1mm、2mm。
(成型性)
生坯成型体的成型中的成型容易度按以下的基准进行评价。
〇(良好)：能够没有问题地收集
△(一部分不良)：极少在成型体的边缘观察到缺口
×(不良)：无法收集到没有缺口等的成型品
(生坯成型体的强度)
通过三点弯曲试验进行了生坯成型体的强度的测定。即，对于上述哑铃状试验片，利用Autograph(英斯特朗公司制造，Dual column flore model 5581)，将支撑夹具的间隔设定为50mm，测定以载荷传感器2mm/分钟的速度下降时的最大强度和弹性模量。计算最大抗弯强度(MPa)与弹性模量(MPa)的乘积，基于该乘积的值，按以下的基准进行评价。
◎(优异)：100,000以上
〇(良好)：大于等于50,000且小于100,000
×(不良)：小于50,000
需要说明的是，最大抗弯强度与弹性模量的乘积高的烧结成型体用组合物表示不易发生塑性变形，并且不易残留永久应变，因此是适合于生坯成型体的材料。
(脱脂性)
(酸脱脂)
实施例1～6、比较例1～4利用酸进行了脱脂。将生坯成型体以50mm的间隔进行两点支撑，并设置在脱脂炉中。首先，将上述脱脂炉加热至110℃，并利用氮气500L/小时置换30分钟。然后，在保持氮气吹扫下供给98％硝酸30ml/小时。在如下条件下进行脱脂：保持酸供给2.5小时，接着对脱脂炉利用氮气500L/小时置换45分钟，并冷却至室温。目视观察脱脂后的生坯成型体的外观，按以下的基准进行评价。
〇(良好)：没有观察到破裂/鼓起等外观异常
×(不良)：观察到破裂/鼓起等外观异常
－(未实施)：不能进行注射成型
(加热脱脂)
实施例7～18、比较例5～11进行了加热脱脂。将生坯成型体以50mm的间隔进行两点支撑，并设置在脱脂炉中。接下来，利用氮气对脱脂炉内进行吹扫，在氮气气流下，作为第一条件以30℃/小时的升温速度、作为第二条件以45℃/小时的升温速度分别升温至500℃，并在500℃下保持2小时，由此进行了脱脂。目视观察脱脂后的生坯成型体的外观，按以下的基准进行评价。
〇(优异)：在第一条件、第二条件下均没有观察到破裂/鼓起等外观异常
△(良好)：在第一条件下没有观察到破裂/鼓起等外观异常，但在第二条件下观察到破裂/鼓起
×(不良)：在第一条件、第二条件下均观察到破裂/鼓起。
－(未实施)：不能进行注射成型
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Claims (10)
1.一种烧结成型体用组合物，其特征在于，所述烧结成型体用组合物包含可烧结的无机粉末和有机粘结剂，
所述有机粘结剂至少包含聚缩醛树脂和聚烯烃树脂，
所述聚缩醛树脂的熔体流动指数为70g/10分钟～200g/10分钟。
2.根据权利要求1所述的烧结成型体用组合物，其中，所述聚烯烃树脂的熔体流动指数(190℃、2.16kg)为40g/10分钟以上。
3.根据权利要求1或2所述的烧结成型体用组合物，其中，以所述有机粘结剂的质量为基准，在所述有机粘结剂中包含5质量％～95质量％的所述聚缩醛树脂和5质量％～95质量％的所述聚烯烃树脂。
4.根据权利要求1～3中任一项所述的烧结成型体用组合物，其中，当将所述烧结成型体用组合物设为100质量份时，所述烧结成型体用组合物包含70质量份～95质量份的所述可烧结的无机粉末。
5.根据权利要求1～4中任一项所述的烧结成型体用组合物，其中，以所述有机粘结剂的质量为基准，在所述有机粘结剂中包含5质量％～60质量％的流动性赋予剂。
6.根据权利要求1～5中任一项所述的烧结成型体用组合物，其中，所述聚缩醛树脂包含氧亚甲基单元和氧亚乙基单元。
7.根据权利要求1～6中任一项所述的烧结成型体用组合物，其中，以所述有机粘结剂的质量为基准，所述有机粘结剂包含5质量％～50质量％的所述聚缩醛树脂。
8.根据权利要求1～7中任一项所述的烧结成型体用组合物，其中，所述有机粘结剂包含含氮化合物和脂肪酸金属盐。
9.一种生坯成型体，其中，所述生坯成型体通过将权利要求1～8中任一项所述的烧结成型体用组合物成型而得到。
10.根据权利要求9所述的生坯成型体，其中，在所述生坯成型体中存在100mm2以上的厚度为1mm以下的部位。
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| PCT/JP2022/012080 WO2022215472A1 (ja) | 2021-04-07 | 2022-03-16 | 焼結成形体用組成物及び焼結成形体 |
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| DE4007345A1 (de) | 1990-03-08 | 1991-09-12 | Basf Ag | Thermoplastische massen fuer die herstellung metallischer formkoerper |
| DE4021739A1 (de) | 1990-07-07 | 1992-01-09 | Basf Ag | Thermoplastische massen fuer die herstellung metallischer formkoerper |
| JPH05125403A (ja) * | 1991-10-31 | 1993-05-21 | Sumitomo Metal Mining Co Ltd | 金属粉末射出成形用組成物 |
| JPH06158107A (ja) * | 1992-11-28 | 1994-06-07 | Sanyo Chem Ind Ltd | 射出成形用組成物 |
| JP2955754B1 (ja) * | 1998-06-01 | 1999-10-04 | 有限会社モールドリサーチ | 金属粉末の射出成形用組成物と、その組成物を用いた射出成形及び焼結法 |
| JP2003212942A (ja) * | 2002-01-28 | 2003-07-30 | Asahi Kasei Corp | 中空射出成形用樹脂材料及び中空成形品 |
| US20060074175A1 (en) * | 2004-10-01 | 2006-04-06 | Kane Paul J | Process for forming shaped articles from polyacetal and polyacetal/non-melt processable polymer blends |
| CN101489704B (zh) | 2006-07-13 | 2011-04-20 | 巴斯夫欧洲公司 | 用于制备金属成型体的含粘合剂的热塑性组合物 |
| CA2923775C (en) * | 2013-09-12 | 2021-09-28 | National Research Council Of Canada | Lubricant for powder metallurgy and metal powder compositions containing said lubricant |
| CN107304249A (zh) * | 2016-04-22 | 2017-10-31 | 中国石油化工股份有限公司 | 用于选择性激光烧结的聚甲醛树脂粉末及其制备方法 |
| WO2019219522A1 (en) * | 2018-05-15 | 2019-11-21 | Höganäs Ab (Publ) | Binder composition for metal injection molding feedstocks; metal injection molding feedstock comprising the same; metal injection molding process using the feedstock, and article obtained by the process |
| CN110483420B (zh) * | 2019-08-27 | 2021-01-15 | 云南民族大学 | 一种四氢喹喔啉类化合物的制备方法 |
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