以下，對本發明進一步詳細說明，但本發明並不限定於此。 [1.硬化性聚矽氧樹脂組合物] 本發明之硬化性聚矽氧樹脂組合物(以下有時稱為「本發明之組合物」)至少含有(A)～(C)成分。以下，對本發明之組合物中所含之各成分進行說明。 ＜(A)成分＞ (A)成分係以下述式[1]所表示，且黏度為10,000 cP以下之聚矽氧樹脂。 [化8] (H-SiMe2
O1/2
)a
(Me2
SiO2/2
)b
(PhSiO3/2
)c
(SiO4/2
)d
[1] 上述式[1]中，a、b、c及d分別為超過0且未達1之數，滿足a＋b＋c＋d＝1。(H-SiMe2
O1/2
)、(Me2
SiO2/2
)、(PhSiO3/2
)及(SiO4/2
)所表示之結構單元中之氧原子分別表示形成矽氧烷鍵之氧原子或形成矽烷醇基之氧原子。 式[1]中，若a之值、b之值、c之值及d之值分別為超過0且未達1之範圍內且滿足a＋b＋c＋d＝1，則並無特別限定。a之值較佳為0.05～0.40，較佳為0.10～0.30。b之值較佳為0.10～0.80，尤佳為0.10～0.40。c之值較佳為0.10～0.80，尤佳為0.30～0.60。d之值較佳為0.0005～0.40，尤佳為0.005～0.30。若a及b、c、d之值為上述範圍，則本發明之組合物及硬化體具有良好之成形性、良好之機械強度。 再者，a之值、b之值、c之值及d之值係使用核磁共振裝置測定式[1]所表示之聚矽氧化合物之29
Si-NMR光譜與1
H-NMR光譜，並使用該等而算出。 式[1]中，(Me2
SiO2/2
)所表示之結構單元可包含下述式[1-2]所表示之結構，即，(Me2
SiO2/2
)所表示之結構單元中之矽原子所鍵結之氧原子之一個形成矽烷醇基的結構。 [化9] Me2
Si(OH)O1/2
[1-2] (Me2
SiO2/2
)所表示之結構單元包含下述式[1-b]所表示之結構單元之虛線所包圍之部分，進而亦可包含下述式[1-2-b]所表示之結構單元之虛線所包圍之部分。即，具有Me所表示之基(甲基)且於末端殘留羥基並與矽原子形成矽烷醇基的結構單元亦包含於(Me2
SiO2/2
)所表示之結構單元中。又，下述式[1-b]、[1-2-b]所表示之結構單元中，Si-O-Si鍵中之氧原子與鄰接之矽原子形成矽氧烷鍵，與鄰接之結構單元共有氧原子。因此，將Si-O-Si鍵中之1個氧原子設為「O1/2
」。 [化10]式[1]中，(PhSiO3/2
)所表示之結構單元可包含下述式[1-2]所表示之結構或式[1-3]所表示之結構，即，(PhSiO3/2
)所表示之結構單元中之矽原子所鍵結之氧原子之兩個分別形成矽烷醇基的結構，或(PhSiO3/2
)所表示之結構單元中之矽原子所鍵結之氧原子之一個形成矽烷醇基的結構。 [化11] (PhSi(OH)2
O1/2
) [1-3] (PhSi(OH)O2/2
) [1-4] 式[1]中，(PhSiO3/2
)所表示之結構單元包含下述式[1-c]所表示之結構單元之虛線所包圍之部分，進而亦可包含下述式[1-3-c]或[1-4-c]所表示之結構單元之虛線所包圍之部分。即，具有Ph所表示之基(苯基)且末端殘留羥基並與矽原子形成矽烷醇基的結構單元亦包含於(PhSiO3/2
)所表示之結構單元中。 [化12]式[1]中，(SiO4/2
)所表示之結構單元包含下述式[1-d]所表示之結構單元之虛線所包圍之部分，進而亦可包含下述式[1-5-d]、[1-6-d]或[1-7-d]所表示之結構單元之虛線所包圍之部分。即，末端殘留羥基並與矽原子形成矽烷醇基的結構單元亦包含於(SiO4/2
)所表示之結構單元中。 [化13](A)成分之黏度若於標準狀態(25℃，1個大氣壓)下為10,000 cP(厘泊)以下，則並無特別限定。就操作作業性之觀點而言，較佳為7,000 cP以下。下限值並無特別限制，黏度越低，越可使所得本發明之組合物低黏度化，進而，使半導體裝置之密封作業變得越容易，故而較佳。(A)成分之黏度於標準狀態(25℃，1個大氣壓)下可為超過0 cP且10,000 cP以下，較佳為超過0 cP且7,000以下。 此處，(A)成分之黏度係藉由旋轉黏度計等測定。具體而言，依據JIS Z8803(2011)中之「藉由圓錐-板形旋轉黏度計之黏度測定方法」，使用旋轉黏度計(ANTON PAAR製造，商品名：PHYSICA MCR51，測定範圍200～1,000,000 cP)與溫度控制單元(ANTON PAAR製造，商品名：P-PTD200)，於標準狀態(25℃，1個大氣壓)下以剪切速度30[1/s]進行測定，將自測定開始經過1分鐘後所得值作為(A)成分之黏度。 (A)成分至少含有與矽原子鍵結之氫原子(H-Si基)，其量並無特別限定。較佳為於一分子中含有兩個以上。就獲得良好之硬化物之方面而言，尤佳為0.5～4.0 mmol/g。 (A)成分之質量平均分子量並無特別限定。較佳為500～10,000，進而較佳為800～7,000。若質量平均分子量為500以上，則本發明之硬化物具有良好之樹脂強度，若為10,000以下，則本發明之組合物具有良好之成形性。 此處，質量平均分子量係藉由凝膠滲透層析法(簡稱：GPC)進行測定，由標準聚苯乙烯校準曲線進行換算所得之值(於本說明書，以下相同)。 (A)成分中含有之HO-Si基之量並無特別限定。較佳為0.5～4.5 mmol/g，尤佳為1.0～3.5 mmol/g。若HO-Si基之含量超過4.5 mmol/g，則有時於硬化物中觀測到氣泡。 ＜(B)成分＞ (B)成分係以下述式[2]所表示，且黏度為10,000 cP以下之聚矽氧樹脂。 [化14] (Vi-SiMe2
O1/2
)e
(Me2
SiO2/2
)f
(PhSiO3/2
)g
(SiO4/2
)h
[2] 上述式[2]中，e、f、g及h分別為超過0且未達1之數，滿足e＋f＋g＋h＝1。(Vi-SiMe2
O1/2
)、(Me2
SiO2/2
)、(PhSiO3/2
)及(SiO4/2
)所表示之結構單元中之氧原子分別表示形成矽氧烷鍵之氧原子或形成矽烷醇基之氧原子。 式[2]中，若e之值、f之值、g之值及h之值分別為超過0且未達1之範圍內，且滿足e＋f＋g＋h＝1，則並無特別限定。e之值較佳為0.05～0.40，較佳為0.10～0.30。f之值較佳為0.10～0.80，尤佳為0.10～0.40。g之值較佳為0.10～0.80，尤佳為0.30～0.60。h之值較佳為0.001～0.40，尤佳為0.05～0.30。若e及f、g、h之值為上述範圍，則本發明之組合物及硬化體具有良好之成形性、良好之機械強度。 再者，e之值、f之值、g之值及h之值係使用核磁共振裝置測定式[2]所表示之聚矽氧化合物之29
Si-NMR光譜與1
H-NMR光譜，使用該等而算出。 式[2]中，(Me2
SiO2/2
)所表示之結構單元與上述[1]中之(Me2
SiO2/2
)所表示之結構單元含義相同，(PhSiO3/2
)所表示之結構單元與上述[1]中之(PhSiO3/2
)所表示之結構單元含義相同，(SiO4/2
)所表示之結構單元與上述[1]中之(SiO4/2
)所表示之結構單元含義相同。 (B)成分之黏度若於標準狀態(25℃，1個大氣壓)下為10,000 cP(厘泊)以下則並無特別限定。就操作作業性之觀點而言，較佳為7,000 cP以下。下限值並無特別限制，黏度越低，越可使所得本發明之組合物低黏度化，進而，使半導體裝置之密封作業變得越容易，故而較佳。(B)成分之黏度於標準狀態(25℃，1個大氣壓)下可為超過0 cP且10,000 cP以下，較佳為超過0 cP且7,000以下。 此處，(B)成分之黏度係藉由與(A)成分之黏度相同之方法而測定。 (B)成分至少含有與矽原子鍵結之乙烯基(Vi-Si基)，其量並無特別限定。較佳為於一分子中含有兩個以上。就獲得良好之硬化物之方面而言，尤佳為0.5～4.0 mmol/g。 (B)成分之質量平均分子量並無特別限定。較佳為500～10,000，進而較佳為800～7,000。若質量平均分子量為500以上，則本發明之硬化物具有良好之樹脂強度，若為10,000以下，則本發明之組合物具有良好之成形性。 (B)成分中含有之HO-Si基之量並無特別限定。較佳為0.5～6.0 mmol/g，尤佳為1.0～3.5 mmol/g。若HO-Si基之含量超過6.0 mmol/g，則有時於硬化物中觀測到氣泡。 ＜(C)成分＞ 作為(C)成分之矽氫化觸媒係以促進下述(A)成分中之H-Si基與(B)成分中之Vi-Si基之矽氫化反應(加成硬化反應)為目的而調配。 作為(C)成分之種類，若為促進上述矽氫化反應者，則並無特別限定。較佳為使用選自由鉑系觸媒、銠系觸媒及鈀系觸媒所組成之群中之至少一種以上。其中，因可提高密封材之透明性，故而尤佳為使用鉑系觸媒。 作為該鉑系觸媒，可列舉：鉑粉末、氯鉑酸、氯鉑酸等之鉑成分與醇、醛、酮等之錯合物、鉑-烯烴錯合物、鉑-烯基矽氧烷錯合物、鉑-羰基錯合物等。可列舉：鉑-羰基乙烯基甲基錯合物、鉑-二乙烯基四甲基二矽氧烷錯合物(卡斯特(Karstedt)觸媒)、鉑-環乙烯基甲基矽氧烷錯合物、鉑-辛醛錯合物、鉑-膦錯合物、二羰基二氯鉑等。其中，較佳為鉑-二乙烯基四甲基二矽氧烷錯合物、鉑-環乙烯基甲基矽氧烷錯合物等。 ＜其他添加物＞ 於本發明之組合物中，除上述(A)～(C)成分外，亦可調配其他添加物。 ((D)成分：硬化延遲劑) 作為其他添加物，例如，為提高該組合物之保存穩定性、操作作業性，調整硬化過程中之矽氫化反應性等，可於本發明之組合物中調配硬化延遲劑(以下，有時稱為(D)成分)。 本發明之組合物可於較低溫度下成為硬化物，故而可較佳地用於對不耐熱之光半導體構件進行塗佈、密封。另一方面，根據塗佈、密封之作業環境，就本發明之組合物之保存經時穩定性或操作作業性之觀點而言，有時較佳為為調整硬化速度而調配硬化延遲劑。 作為(D)成分之種類，若為對(C)成分具有硬化延遲效果之化合物，則並無特別限定。可使用先前公知之硬化延遲劑，例如可列舉：含有脂肪族不飽和鍵之化合物、有機磷化合物、含氮化合物、有機硫化合物、有機過氧化物等。該等化合物可使用單一種類，亦可併用複數種。 本發明之組合物中之(D)成分之含量並無特別限定。通常相對於組合物中含有之(C)成分中之鉑原子1當量，添加硬化延遲劑20～200當量即可。藉由硬化延遲劑之硬化延遲效果之程度根據該硬化延遲劑之化學結構而有所不同。因此，較佳為根據所使用之硬化延遲劑之種類，將其調配量調整為最適合之量。藉由添加最適合之量之硬化延遲劑，可使本發明之組合物成為於室溫(尤其指未加熱或冷卻之環境溫度，通常為15～30℃；以下相同)下之長期儲存穩定性及加熱硬化性優異者。 ((E)成分：接著賦予劑) 於本發明之組合物中，除上述(A)～(C)成分外，為提高其接著性，亦可調配接著賦予劑(以下，有時稱為(E)成分)。 作為(E)成分之種類，可使用先前公知之矽烷偶合劑或其水解縮合物等，例如可列舉：含環氧基之矽烷偶合劑、含(甲基)丙烯醯基之矽烷偶合劑、含異氰酸酯基之矽烷偶合劑、含異氰尿酸酯基之矽烷偶合劑、含胺基之矽烷偶合劑、含巰基之矽烷偶合劑等。該等可使用單一種類，亦可併用複數種。 本發明之組合物中之(E)成分之含量並無特別限定。相對於(A)～(C)成分之總質量較佳為調配1～20質量%，尤佳為5～15質量%。 ((F)成分：抗氧化劑) 為抑制硬化物之著色、氧化劣化等之發生，可於本發明之組合物中添加抗氧化劑(以下，有時稱為(F)成分)。 作為(F)成分之種類，可使用先前公知之抗氧化劑，例如可列舉：酚系抗氧化劑、硫醚系抗氧化劑、磷系抗氧化劑等。其中，較佳為酚系抗氧化劑、硫醚系抗氧化劑，尤佳為硫醚系抗氧化劑。該等抗氧化劑可單獨使用一種，亦可併用兩種以上。 本發明之組合物中之(F)成分之含量若為不損害本發明之硬化物之透明性等特徵之範圍且為作為抗氧化劑之有效量，則並無特別限定。相對於(A)～(C)成分之總質量，可調配0.001～2質量%，較佳為調配0.01～1質量%。若為該範圍內，則充分發揮抗氧化能力，故而可抑制著色、白濁、氧化劣化等之發生，並且獲得工程特性優異之硬化物。 ((G)成分：光穩定劑) 為賦予對太陽光線、螢光燈等光能所導致之光劣化之阻抗性，可於本發明之組合物中添加光穩定劑(以下，有時稱為(G)成分)。 作為(G)成分之種類，可使用先前公知之光穩定劑。其中，可較佳使用捕捉因光氧化(光劣化)而生成之自由基之受阻胺系穩定劑，亦可藉由與上述(F)成分併用，而進一步提高抗氧化效果。 本發明之組合物中之(G)成分之調配量若為不損害本發明之硬化物之透明性等特徵之範圍且為作為光穩定劑之有效量，則並無特別限定。相對於(A)～(C)成分之總質量，可調配0.01～5質量%，較佳為調配0.05～0.5質量%。 ((H)成分：螢光體) 於本發明之組合物中可調配作為任意成分之螢光體(以下，有時稱為(H)成分)。 作為(H)成分之種類，可使用先前公知者。例如可列舉：廣泛用於發光二極體(LED)之包含氧化物系螢光體、氮氧化物系螢光體、氮化物系螢光體、硫化物系螢光體、氧硫化物系螢光體等之黃色、紅色、綠色、藍色發光螢光體。 (H)成分之調配量若為不損害本發明之硬化物之透明性等特徵之範圍且為作為螢光體之有效量，則並無特別限定。相對於(A)～(C)成分之總質量，較佳為調配10～70質量%，尤佳為20～50質量%。 ((I)成分：無機粒子) 於本發明之組合物中，為提高其硬化物之光學特性或作業性、機械特性、物理化學特性，可調配無機粒子(以下，有時稱為(I)成分)。(I)成分之種類可根據目的而選擇，又，可調配單一種類，亦可組合複數種調配。又，為改善分散性，無機粒子可藉由矽烷偶合劑等表面處理劑而進行表面處理。 作為(I)成分之種類，可例示：二氧化矽、鈦酸鋇、氧化鈦、氧化鋯、氧化鈮、氧化鋁、氧化鈰、氧化釔等無機氧化物粒子，或氮化矽、氮化硼、碳化矽、氮化鋁等氮化物粒子或碳化合物粒子、金剛石粒子等，亦可根據目的而選擇其他物質，並不限定於該等。 (I)成分之形態可根據目的為粉體狀、漿體狀等任意形態。根據所要求之透明性，以儘可能使折射率與本發明之硬化物相同之方式調配於本發明之組合物中。又，較佳為作為水系、溶劑系之透明溶膠而調配於本發明之組合物中。 調配之(I)成分之平均粒徑並無特別限定，使用與目的相應之平均粒徑者。通常為上述螢光體之粒徑之1/10以下左右。再者，粒徑係藉由SEM(掃描式電子顯微鏡)觀察而測定粒子之短徑及長徑，計算(短徑＋長徑)/2所得之值。該作業係對SEM圖像中之一定區間中之粒子進行，將所得各個粒徑之算術平均值作為(I)成分之平均粒徑。 (I)成分之調配量若不損害本發明之硬化物之耐熱透明性等特徵，則為任意。若(I)成分之調配量過少，則有時無法獲得所期望之效果，若過多，則有時對硬化物之耐熱透明性、密著性、透明性、成形性、硬度等諸特性帶來不良影響。相對於(A)～(C)成分之總質量，可調配1～50質量%左右，較佳為調配5～35質量%左右。 除(D)～(I)成分外，亦可於不損害硬化物之透明性等特徵之範圍內，於本發明之組合物中調配脫模劑、樹脂改質劑、著色劑、稀釋劑、抗菌劑、防黴劑、調平劑、防垂流劑等。 ＜(A)成分、(B)成分及(C)成分之調配比＞ 本發明之組合物中之(A)成分與(B)成分之調配比並無特別限定。基本上以(A)成分中含有之H-Si基與(B)成分中含有之Vi-Si基之莫耳比為基準進行調配。具體而言，較佳為(A)成分中含有之H-Si基之莫耳數/(B)成分中含有之Vi-Si基之莫耳數＝1～4之範圍，尤佳為1～3。若為該範圍內，則本發明之組合物顯示良好之成形性，又，本發明之硬化物具有優異之耐熱透明性。 本發明之組合物中之(C)成分之調配量並無特別限定。較佳為基於(A)成分與(B)成分與(C)成分之總質量，(C)成分中之金屬原子以質量單位計成為0.003～30 ppm之範圍內的量。其中，因存在所得硬化物具有優異之耐熱透明性之傾向，故而更佳為0.003～5.0 ppm，進而較佳為0.003～3.0 ppm，尤佳為0.003～2.0 ppm。若(C)成分之調配量為0.003～30 ppm，則(A)成分與(B)成分之矽氫化反應順利進行。 本發明之組合物之黏度若於標準狀態(25℃，1個大氣壓)下為10,000 cP(厘泊)以下，則並無特別限定。若為10,000 cP以下，則較佳為7,000 cP以下。下限值並無特別限制，黏度越低，半導體裝置之密封作業變得越容易，故而較佳。本發明之組合物之黏度於標準狀態(25℃，1個大氣壓)下可為超過0 cP且10,000 cP以下，較佳為超過0 cP且7,000以下。 此處，本發明之組合物之黏度係藉由與(A)成分之黏度相同之方法而測定。 本發明之組合物為低黏度之樹脂組合物，故而流動性良好，尤其於半導體裝置之密封作業中，難以產生樹脂組合物之中斷或氣泡之捲入，易於塗佈。故而，可高效地進行密封作業。進而，自本發明之組合物獲得之硬化物於半導體裝置之密封材用途中具有充分之耐久性。故而，本發明之組合物適合於半導體裝置之密封材用途。 本發明之組合物中之(A)成分與(B)成分中之HO-Si基之總含量並無特別限定。可為0.5～5.0 mmol/g，較佳為1.0～4.5 mmol/g，尤佳為1.5～4.5 mmol/g。若為該範圍內，則組合物之硬化充分進行，易於獲得所期望之硬化物。 ＜硬化性聚矽氧樹脂組合物之製備＞ 本發明之組合物可藉由調配(A)成分與(B)成分與(C)成分，視需要進而調配其他添加物而製備。 較佳為藉由混合(A)成分、(B)成分、(C)成分、視需要而添加之添加物，而使該等實質均勻分散。混合方法並無特別限定，可採用先前公知之混合方法。例如，可採用使用萬能混練機、捏合機等混合裝置之混合方法。 又，(C)成分可預先與(A)成分及/或(B)成分混合。又，為了穩定地長時間儲存，將(B)成分與(C)成分保存於不同之容器中，例如，可預先將含有(A)成分之一部分與(C)成分之第一組合物、及含有(A)成分之剩餘部分與(B)成分之第二組合物，分別保持於不同之容器中，於即將使用前混合從而製備本發明之組合物後供給使用，亦可將製備之組合物進而藉由減壓而脫泡後供給使用。 ((A)成分之製造方法) 作為(A)成分之製造方法之一例，可藉由至少包含以下第1步驟～第3步驟之方法而製造(A)成分。 第1步驟：使下述通式[3]所表示之二烷氧基矽烷與下述通式[4]所表示之三烷氧基矽烷反應而獲得第1水解縮聚物的步驟； 第2步驟：使第1水解縮聚物與下述通式[5]所表示之四烷氧基矽烷於強酸條件下反應而獲得第2水解縮聚物的步驟； 第3步驟：使第2水解縮聚物與下述通式[6]、[7]或[8]所表示之矽烷化合物於強酸條件下反應，藉此獲得(A)成分的步驟； [化15] Me2
Si(OR5
)2
[3] PhSi(OR6
)3
[4] Si(OR7
)4
[5] H-SiMe2
(OH) [6] H-SiMe2
(OR8
) [7] (H-SiMe2
)2
O [8] 式[3]中，R5
表示碳數1～3之烷基，兩個R5
可為相互相同或不同之種類。式[4]中，R6
表示碳數1～3之烷基，三個R6
可為相互相同或不同之種類。式[5]中，R7
表示碳數1～3之烷基，四個R7
可為相互相同或不同之種類。式[7]中，R8
表示碳數1～3之烷基。 以下，對第1步驟～第3步驟進行說明。 「第1步驟」 於第1步驟中，首先，將特定量之通式[3]所表示之二烷氧基矽烷(以下，有時稱為「二烷氧基矽烷[3]」)與通式[4]所表示之三烷氧基矽烷(以下，有時稱為「三烷氧基矽烷[4]」)於室溫下投入反應容器內後，添加用以水解縮聚之水，根據所需而添加反應溶劑，根據所需而添加用以使縮合反應順利進行之觸媒，製為反應溶液。此時之反應材料之投入順序並無特別限定，可以任意順序投入而製為反應溶液。繼而，一面攪拌該反應溶液一面以特定時間、特定溫度進行反應，藉此可獲得第1水解縮聚物。此時，為防止反應系統中之未反應原料之烷氧基矽烷化合物、水、反應溶劑及/或觸媒餾出至反應系統外，較佳為於反應容器中具備回流裝置。 於第1步驟中，二烷氧基矽烷[3]、三烷氧基矽烷[4]之使用量並無特別限定。較佳為以二烷氧基矽烷[3]：三烷氧基矽烷[4]以莫耳比表示為85：15～15：85而調配，尤佳為以85：15～30：70調配。若二烷氧基矽烷[3]之莫耳比低於15，則有時會高於所期望之分子量，若超過85，則有時水解縮聚反應難以進行，低於所期望之分子量。 於第1步驟中，水之使用量並無特別限定。就反應效率之觀點而言，相對於反應原料之烷氧基矽烷化合物中含有之烷氧基，即，二烷氧基矽烷[3]、三烷氧基矽烷[4]中含有之烷氧基之總莫耳當量，較佳為1.5倍以上且5倍以下。若為1.5倍莫耳當量以上，則二烷氧基矽烷[3]、三烷氧基矽烷[4]之水解高效進行，又，不必添加多於5倍莫耳當量。 於第1步驟中，於無溶劑條件下亦可反應，但亦可使用反應溶劑。作為反應溶劑之種類，若不阻礙用以獲得第1水解縮聚物之反應，則並無特別限定。其中，較佳為醇類等親水性之有機溶劑。作為該醇類，具體可例示：甲醇、乙醇、正丙醇、異丙醇、丁醇等，但並不限定於該等。反應溶劑之使用量相對於反應原料之烷氧基矽烷化合物之總量較佳為0.1～1000質量%，尤佳為1～300質量%。 再者，於反應過程中自反應原料之烷氧基矽烷化合物生成之醇類可作為反應溶劑而發揮功能，故而有時並非必須添加。 於第1步驟中，於使用觸媒之情形時，可使用酸性觸媒或鹼性觸媒。其中，因所得第1水解縮聚物之分子量容易控制，故而較佳為使用酸性觸媒。該酸性觸媒之種類並無特別限定。例如可列舉：乙酸、鹽酸、硝酸、硫酸、氫氟酸、三氟甲磺酸、對甲苯磺酸、三氟乙酸等。其中，因反應結束後之酸觸媒之去除處理較容易，故而較佳為乙酸、鹽酸、硝酸、硫酸、氫氟酸，更佳為乙酸。又，鹼性觸媒之種類並無特別限定。例如可列舉：氫氧化鈉、氫氧化鉀、氫氧化鋰、氫氧化鎂、碳酸鈉、碳酸鉀、碳酸銫、三乙胺、吡啶等。 觸媒之使用量相對於反應原料之烷氧基矽烷化合物、水及溶劑之總量，較佳為0.001～5質量%，尤佳為0.005～1質量%。 於第1步驟中，反應時間、反應溫度並無特別限定。反應時間通常為3～15小時。反應溫度通常為60～120℃，較佳為80～100℃。 反應後，就第1水解縮聚物之處理性之觀點而言，較佳為自反應系統內分離第1水解縮聚物並精製。該分離方法並無特別限定。作為分離方法，例如可列舉萃取方法。具體而言，將上述反應後之反應溶液降溫至室溫後，與作為萃取溶劑之非水溶性有機溶劑接觸，藉此萃取反應系統中存在之第1水解縮聚物。繼而，進行萃取後之溶液中所含之觸媒之去除。觸媒之去除方法並無特別限定。例如，若所使用之觸媒(例如乙酸)為水溶性，則可藉由以水清洗萃取後之溶液而去除該觸媒。繼而，於去除觸媒後之溶液中添加乾燥劑，將系統中溶解之水去除。進而，經歷乾燥劑之去除、萃取溶劑之減壓去除，藉此可分離高純度之第1水解縮聚物。此時，亦可不使用乾燥劑，於自去除觸媒後之溶液將萃取溶劑減壓去除之過程中同時減壓去除水。 作為上述萃取溶劑，可使用非水溶性有機溶劑。該非水溶性有機溶劑之種類並無特別限定。例如可列舉：芳香族烴類、醚類等。具體可列舉：甲苯、二乙醚、異丙醚、二丁醚等，但並不限定於該等。 作為上述乾燥劑，若為可自系統中去除水，與第1水解縮聚物分離者，則並無特別限定。作為此種乾燥劑，較佳為使用固體乾燥劑，具體可列舉：硫酸鎂等，但並不限定於其。 分離、精製之第1水解縮聚物可藉由於溶劑中進行加熱回流或於無溶劑下進行加熱攪拌，而進而進行縮合反應。藉此，可增加第1水解縮聚物之分子量。於使用溶劑之情形時，於可加熱回流之反應容器中投入第1水解縮聚物與溶劑，製為溶解液。將該溶解液進行加熱回流，於進行縮合之同時與系統中生成之水共沸。此時，亦可於溶解液中添加對甲苯磺酸等而進行加熱回流。作為所使用之溶劑之種類，若為可溶解第1水解縮聚物且可加熱回流之溶劑，則並無特別限定。具體可列舉：芳香族烴類、醚類、酯類等。作為芳香族烴類，可列舉：甲苯、二甲苯、苯等，作為醚類，可列舉：二乙醚、二異丙醚等，作為酯類，可列舉：乙酸乙酯等。又，於無溶劑下之情形時，於可加熱攪拌之反應容器中投入第1水解縮聚物，加熱至100～150℃攪拌6～18小時。此時，為抑制第1水解縮聚物之組成比之變化，較佳為於反應容器中具備回流裝置(例如冷凝器)。加熱攪拌後將內容液降溫至室溫。該等一系列之操作可重複進行，重複次數並無特別限定。較佳為進行1～4次。 「第2步驟」 於第2步驟中，使第1步驟中獲得之第1水解縮聚物與通式[5]所表示之四烷氧基矽烷(以下，有時稱為「四烷氧基矽烷[5]」)於強酸存在下進行反應，獲得第2水解縮聚物。具體而言，將特定量之第1水解縮聚物與四烷氧基矽烷[5]於室溫下投入反應容器內後，根據所需添加反應溶劑，添加強酸作為用以進行縮合反應之觸媒，製為反應液。此時之投入順序並不限定於此，可以任意之順序投入而製為反應溶液。繼而，一面攪拌該反應液一面以特定時間、特定溫度進行反應，藉此可獲得第2水解縮聚物。此時，為防止反應系統中之未反應原料之烷氧基矽烷化合物、反應溶劑及/或觸媒餾出至反應系統外，較佳為於反應容器中具備回流裝置。 於第2步驟中，第1水解縮聚物與四烷氧基矽烷[5]之使用量並無特別限定。就反應性之觀點而言，相對於第1水解縮聚物，四烷氧基矽烷[5]較佳為0.001～600質量%，尤佳為以0.01～400質量%調配。 於第2步驟中，可於反應液中含有少量之水，但若含有大量之水，則有時反應過程中生成二氧化矽，無法獲得所期望之第2水解縮聚物。作為反應液中水之含量，若可獲得所期望之第2水解縮聚物，則並無特別限定，相對於四烷氧基矽烷[5]較佳為1質量%以下，尤佳為0.001質量%以下。該水之含量亦包含有時含有於硝酸或鹽酸等強酸中之水。 於第2步驟中，於無溶劑條件下亦可反應，但亦可使用反應溶劑，較佳為使用。作為反應溶劑之種類，若不阻礙用以獲得第2水解縮聚物之反應，則並無特別限定。其中，較佳為醇類等親水性之有機溶劑。作為該醇類，具體可例示：甲醇、乙醇、正丙醇、異丙醇、丁醇等，但並不限定於該等。反應溶劑之使用量相對於第1水解縮合物與四烷氧基矽烷[5]之總量較佳為0.1～1000質量%，尤佳為1～300質量%。再者於反應過程中自反應原料之烷氧基矽烷化合物生成之醇類可作為反應溶劑而發揮功能，故而有時並非必須添加。 於第2步驟中，所使用之強酸較佳為酸解離常數pKa為3以下之酸。具體可列舉：硝酸、硫酸、鹽酸、氫氟酸、三氟甲磺酸、對甲苯磺酸、三氟乙酸等。其中，因反應結束後之酸之去除處理較容易，故而較佳為硝酸、硫酸、鹽酸、氫氟酸，更佳為硝酸。 該強酸之使用量相對於第1水解縮聚物與四烷氧基矽烷[5]與反應溶劑之總量，較佳為0.0001～5質量%，尤佳為0.001～1質量%。 於第2步驟中，反應時間、反應溫度並無特別限定。反應時間通常為1～48小時。反應溫度通常為60～120℃，較佳為80～100℃。 反應後，可自反應系統內分離第2水解縮聚物並精製。該分離方法並無特別限定。作為分離方法，例如可列舉與上述第1步驟中列舉之分離方法相同之方法，可以與第1步驟相同之方式分離第2水解縮聚物並精製。 「第3步驟」 於第3步驟中，使第2水解縮聚物與上述通式[6]、[7]或[8]所表示之矽烷化合物於強酸條件下進行反應，獲得(A)成分。該第2水解縮聚物可於第2步驟中自反應系統分離而供於反應，亦可不自反應系統分離而直接供於反應。具體而言，將特定量之第2水解縮聚物、通式[6]所表示之矽烷化合物、通式[7]所表示之矽烷化合物或通式[8]所表示之矽烷化合物、根據所需之反應溶劑，於室溫下添加至反應容器內後，添加強酸作為用以進行縮合反應之觸媒，製為反應液。此時之投入順序並不限定於此，可以任意之順序投入而製為反應液，但較佳為觸媒於最後投入。繼而，一面攪拌該反應液一面以特定時間、特定溫度進行反應，藉此可獲得(A)成分。此時，為防止反應系統中之未反應原料、反應溶劑及/或觸媒餾出至反應系統外，較佳為於反應容器中具備回流裝置。 於第3步驟中，第2水解縮聚物、通式[6]所表示之矽烷化合物、通式[7]所表示之矽烷化合物或通式[8]所表示之矽烷化合物之使用量並無特別限定。就(A)成分之物性之觀點而言，較佳為相對於第2水解縮聚物1 g，於所使用之通式[6]所表示之矽烷化合物、通式[7]所表示之矽烷化合物、通式[8]所表示之矽烷化合物中之H-Si基之總量成為0.2～10 mmol之範圍內使用。 於第3步驟中所使用之強酸較佳為酸解離常數pKa為3以下之酸。具體可列舉：硝酸、硫酸、鹽酸、氫氟酸、三氟甲磺酸、對甲苯磺酸、三氟乙酸等。其中，因反應結束後之酸之去除處理較容易，故而較佳為硝酸、硫酸、鹽酸、氫氟酸，更佳為硝酸。強酸之使用量相對於第2水解縮聚物1 g，較佳為0.0001～10 mmol%，尤佳為0.005～5 mmol%。 於第3步驟中使用反應溶劑之情形時，作為其種類，若不阻礙用以獲得(A)成分之反應，則並無特別限定。第3步驟中所使用之反應溶劑可使用水溶性有機溶劑、非水溶性有機溶劑。藉由使用該等反應溶劑，可降低反應溶液之黏度。其中，較佳為水溶性有機溶劑。藉由使用水溶性有機溶劑，可降低反應溶液之黏度，並且可使第2水解縮聚物與第3步驟中使用之強酸於反應系統內均勻分散。作為水溶性有機溶劑之具體例，可列舉醇類等，更具體而言，可例示：甲醇、乙醇、正丙醇、異丙醇、丁醇等，但並不限定於該等。作為非水溶性有機溶劑之具體例，可列舉：芳香族烴類、醚類等，更具體而言，可例示：甲苯、二乙醚、四氫呋喃、二異丙醚等，但並不限定於該等。第3步驟中之反應溶劑之使用量相對於第2水解縮聚物1 g，較佳為超過0質量%且1000質量%以下，尤佳為50～500質量%。 於不將第2步驟中獲得之第2水解縮合物自反應系統分離而供於第3步驟之情形時，亦不特別限定是否使用該反應溶劑。於使用反應溶劑之情形時，相對於第2水解縮聚物1 g，與第2步驟中使用之反應溶劑之總量較佳為超過0質量%且1000質量%以下，尤佳為10～500質量%。 再者，第3步驟中反應溶劑之使用為任意，於不使用之情形時亦可獲得目標(A)成分。 於第3步驟中，使反應結束之方法並無特別限定。例如，可藉由於反應系統內添加水(較佳為離子交換水)而使反應結束。反應後，就(A)成分之處理性之觀點而言，較佳為自反應系統內分離(A)成分並精製。 該分離方法並無特別限定。例如可列舉萃取之方法，具體而言，自上述反應後之溶液分取有機層。繼而，以水(較佳為離子交換水)清洗該有機層，進而添加酸捕捉劑及乾燥劑，去除系統中溶解之酸與水。其後，經歷自有機層中去除酸捕捉劑與乾燥劑、非水溶性有機溶劑之減壓去除，藉此可將(A)成分以高純度分離。此時，亦可不使用乾燥劑，於去除非水溶性有機溶劑之過程中，同時將水去除。分離後之(A)成分較佳為藉由於無溶劑、減壓下加熱，而將(A)成分中所含之水分進而去除。此時加熱溫度並無特別限定，通常為100～190℃。 作為上述萃取溶劑，可使用非水溶性有機溶劑。該非溶水性有機溶劑之種類並無特別限定。例如可列舉：芳香族烴類、醚類等。具體可列舉：甲苯、二乙醚、異丙醚、二丁醚等，但並不限定於該等。 作為上述酸捕捉劑之種類，若可自系統中去除強酸，則並無特別限定。作為此種酸捕捉劑，可較佳使用固體酸捕捉劑。又，視需要可使用市售之酸捕捉劑。作為市售品，可列舉協和化學工業股份有限製造之Kyoword 500等，但不限定於此。 作為上述乾燥劑，若為可自系統中去除水者，則並無特別限定。作為此種乾燥劑，可較佳使用固體乾燥劑。具體可列舉硫酸鎂等，但並不限定於此。 ((B)成分之製造方法) 作為(B)成分之製造方法之一例，可藉由至少包含以下第4步驟之方法而製造(B)成分。 第4步驟：使第2水解縮聚物與下述通式[9]、[10]或[11]所表示之矽烷化合物於強酸條件下反應，藉此獲得(B)成分的步驟。 [化16] Vi-SiMe2
(OH) [9] Vi-SiMe2
(OR9
) [10] (Vi-SiMe2
)2
O [11] 式[10]中，R9
表示碳數1～3之烷基。 以下，對第4步驟進行說明。 「第4步驟」 於第4步驟中，使第2水解縮聚物與上述通式[9]、[10]或[11]所表示之矽烷化合物於強酸條件下進行反應，藉此獲得(B)成分。作為該第2水解縮聚物，可使用製造(A)成分時所獲得之第2水解縮聚物，亦可使用另外製備之第2水解縮聚物。 其反應條件、(B)成分之分離操作等可適用上述第3步驟之反應條件、分離操作等。即，可藉由將第3步驟中之通式[6]所表示之矽烷化合物、通式[7]所表示之矽烷化合物、通式[8]所表示之矽烷化合物、H-Si基、(A)成分分別置換為通式[9]所表示之矽烷化合物、通式[10]所表示之矽烷化合物、通式[11]所表示之矽烷化合物、Vi-Si基、(B)成分，而說明第4步驟。 [2.硬化性聚矽氧樹脂組合物之硬化物] 本發明之硬化性聚矽氧樹脂組合物之硬化物(以下，有時稱為「本發明之硬化物」)可將本發明之組合物加熱而獲得。 本發明之硬化物可用作半導體裝置用之密封材，其中較佳為用作光半導體裝置用、功率半導體裝置用之密封材。作為光半導體裝置用之密封材，可較佳用作LED用光學構件之密封材或半導體雷射用光學構件之密封材等，其中，尤佳為作為LED用光學構件之密封材。 通常，光半導體裝置藉由各種技術而提高其光提取效率，但若光半導體元件之密封材之透明度較低，則該密封材吸收光，使用其之光半導體裝置之光提取效率降低。其結果，存在難以獲得高亮度之光半導體裝置製品之傾向。進而，與光提取效率降低相當之能量轉化為熱，成為光半導體裝置之熱劣化之原因，故而欠佳。 本發明之硬化物之透明性優異。具體而言，本發明之硬化物於通常300 nm以上，較佳為350 nm以上，又通常900 nm以下，較佳為500 nm以下之區域之波長下具有良好之透光率。因此，若將本發明之硬化物作為上述密封材用在於該區域具有發光波長之光半導體裝置上，則可獲得高亮度之光半導體裝置，故而較佳。再者，將本發明之硬化物作為密封材用在於上述區域外具有發光波長之光半導體裝置上亦無妨。再者，上述透光率可藉由利用紫外/可見分光光度計之透過率測定而測定。 使本發明之組合物硬化之方法並無特別限定。例如，將本發明之組合物於欲使用之部位上藉由注入、滴下、流延、注模、自容器之擠出等方法，或藉由利用轉移成形或射出成形之一體成形，與如LED之密封對象物組合，通常於45～300℃，較佳為60～200℃下加熱，藉此使該組合物硬化而成為硬化物，從而可密封該密封對象物。若加熱溫度為45℃以上，則難以於所得硬化物中觀測到黏著性，若為300℃以下，則難以於所得硬化物中觀測到發泡，較實用。加熱時間並無特別限定。通常為0.5～12小時左右，較佳為1～10小時左右。若加熱時間為0.5小時以上，則硬化充分進行，但於LED密封用等要求精度之情形時，較佳為延長硬化時間。 [3.密封材] 本發明之硬化物可用作半導體裝置用之密封材，尤其較佳為用作光半導體裝置用、功率半導體裝置用等之密封材。包含本發明之硬化物之密封材如上所述透明性優異。又，與通常先前之加成硬化性聚矽氧樹脂組合物之硬化物相同，耐熱性、耐寒性、電絕緣性優異。 [4.光半導體裝置] 本發明之光半導體裝置係至少具備光半導體元件之光半導體裝置，藉由本發明之硬化物而至少密封該光半導體元件。本發明之光半導體裝置中之其他構成並無特別限定，亦可具備除光半導體元件外之構件。作為此種構件之一例，例如可列舉：基底基板、引出配線、導線配線、控制元件、絕緣基板、反射材、散熱片、導電構件、黏晶材、接合墊等。又，除光半導體元件外，構件之一部分或全部可經本發明之硬化物密封。 作為本發明之光半導體裝置，具體而言，可列舉：發光二極體(LED)裝置、半導體雷射裝置及光電耦合器等，但並不限定於該等。本發明之光半導體裝置例如可較佳用於液晶顯示器等之背光源、照明、各種感測器、印表機及影印機等之光源、車輛用計測器光源、信號燈、顯示燈、顯示裝置、面狀發光體之光源、顯示器、裝飾、各種燈以及開關元件等。 圖1表示本發明之光半導體裝置之一例。如圖1所例示，光半導體裝置10於光半導體基板6上至少具備密封材1、光半導體元件2及接合線3。光半導體基板6具有包括包含引線框架5之底面與包含反射材4之內周側面之凹部。 光半導體元件2係使用黏晶材(未圖示)而連接於引線框架5上。具備於光半導體元件2上之接合墊(未圖示)與引線框架5藉由接合線3而電性連接。反射材4具有使來自光半導體元件2之光於特定方向反射的作用。於光半導體基板6所具有之上述凹部之區域內，以至少密封光半導體元件2之方式填充密封材1。此時，亦可以亦密封接合線3之方式填充密封材1。密封材1包含本發明之硬化物。密封材1之內部可含有上述螢光體(未圖示)。藉由密封材1，可保護光半導體元件2不受濕氣、灰塵等之影響，維持長時間之可靠性。進而，藉由使密封材1亦密封接合線3，可同時防止因接合線3脫落、斷裂、短路而產生之電性不良影響。 本發明之硬化物如下所述，可用作半導體用接著劑。因此，亦可用作上述黏晶材等。 光半導體裝置10中，作為藉由包含本發明之硬化物之密封材1而密封之光半導體元件2，例如可列舉：LED、半導體雷射、光電二極體、光電晶體、太陽電池、CCD(charge couple device，電荷藕合元件)等。再者，圖1所示之結構僅為本發明之光半導體裝置之一例，反射材之結構、引線框架之結構、光半導體元件之安裝結構等可適宜變化。 圖1所表示之光半導體裝置10之製造方法並無特別限定。例如可列舉以下方法：於具備反射材4之引線框架5上黏接光半導體元件2，將該光半導體元件2與引線框架5藉由接合線3進行打線接合，繼而，於設置於光半導體元件之周圍之反射材之內側(包含引線框架與反射材之凹部)填充本發明之組合物後，於50～250℃下加熱，藉此使之硬化而成為密封材1。 [5.半導體裝置用接著劑] 本發明之組合物具有良好之密著性，故而可用作半導體裝置用接著劑。具體而言，例如，於接著半導體元件與封裝體之情形時、於接著半導體元件與子安裝基板之情形時、於接著封裝體構成元件彼此之情形時、於接著半導體裝置與外部光學構件之情形時等，可藉由塗佈、印刷、罐封等而使用本發明之組合物。 [實施例] 以下，藉由實施例具體說明本發明，但本發明不受該等實施例之限定。 1.原料之物性評價方法 [組成比之確定及HO-Si基之定量] 於聚矽氧樹脂200 mg中添加0.5 mL之氘氯仿並使之溶解，添加作為緩和劑之乙醯丙酮鉻(III)錯合物10 mg。以29
Si-NMR測定藉此製備之溶液。檢測出之訊號如表1所示，分類為波峰(a)～(k)，自總積分值之和以百分率(積分比)算出各個波峰。再者，聚矽氧樹脂之29
Si-NMR測定係使用共振頻率400 MHz之核磁共振裝置(日本電子股份有限公司製造，型號：JNM-AL400)。 [表1]
[化17] (H-SiMe2
O1/2
)a
(Me2
SiO2/2
)b
(PhSiO3/2
)c
(SiO4/2
)d
[1] 上述式[1]中之a、b、c、d之值可藉由自下式算出而確定： a＝(波峰(a)面積＋波峰(b)面積)/總波峰面積之和、 b＝(波峰(c)面積＋波峰(d)面積＋波峰(e)面積)/總波峰面積之和、 c＝(波峰(f)面積＋波峰(g)面積＋波峰(h)面積＋波峰(i)面積)/總波峰面積之和、 d＝波峰(j)面積/總波峰面積之和。 [化18] (Vi-SiMe2
O1/2
)e
(Me2
SiO2/2
)f
(PhSiO3/2
)g
(SiO4/2
)h
[2] 上述式[2]中之e、f、g、h之值可藉由自下式算出而確定： e＝(波峰(a)面積＋波峰(b)面積)/總波峰面積之和、 f＝(波峰(c)面積＋波峰(d)面積＋波峰(e)面積)/總波峰面積之和、 g＝(波峰(f)面積＋波峰(g)面積＋波峰(h)面積＋波峰(i)面積)/總波峰面積之和、 h＝波峰(k)面積/總波峰面積之和。 於29
Si-NMR中，Me-Si基、Ph-Si基、H-Si基、CH2
=CH-Si基(Vi-Si基)或其他基之波峰重疊之情形時，基於1
H-NMR中之Me-Si基、Ph-Si基、H-Si基、CH2
=CH-Si基或其他基之波峰之積分面積而算出。 HO-Si基之含量(mmol/g)可自藉由上述方法算出之積分比依據下式而確定： [A]＝波峰(a)積分比＋2×波峰(c)積分比＋波峰(d)積分比＋3×波峰(f)積分比＋2×波峰(g)積分比＋波峰(h)積分比、 [B]＝波峰(a)積分比×83.16＋波峰(b)積分比×74.15＋波峰(c)積分比×147.2＋波峰(d)積分比×138.2＋波峰(e)積分比×129.2＋波峰(f)積分比×87.92＋波峰(g)積分比×78.10＋波峰(h)積分比×69.09＋波峰(i)積分比×60.08＋波峰(j)積分比×67.16＋波峰(k)積分比×93.20、 HO-Si基之含量(mmol/g)＝([A]/[B])×1000。 [H-Si基及Vi-Si基之定量] 於6 mL之試樣管中稱量聚矽氧樹脂20～30 mg，添加0.8 mL之氘代二氯甲烷，使聚矽氧樹脂溶解。於該溶液中以微量注射器添加2.0 μL之二甲基亞碸(0.0282 mmol)，關閉試樣管，攪拌溶液使之均勻製為測定試料。以1
H-NMR測定該試料，算出二甲基亞碸之質子比與H-Si基或Vi-Si基之質子比，確定測定試料中之H-Si基或Vi-Si基之莫耳數。繼而，依據下式，算出測定試料1 g中之各官能基之含量： 聚矽氧樹脂中之官能基之莫耳數(mmol)/測定試料量(mg)×1000＝測定試料1 g中之官能基量(mmol/g)。 再者，聚矽氧樹脂之1
H-NMR測定係使用共振頻率400 MHz之核磁共振裝置(日本電子股份有限公司製造，型號：ECA-400)。聚矽氧樹脂中之各官能基之化學位移如下所示： Me-Si：0.0～0.5 ppm(3H)， H-Si：4.0～5.0 ppm(1H)， Vi-Si：5.5～6.5 ppm(3H)， Ph-Si：7.0～8.0 ppm(5H)。 [質量平均分子量(Mw)測定] 聚矽氧樹脂之質量平均分子量(Mw)係藉由下述條件之凝膠滲透層析法(簡稱：GPC)，以聚苯乙烯為基準物質製作校準曲線而算出值： 裝置：Tosoh股份有限公司製造，製品名：HLC-8320GPC， 管柱：Tosoh股份有限公司製造，製品名：TSK Gel Super HZ 2000×4，3000×2， 溶離液：四氫呋喃。 [折射率] 聚矽氧樹脂之折射率係使用折射率計(京都電子工業股份有限公司製造，型式：RA-600)而測定。 [黏度測定] 聚矽氧樹脂之黏度係依據JIS Z8803(2011)中之「藉由圓錐-板形旋轉黏度計之黏度測定方法」，使用旋轉黏度計(ANTON PAAR製造，商品名：PHYSICA MCR51，測定範圍200～1,000,000 cP)與溫度控制單元(ANTON PAAR製造，商品名：P-PTD200)，於標準狀態(25℃，1個大氣壓)下以剪切速度30[1/s]進行測定，採用自測定開始經過1分鐘後所得值。於未達測定範圍之低黏度之情形記為「＜200」。 [透明性] 使用紫外可見分光光度計(島津製作所股份有限公司製造，型號：UV-3150)，測定405 nm、365 nm之波長區域之樹脂之透過率。測定單元係使用石英製造，單元之厚度為1 cm。 2.原料合成例及比較合成例 [原料合成例1-1]聚矽氧樹脂(I)之合成 於具備氟樹脂製之攪拌翼、戴氏回流器之體積10 L之玻璃反應容器中，採取961.6 g(8.0 mol)之Me2
Si(OMe)2
、1586.4 g(8.0 mol)之PhSi(OMe)3
。繼而，於反應容器中添加1440 g之水及0.96 g之乙酸，將反應容器內於75℃下連續加溫6小時，進行水解及縮合反應。其後，將反應液返回至室溫，僅去除水層。於殘留有機層之反應容器中添加3520 g之甲苯及1440 g之水，進行分液操作後，去除水層。繼而藉由1440 g之水進行4次有機層之清洗操作。其後，回收有機層，藉由蒸發器，減壓餾去甲苯，獲得作為無色黏性液體之聚矽氧樹脂(I)。 聚矽氧樹脂(I)之產量為1388.0 g，質量平均分子量(Mw)為900，組成比為(Me2
SiO2/2
)0.49
(PhSiO3/2
)0.51
，HO-Si基之含量為7.2 mmol/g(12質量%)。 [原料合成例1-2]聚矽氧樹脂(A1)之合成 於100 mL燒瓶中採取20.00 g之聚矽氧樹脂(I)、14.96 g之Si(OEt)4
。繼而添加8.74 g之2-丙醇，添加1.84 μL之70%濃硝酸，於100℃下進行攪拌。6小時後，將燒瓶內溫度設為室溫，添加4.82 g之1,1,3,3-四甲基二矽氧烷及0.12 mL之70%濃硝酸，於室溫下攪拌。17小時後，將反應溶液轉移至分液漏斗，添加50 mL之甲苯、80 mL之水，進行萃取操作後，回收有機層。進而，添加80 mL之水及20 mL之2-丙醇，進行萃取操作，回收有機層。將該同樣之操作反覆3次，藉此清洗有機層。於該有機層中添加1 g之酸捕捉劑(協和化學工業股份有限公司製造，製品名：Kyoword 500)加以攪拌，1小時後藉由氟樹脂製之濾紙(PORE SIZE(孔隙尺寸)：1 μm)過濾。對濾液藉由蒸發器自有機相去除甲苯後，進行藉由150℃、1小時之加熱之減壓餾去，進而進行2次藉由170℃、1小時之加熱之減壓餾去，獲得作為無色透明之黏性液體之聚矽氧樹脂(A1)。 聚矽氧樹脂(A1)之產量為28.58 g，質量平均分子量(Mw)為1400，黏度未達200 cP，組成比為(H-SiMe2
O1/2
)0.18
(Me2
SiO2/2
)0.32
(PhSiO3/2
)0.43
(SiO4/2
)0.07
，H-Si基之含量為1.36 mmol/g，HO-Si基之含量為4.8 mmol/g(8.2質量%)。 [原料合成例1-3]聚矽氧樹脂(B1)之合成 於100 mL燒瓶中採取20.00 g之聚矽氧樹脂(I)、14.96 g之Si(OEt)4
。繼而添加8.74 g之2-丙醇，添加1.84 μL之70%濃硝酸，於100℃下進行攪拌。6小時後，將燒瓶內溫度設為室溫，添加6.69 g之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷及2.30 mL之70%濃硝酸，於室溫下攪拌。15小時後，將反應溶液轉移至分液漏斗，添加80 mL之甲苯、50 mL之水及40 mL之2-丙醇，進行萃取操作後，回收有機層。進而，添加80 mL之水及20 mL之2-丙醇，進行萃取操作，回收有機層。將該同樣之操作反覆3次，藉此清洗有機層。其後，於該有機層中添加1 g之酸捕捉劑(協和化學工業股份有限公司製造，製品名：Kyoword 500)加以攪拌，1小時後藉由氟樹脂製之濾紙(PORE SIZE：1 μm)過濾。對濾液藉由蒸發器自有機相去除甲苯後，進行藉由150℃、1小時之加熱之減壓餾去，進而進行2次藉由170℃、1小時之加熱之減壓餾去，獲得作為無色透明之黏性液體之聚矽氧樹脂(B1)。 聚矽氧樹脂(B1)之產量為29.67 g，質量平均分子量(Mw)為2000，黏度為410 cP，組成比為(Vi-SiMe2
O1/2
)0.25
(Me2
SiO2/2
)0.25
(PhSiO3/2
)0.32
(SiO4/2
)0.18
，Vi-Si基之含量為2.23 mmol/g，HO-Si基之含量為3.1 mmol/g(5.3質量%)。 [原料合成例2-1]聚矽氧樹脂(II)之合成 於300 mL燒瓶中採取100.00 g之聚矽氧樹脂(I)、74.78 g之Si(OEt)4
。繼而添加43.69 g之2-丙醇，添加9.21 μL之70%濃硝酸，於100℃下進行攪拌。6小時後，將反應溶液轉移至分液漏斗，添加100 mL之甲苯、200 mL之水及50 mL之2-丙醇，進行萃取操作後，回收有機層。進而添加200 mL之水及100 mL之2-丙醇，進行萃取操作，回收有機層。再次重複該同樣之操作，藉此清洗有機層。其後，藉由蒸發器自有機相去除甲苯，獲得作為無色透明之黏性液體之聚矽氧樹脂(II)。 聚矽氧樹脂(II)之產量為132.01 g，質量平均分子量(Mw)為1600，黏度未達200 cP，組成比為(Me2
SiO2/2
)0.40
(PhSiO3/2
)0.51
(SiO4/2
)0.09
，HO-Si基之含量為7.36 mmol/g(13質量%)。 [原料合成例2-2]聚矽氧樹脂(A2)之合成 將20.00 g之聚矽氧樹脂(II)、60.00 g之甲苯、20.00 g之甲醇、4.94 g之1,1,3,3-四甲基二矽氧烷及0.12 mL之70%濃硝酸添加至燒瓶內，於室溫下進行攪拌。4小時後，將反應溶液轉移至分液漏斗，添加60 g之水，進行萃取操作後，回收有機層。重複4次同樣之操作，藉此清洗有機層。藉由蒸發器自有機層餾去甲苯後，進行藉由150℃、1小時之加熱之減壓餾去後，進行2次藉由170℃、1小時之加熱之減壓餾去，獲得作為無色透明之黏性液體之聚矽氧樹脂(A2)。 聚矽氧樹脂(A2)之產量為16.05 g，質量平均分子量(Mw)為1500，黏度未達200 cP，組成比為(H-SiMe2
O1/2
)0.24
(Me2
SiO2/2
)0.30
(PhSiO3/2
)0.45
(SiO4/2
)0.01
，H-Si基之含量為2.19 mmol/g，HO-Si基之含量為2.9 mmol/g(4.9質量%)。 [原料合成例2-3]聚矽氧樹脂(B2)之合成 將20.00 g之聚矽氧樹脂(II)、60.00 g之甲苯、20.00 g之甲醇、6.86 g之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷及2.36 mL之70%濃硝酸添加至燒瓶內，於室溫下進行攪拌。4小時後，將反應溶液轉移至分液漏斗，添加60 g之水，進行萃取操作後，回收有機層。重複4次同樣之操作，藉此清洗有機層。藉由蒸發器自有機層餾去甲苯後，進行藉由150℃、1小時之加熱之減壓餾去後，進行2次藉由170℃、1小時之加熱之減壓餾去，獲得作為無色透明之黏性液體之聚矽氧樹脂(B2)。 聚矽氧樹脂(B2)之產量為19.38 g，質量平均分子量(Mw)為1500，黏度為210 cP，組成比為(Vi-SiMe2
O1/2
)0.32
(Me2
SiO2/2
)0.25
(PhSiO3/2
)0.33
(SiO4/2
)0.10
，Vi-Si基之含量為2.19 mmol/g，HO-Si基之含量為3.2 mmol/g(3.0質量%)。 [比較合成例1] 於具備氟樹脂製之攪拌翼、戴氏回流器之體積2 L之3口燒瓶中採取96.16 g(0.80 mol)之Me2
Si(OMe)2
、158.64 g(0.80 mol)之PhSi(OMe)3
。繼而，將180.15 g之水及0.12 g之乙酸添加至該燒瓶內，將該燒瓶內於100℃下連續加溫6小時，進行水解及縮合反應。其後，將反應液返回至室溫，將52.08 g之Si(OEt)4
添加至該燒瓶內，將該燒瓶內於100℃下連續加溫6小時，進行水解及縮合反應。 其結果，獲得白色固體，但未獲得具有(Me2
SiO2/2
)所表示之結構單元、(PhSiO3/2
)所表示之結構單元及(SiO4/2
)所表示之結構單元之目標聚矽氧樹脂。 [比較合成例2] 於具備氟樹脂製之攪拌翼、戴氏回流器之體積200 mL之燒瓶中採取20.00 g聚矽氧樹脂(I)。繼而，將7.64 g之Si(OEt)4
、5.29 g之11 mmol/L乙酸水溶液添加至該燒瓶內，將該燒瓶內於100℃下連續加溫6小時，進行水解及縮合反應。 其結果，獲得白色固體及凝膠狀物質，但未獲得具有(Me2
SiO2/2
)所表示之結構單元、(PhSiO3/2
)所表示之結構單元及(SiO4/2
)所表示之結構單元之目標聚矽氧樹脂。 [比較合成例3] 除使用3.4 μL之乙酸代替乙酸水溶液以外，藉由與比較合成例2相同之方法，進行水解及縮合反應。 其結果，於燒瓶內獲得白色固體，但未獲得具有(Me2
SiO2/2
)所表示之結構單元、(PhSiO3/2
)所表示之結構單元及(SiO4/2
)所表示之結構單元之目標聚矽氧樹脂。 [比較合成例4] 除使用3.4 μL之乙酸、7.06 g之2-丙醇代替乙酸水溶液以外，藉由與比較合成例2相同之方法，進行水解及縮合反應。 其後，將反應液轉移至分液漏斗，添加50 mL之甲苯與50 mL之水，進行萃取操作後，回收有機層。繼而藉由50 mL之水進行2次有機層之清洗操作。藉由蒸發器自有機層餾去甲苯。 其結果，獲得作為無色透明之液體之聚矽氧樹脂，但未獲得具有(Me2
SiO2/2
)所表示之結構單元、(PhSiO3/2
)所表示之結構單元及(SiO4/2
)所表示之結構單元之目標聚矽氧樹脂。 [比較合成例5-1]聚矽氧樹脂(PI)之合成 除96.16 g(0.8 mol)之Me2
Si(OMe)2
及158.64 g(0.8 mol)之PhSi(OMe)3
外，進而採取52.08 g(0.25 mol)之Si(OEt)4
，除此之外藉由與比較合成例1相同之方法，進行水解及縮合反應。 其後，將反應液返回至室溫，轉移至2 L之分液漏斗，添加400 mL之甲苯及400 mL之水，進行分液操作後，去除水層。繼而藉由400 mL之水進行2次有機層之清洗操作。其後，回收有機層，藉由蒸發器，減壓餾去甲苯。 其結果，獲得作為無色之黏性液體之聚矽氧樹脂(PI)。聚矽氧樹脂(PI)之產量為288.82 g，質量平均分子量(Mw)為1200，組成比為(Me2
SiO2/2
)0.36
(PhSiO3/2
)0.48
(SiO4/2
)0.16
，HO-Si基之含量為8.4 mmol/g(14質量%)。 [比較合成例5-2]聚矽氧樹脂(PA1)之合成 除使用179.22 g之聚矽氧樹脂(PI)、537.66 g之甲苯、179.22 g之甲醇、35.30 g之1,1,3,3-四甲基二矽氧烷及0.84 mL之70%濃硝酸代替20.00 g之聚矽氧樹脂(II)、60.00 g之甲苯、20.00 g之甲醇、4.94 g之1,1,3,3-四甲基二矽氧烷及0.12 mL之70%濃硝酸以外，藉由與原料合成例2-2相同之方法，進行反應。其後，除使用540 g之水代替60 g之水以外，進行與原料合成例2-2相同之操作。其結果，獲得作為無色透明之黏性液體之聚矽氧樹脂(PA1)。 聚矽氧樹脂(PA1)之產量為159.76 g，質量平均分子量(Mw)為2400，黏度為42000 cP，組成比為(H-SiMe2
O1/2
)0.23
(Me2
SiO2/2
)0.14
(PhSiO3/2
)0.52
(SiO4/2
)0.11
，H-Si基之含量為2.1 mmol/g，HO-Si基之含量為3.2 mmol/g(6質量%)。 [比較合成例5-3]聚矽氧樹脂(PB1)之合成 除使用89.61 g之聚矽氧樹脂(PI)、268.83 g之甲苯、89.61 g之甲醇、24.56 g之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷及24.50 mL之70%濃硝酸代替20.00 g之聚矽氧樹脂(II)、60.00 g之甲苯、20.00 g之甲醇、6.86 g之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷及2.36 mL之70%濃硝酸以外，藉由與原料合成例2-3相同之方法，進行反應。其後，除使用270 g之水代替60 g之水以外，進行與原料合成例2-3相同之操作。其結果，獲得作為無色透明之黏性液體之聚矽氧樹脂(PB1)。 聚矽氧樹脂(PB1)之產量為92.52 g，質量平均分子量(Mw)為1700，黏度為11000 cP，組成比為(Vi-SiMe2
O1/2
)0.22
(Me2
SiO2/2
)0.21
(PhSiO3/2
)0.44
(SiO4/2
)0.13
，Vi-Si基之含量為2.0 mmol/g，HO-Si基之含量為2.1 mmol/g(4質量%)。 [比較合成例6-1]聚矽氧樹脂(QI)之合成 除將水及乙酸添加至燒瓶內時，進而添加239.6 g之2-丙醇以外，藉由與比較合成例5相同之方法，進行水解及縮合反應。其後，進行與比較合成例5相同之操作，結果獲得作為無色之黏性液體之聚矽氧樹脂(QI)。 聚矽氧樹脂(QI)之產量為143.4 g，質量平均分子量(Mw)為1,100，組成比為(Me2
SiO2/2
)0.36
(PhSiO3/2
)0.50
(SiO4/2
)0.14
，HO-Si基之含量為7.9 mmol/g(14質量%)。 [比較合成例6-2]聚矽氧樹脂(QA1)之合成 除使用173.7 g之聚矽氧樹脂(QI)、521.1 g之甲苯、173.7 g之甲醇、32.3 g之1,1,3,3-四甲基二矽氧烷及0.77 mL之70%濃硝酸代替20.00 g之聚矽氧樹脂(II)、60.00 g之甲苯、20.00 g之甲醇、4.94 g之1,1,3,3-四甲基二矽氧烷及0.12 mL之70%濃硝酸以外，藉由與原料合成例2-2相同之方法，進行反應。其後，除使用521.1 g之水代替60 g之水以外，進行與原料合成例2-2相同之操作。其結果，獲得作為無色透明之黏性液體之聚矽氧樹脂(QA1)。 聚矽氧樹脂(QA1)之產量為165.7 g，質量平均分子量(Mw)為3300，黏度為94000 cP，組成比為(H-SiMe2
O1/2
)0.24
(Me2
SiO2/2
)0.15
(PhSiO3/2
)0.48
(SiO4/2
)0.13
，H-Si基之含量為2.3 mmol/g，HO-Si基之含量為3.1 mmol/g(5質量%)。 [比較合成例6-3]聚矽氧樹脂(QB1)之合成 除使用91.4 g之聚矽氧樹脂(QI)、274.2 g之甲苯、91.4 g之甲醇、23.6 g之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷及8.10 mL之70%濃硝酸代替20.00 g之聚矽氧樹脂(II)、60.00 g之甲苯、20.00 g之甲醇、6.86 g之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷及2.36 mL之70%濃硝酸以外，藉由與原料合成例2-3相同之方法，進行反應。其後，除使用274.2 g之水代替60 g之水以外，進行與原料合成例2-3相同之操作。其結果，獲得作為無色透明之黏性液體之聚矽氧樹脂(QB1)。 聚矽氧樹脂(QB1)之產量為99.2 g，質量平均分子量(Mw)為1900，黏度為9600 cP，組成比為(Vi-SiMe2
O1/2
)0.23
(Me2
SiO2/2
)0.19
(PhSiO3/2
)0.43
(SiO4/2
)0.15
，Vi-Si基之含量為2.2 mmol/g，HO-Si基之含量為1.7 mmol/g(3質量%)。 [比較合成例7-2]聚矽氧樹脂(RA1)之合成 除使用39.7 g之聚矽氧樹脂(I)、119 g之甲苯、39.7 g之甲醇、8.3 g之1,1,3,3-四甲基二矽氧烷及0.20 mL之70%濃硝酸代替20.00 g之聚矽氧樹脂(II)、60.00 g之甲苯、20.00 g之甲醇、4.94 g之1,1,3,3-四甲基二矽氧烷及0.12 mL之70%濃硝酸以外，藉由與原料合成例2-2相同之方法，進行反應。其後，除使用119 g之水代替60 g之水以外，進行與原料合成例2-2相同之操作。其結果，獲得作為無色透明之黏性液體之聚矽氧樹脂(RA1)。 聚矽氧樹脂(RA1)之產量為42.5 g，質量平均分子量(Mw)為1900，黏度為200 cP，組成比為(H-SiMe2
O1/2
)0.27
(Me2
SiO2/2
)0.31
(PhSiO3/2
)0.42
，H-Si基之含量為2.8 mmol/g，HO-Si基之含量為2.0 mmol/g(3.4質量%)。 [比較合成例7-3]聚矽氧樹脂(RB1)之合成 除使用19.9 g之聚矽氧樹脂(I)、59.7 g之甲苯、19.9 g之甲醇、5.76 g之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷及1.98 mL之70%濃硝酸代替20.00 g之聚矽氧樹脂(II)、60.00 g之甲苯、20.00 g之甲醇、6.86 g之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷及2.36 mL之70%濃硝酸以外，藉由與原料合成例2-3相同之方法，進行反應。其後，除使用59.7 g之水代替60 g之水以外，進行與原料合成例2-3相同之操作。其結果，獲得作為無色透明之黏性液體之聚矽氧樹脂(RB1)。 聚矽氧樹脂(RB1)之產量為20.6 g，質量平均分子量(Mw)為1800，黏度為350 cP，組成比為(Vi-SiMe2
O1/2
)0.23
(Me2
SiO2/2
)0.32
(PhSiO3/2
)0.45
，Vi-Si基之含量為2.3 mmol/g，HO-Si基之含量為2.1 mmol/g(3.6質量%)。 關於合成之聚矽氧樹脂(A1)、(B1)、(A2)、(B2)、(PA1)、(PB1)、(QA1)、(QB1)、(RA1)、(RB1)，將組成比及各物性值(HO-Si基之含量、H-Si基或Vi-Si基之含量、質量平均分子量、黏度、折射率、透明性)示於表2。 [表2]
如表2所示，原料合成例中獲得之聚矽氧樹脂(A1)、(B1)、(A2)、(B2)與比較合成例中獲得之聚矽氧樹脂(PA1)、(PB1)、(QA1)、(QB1)比較，均顯示極低之黏性。又，與比較合成例中獲得之作為不具有(SiO4/2
)所表示之結構單元之聚矽氧樹脂之聚矽氧樹脂(RA1)、(RB1)比較，亦顯示同等程度或較低之黏性。 原料合成例中獲得之聚矽氧樹脂(A1)、(B1)、(A2)、(B2)均具有(SiO4/2
)所表示之結構單元，故而與不具有(SiO4/2
)所表示之結構單元之聚矽氧樹脂相比，交聯密度變高。如此，雖然通常交聯密度變得越高，黏性變得越高，但聚矽氧樹脂(A1)、(B1)、(A2)、(B2)均顯示低黏性。 又，如比較合成例1～4所示，於作為用以水解縮聚之觸媒使用乙酸之情形時、使用乙酸水溶液之情形時、或使用乙酸與作為溶劑之2-丙醇之情形時，均無法合成具有(Me2
SiO2/2
)所表示之結構單元、(PhSiO3/2
)所表示之結構單元及(SiO4/2
)所表示之結構單元之目標聚矽氧樹脂。 另一方面，如原料合成例所示，於使用如硝酸之強酸性觸媒之情形時，可合成至少具有(Me2
SiO2/2
)所表示之結構單元、(PhSiO3/2
)所表示之結構單元及(SiO4/2
)所表示之結構單元之目標聚矽氧樹脂。 3.硬化性聚矽氧樹脂組合物之製備 於下述實施例1～2、比較例1～3中，將選自由聚矽氧樹脂(A1)、(A2)、(PA1)、(QA1)及(RA1)所組成之群中之一種作為(A)成分，將選自由聚矽氧樹脂(B1)、(B2)、(PB1)、(QB1)及(RB1)所組成之群中之一種作為(B)成分，將(A)成分與(B)成分以(A)成分之質量：(B)成分之質量＝2：1之方式進行調配，進而，與作為(C)成分之鉑觸媒混合，製備組合物1～5。 此處，作為鉑觸媒，以相對於組合物總量，鉑原子之含量以質量單位計成為0.03 ppm之方式使用鉑-二乙烯基四甲基二矽氧烷錯合物。製備之組合物1～5之各組成示於表3。 4.組合物及其硬化物之物性評價方法 以如下方法測定製備之組合物之黏度、HO-Si基含量、自該組合物獲得之硬化物之物理特性(硬度、密著性、透明性、線熱膨脹係數、接著強度)、硬化時之外觀及衝壓成形性。 [組合物之黏度] 製備之組合物之黏度係依據JIS Z8803(2011)中之「藉由圓錐-板形旋轉黏度計之黏度測定方法」，使用旋轉黏度計(ANTON PAAR製造，商品名：PHYSICA MCR51，測定範圍200～1,000,000 cP)與溫度控制單元(ANTON PAAR製造，商品名：P-PTD200)，於標準狀態(25℃，1個大氣壓)下以剪切速度30[1/s]進行測定，採用自測定開始經過1分鐘後所得值。未達測定範圍之低黏度液體時記為「＜200」。 [組合物之HO-Si基含量] 藉由下述計算式，算出製備之組合物之HO-Si基含量。 [組合物之HO-Si基含量]＝｛((A)成分之HO-Si基含量)×2＋((B)成分之HO-Si基含量)｝/2 [硬化物之硬度] 將製備之組合物流入模具(25 mm)，於空氣中於90℃下加熱1小時，進而於150℃下加熱4小時，製作厚4～5 mm之硬化物。使用硬度計(Durometer)(Teclock股份有限公司製造，型號：GS-719R、GS-720R)，藉由JIS K 7215「塑膠之硬度計硬度試驗方法」中規定之方法，測定該硬化物之蕭氏A或蕭氏D之硬度。 [硬化物之密著性試驗(SMD3528型PPA樹脂封裝體)] 將製備之組合物流入SMD3528型PPA樹脂封裝體(表面安裝零件3528型聚鄰苯二甲醯胺樹脂封裝體)(3.5 mm×2.8 mm×0.9 mm)，於空氣中於90℃下加熱1小時，進而於150℃下加熱4小時，製作24個作為硬化物之檢體。以光學顯微鏡(光學倍率：3倍～30倍)確認該等檢體，將硬化物自封裝體剝離者評價為「剝離」，將未剝離者評價為「密著」。24個檢體中，計入評價為「密著」之檢體之個數作為「合格數」。 [硬化物之密著性試驗(SMD6050型PPA樹脂封裝體)] 將製備之組合物流入SMD6050型PPA樹脂封裝體(6.0 mm×5.0 mm×2.0 mm)，於空氣中於90℃下加熱1小時，進而於150℃下加熱4小時，製作12個作為硬化物之檢體。以光學顯微鏡(光學倍率：3倍～30倍)確認該等檢體，將硬化物自封裝體剝離者評價為「剝離」，將未剝離者評價為「密著」。12個檢體中，計入評價為「密著」之檢體之個數作為「合格數」。 [硬化物之透明性] 將製備之組合物流入模具(22 mm)，於空氣中於90℃下加熱1小時，進而於150℃下加熱4小時，製作22 mm、2 mm厚之硬化物。使用紫外可見分光光度計(島津製作所股份有限公司製造，型號：UV-3150)，測定該硬化物之405 nm、365 nm波長區域之透過率。 [硬化物之耐熱透明性] 將製備之組合物流入模具(22 mm)，於空氣中於90℃下加熱1小時，進而於150℃下加熱4小時，製作22 mm、2 mm厚之硬化物。將該硬化物於200℃下加熱100小時後，使用紫外可見分光光度計(島津製作所股份有限公司製造，型號：UV-3150)，測定該硬化物之405 nm、365 nm波長區域之透過率。 [硬化物之線熱膨脹係數] 將製備之組合物0.7 g添加至氟樹脂製管體(內徑：5.8 mm，高：1.8 mm)中，於空氣中於90℃下加熱1小時，進而於150℃下加熱4小時製作硬化物。使用ThermoPlusTMA8310(RIGAKU股份有限公司製造)，將該硬化物於空氣中，以5℃/分鐘之升溫速度自25℃加熱至200℃，測定線熱膨脹係數。該測定進行2次，測定值採用第二次者。 [硬化物之接著強度] 將製備之組合物與直徑50 μm之氧化鋯球混合者，於加持於玻璃片(5.0 mm×5.0 mm×1.1 mm)與玻璃基板(50 mm×50 mm×3.0 mm)之間之狀態下，於空氣中於90℃下加熱1小時，進而於150℃下加熱4小時使之硬化。藉由黏合力測試機(DAGE JAPAN股份有限公司製造，型號：Dage4000Plus)測定製作之試料之接著力(接著強度)。將硬化物之強度較弱，測定時硬化物遭破壞而無法獲得接著強度之值者記為「凝集破壞」。 [硬化物之外觀] 將製備之組合物1 g展開於玻璃模具(22 mm)上，於空氣中於90℃下加熱1小時，進而於150℃下加熱4小時，製作22 mm、2 mm厚之硬化物。製作3個試驗體，目視確認試驗體之外觀，於所有試驗體中，將硬化物中未觀測到發泡及裂痕之產生之狀態評為「良好」。將其以外之情形評為「不良」。 [衝壓成形性試驗] 將製備之組合物流入模具(90 mm×90 mm×2 mm)，於空氣中於90℃下加熱1小時，進而於150℃下加熱4小時，製作板狀硬化物。依據JIS K6251將該板狀硬化物衝壓成形為啞鈴狀8號形。將硬化體之衝壓時未發生龜裂或樹脂缺漏而可衝壓成形者評價為「良好」。將其以外之情形評價為「不良」。 5.實施例及比較例 [實施例1～2、比較例1～3] 使用製備之組合物1～2，進行上述物性評價試驗(實施例1～2)。同樣地，使用製備之組合物3～5，進行上述物性評價試驗(比較例1～3)。該等結果示於表3。 [表3]
如表3所示，實施例1～2中製備之組合物1～2與比較例1～2中製備之組合物3～4相比較，均具有極低之黏度。進而，自組合物1～2獲得之硬化物顯示良好之外觀、衝壓成形性，於密著性、透明性方面具有同等之物性。又，與自如比較例3之低黏度之組合物5獲得之硬化物相比較，於密著性及樹脂強度方面具有優異之物性。 以上內容表示，屬於本發明之範疇之實施例1～2中製備之組合物1～2具有極低之黏性，其硬化物具有良好之物性。Hereinafter, the present invention will be described in further detail, but the present invention is not limited thereto. [1. Curable Polyxene Oxide Resin Composition] The curable polyoxyxylene resin composition of the present invention (hereinafter sometimes referred to as "the composition of the present invention") contains at least components (A) to (C). Hereinafter, each component contained in the composition of the present invention will be described. <(A) component> The component (A) is a polyoxyxylene resin represented by the following formula [1] and having a viscosity of 10,000 cP or less. [化8] (H-SiMe 2 O 1/2 ) a (Me 2 SiO 2/2 ) b (PhSiO 3/2 ) c (SiO 4/2 ) d [1] In the above formula [1], a, b, c, and d are each a number exceeding 0 and not reaching 1, and satisfying a+b+c+d=1. (H-SiMe 2 O 1/2 ), (Me 2 SiO 2/2 ), (PhSiO 3/2 ) and (SiO 4/2 The oxygen atom in the structural unit represented represents an oxygen atom forming a siloxane chain or an oxygen atom forming a stanol group, respectively. In the formula [1], the value of a, the value of b, the value of c, and the value of d are each not more than 0 and not within the range of 1 and satisfy a+b+c+d=1, and are not particularly limited. The value of a is preferably from 0.05 to 0.40, preferably from 0.10 to 0.30. The value of b is preferably from 0.10 to 0.80, and more preferably from 0.10 to 0.40. The value of c is preferably from 0.10 to 0.80, and more preferably from 0.30 to 0.60. The value of d is preferably 0.0005 to 0.40, and particularly preferably 0.005 to 0.30. When the values of a and b, c, and d are in the above range, the composition and the cured body of the present invention have good moldability and good mechanical strength. Further, the value of a, the value of b, the value of c, and the value of d are measured by a nuclear magnetic resonance apparatus using a polyoxygen compound represented by the formula [1]. 29 Si-NMR spectra and 1 H-NMR spectrum was calculated using these. In [1], (Me 2 SiO 2/2 The structural unit represented by the structure may include a structure represented by the following formula [1-2], that is, (Me 2 SiO 2/2 A structure in which one of the oxygen atoms bonded to the germanium atom in the structural unit represented forms a stanol group. [Chemistry 9] Me 2 Si(OH)O 1/2 [1-2] (Me 2 SiO 2/2 The structural unit represented by the structure unit includes a portion surrounded by a broken line of the structural unit represented by the following formula [1-b], and may further include a dotted line surrounded by the structural unit represented by the following formula [1-2-b] Part of it. That is, a structural unit having a group (methyl) represented by Me and having a hydroxyl group at the terminal and forming a stanol group with a ruthenium atom is also included in (Me 2 SiO 2/2 ) in the structural unit represented. Further, in the structural unit represented by the following formulas [1-b] and [1-2-b], the oxygen atom in the Si-O-Si bond forms a decane bond with the adjacent ruthenium atom, and the adjacent structure The unit shares an oxygen atom. Therefore, one of the Si-O-Si bonds is set to "O" 1/2 "." [化10] In the formula [1], (PhSiO 3/2 The structural unit represented by the formula [1-2] or the structure represented by the formula [1-3], that is, (PhSiO) 3/2 a structure in which two oxygen atoms bonded to a ruthenium atom in a structural unit are respectively formed to form a stanol group, or (PhSiO 3/2 A structure in which one of the oxygen atoms bonded to the germanium atom in the structural unit represented forms a stanol group. [Chemistry 11] (PhSi(OH) 2 O 1/2 ) [1-3] (PhSi(OH)O 2/2 ) [1-4] In the formula [1], (PhSiO 3/2 The structural unit represented by the structure includes a portion surrounded by a broken line of the structural unit represented by the following formula [1-c], and may further include the following formula [1-3-c] or [1-4-c] The portion enclosed by the dotted line of the structural unit. That is, a structural unit having a group represented by Ph (phenyl group) and having a terminal hydroxyl group at the terminal and forming a stanol group with a ruthenium atom is also contained in (PhSiO). 3/2 ) in the structural unit represented. [化12] In the formula [1], (SiO 4/2 The structural unit represented by the structure includes a portion surrounded by a broken line of the structural unit represented by the following formula [1-d], and may further include the following formula [1-5-d], [1-6-d] or The portion surrounded by the broken line of the structural unit represented by [1-7-d]. That is, a structural unit in which a terminal hydroxyl group is left and a decyl alcohol group is formed with a ruthenium atom is also contained in (SiO 4/2 ) in the structural unit represented. [Chemistry 13] The viscosity of the component (A) is not particularly limited as long as it is 10,000 cP (centipoise) or less in a standard state (25 ° C, 1 atm). From the viewpoint of handling workability, it is preferably 7,000 cP or less. The lower limit is not particularly limited, and the lower the viscosity, the lower the viscosity of the obtained composition of the present invention, and the easier the sealing operation of the semiconductor device, which is preferable. The viscosity of the component (A) may be more than 0 cP and less than 10,000 cP in a standard state (25 ° C, 1 atm), preferably more than 0 cP and 7,000 or less. Here, the viscosity of the component (A) is measured by a rotary viscometer or the like. Specifically, according to JIS Z8803 (2011) "Viscosity measurement method by a cone-plate-shaped rotational viscometer", a rotational viscometer (manufactured by ANTON PAAR, trade name: PHYSICA MCR51, measurement range 200 to 1,000,000 cP) is used. With a temperature control unit (manufactured by ANTON PAAR, trade name: P-PTD200), the measurement was performed at a shear rate of 30 [1/s] in a standard state (25 ° C, 1 atm), and 1 minute after the start of the measurement. The obtained value is used as the viscosity of the component (A). The component (A) contains at least a hydrogen atom (H-Si group) bonded to a ruthenium atom, and the amount thereof is not particularly limited. It is preferred to contain two or more in one molecule. It is particularly preferably from 0.5 to 4.0 mmol/g in terms of obtaining a good cured product. The mass average molecular weight of the component (A) is not particularly limited. It is preferably 500 to 10,000, and more preferably 800 to 7,000. When the mass average molecular weight is 500 or more, the cured product of the present invention has good resin strength, and if it is 10,000 or less, the composition of the present invention has good formability. Here, the mass average molecular weight is measured by gel permeation chromatography (abbreviation: GPC), and is converted from a standard polystyrene calibration curve (the same applies to the present specification). The amount of the HO-Si group contained in the component (A) is not particularly limited. It is preferably from 0.5 to 4.5 mmol/g, particularly preferably from 1.0 to 3.5 mmol/g. When the content of the HO-Si group exceeds 4.5 mmol/g, bubbles are sometimes observed in the cured product. <Component (B)> The component (B) is a polyoxyxylene resin represented by the following formula [2] and having a viscosity of 10,000 cP or less. [Vi 14] (Vi-SiMe 2 O 1/2 ) e (Me 2 SiO 2/2 ) f (PhSiO 3/2 ) g (SiO 4/2 ) h [2] In the above formula [2], e, f, g, and h are each a number exceeding 0 and not reaching 1, and satisfying e+f+g+h=1. (Vi-SiMe 2 O 1/2 ), (Me 2 SiO 2/2 ), (PhSiO 3/2 ) and (SiO 4/2 The oxygen atom in the structural unit represented represents an oxygen atom forming a siloxane chain or an oxygen atom forming a stanol group, respectively. In the formula [2], if the value of e, the value of f, the value of g, and the value of h are each in a range of more than 0 and less than 1, and e+f+g+h=1 is satisfied, it is not particularly limited. The value of e is preferably from 0.05 to 0.40, preferably from 0.10 to 0.30. The value of f is preferably from 0.10 to 0.80, and more preferably from 0.10 to 0.40. The value of g is preferably from 0.10 to 0.80, and more preferably from 0.30 to 0.60. The value of h is preferably from 0.001 to 0.40, particularly preferably from 0.05 to 0.30. When the values of e and f, g, and h are in the above range, the composition and the cured body of the present invention have good formability and good mechanical strength. Further, the value of e, the value of f, the value of g, and the value of h are measured by a nuclear magnetic resonance apparatus using a polyoxygen compound represented by the formula [2]. 29 Si-NMR spectra and 1 The H-NMR spectrum was calculated using these. In [2], (Me 2 SiO 2/2 ) the structural unit represented by the above [1] (Me 2 SiO 2/2 The structural unit represented by the same meaning, (PhSiO 3/2 The structural unit represented by the above [1] (PhSiO) 3/2 The structural unit represented by the same meaning, (SiO 4/2 ) the structural unit represented by the above [1] (SiO 4/2 The structural units represented by the same meaning. The viscosity of the component (B) is not particularly limited as long as it is 10,000 cP (centipoise) or less in a standard state (25 ° C, 1 atm). From the viewpoint of handling workability, it is preferably 7,000 cP or less. The lower limit is not particularly limited, and the lower the viscosity, the lower the viscosity of the obtained composition of the present invention, and the easier the sealing operation of the semiconductor device, which is preferable. The viscosity of the component (B) may be more than 0 cP and less than 10,000 cP in a standard state (25 ° C, 1 atm), preferably more than 0 cP and 7,000 or less. Here, the viscosity of the component (B) is measured by the same method as the viscosity of the component (A). The component (B) contains at least a vinyl group (Vi-Si group) bonded to a ruthenium atom, and the amount thereof is not particularly limited. It is preferred to contain two or more in one molecule. It is particularly preferably from 0.5 to 4.0 mmol/g in terms of obtaining a good cured product. The mass average molecular weight of the component (B) is not particularly limited. It is preferably 500 to 10,000, and more preferably 800 to 7,000. When the mass average molecular weight is 500 or more, the cured product of the present invention has good resin strength, and if it is 10,000 or less, the composition of the present invention has good formability. The amount of the HO-Si group contained in the component (B) is not particularly limited. It is preferably from 0.5 to 6.0 mmol/g, particularly preferably from 1.0 to 3.5 mmol/g. When the content of the HO-Si group exceeds 6.0 mmol/g, bubbles may be observed in the cured product. <(C) component> The hydrogenation catalyst of the (C) component promotes the hydrogenation reaction of the Vi-Si group in the H-Si group and the (B) component in the following (A) component (addition hardening) Reaction) is formulated for the purpose. The type of the component (C) is not particularly limited as long as it promotes the above hydrogenation reaction. It is preferred to use at least one selected from the group consisting of a platinum-based catalyst, a ruthenium-based catalyst, and a palladium-based catalyst. Among them, since the transparency of the sealing material can be improved, it is particularly preferable to use a platinum-based catalyst. Examples of the platinum-based catalyst include a platinum component, a platinum component such as chloroplatinic acid or chloroplatinic acid, and a complex of an alcohol, an aldehyde or a ketone, a platinum-olefin complex, and a platinum-alkenyl alkane. Complex, platinum-carbonyl complex, and the like. Preferable examples include platinum-carbonylvinylmethyl complex, platinum-divinyltetramethyldioxane complex (Karstedt catalyst), and platinum-cyclovinylmethyloxirane. Complex, platinum-octanal complex, platinum-phosphine complex, dicarbonyl dichloroplatinum, and the like. Among them, a platinum-divinyltetramethyldioxane complex, a platinum-cyclovinylmethyloxane complex, and the like are preferable. <Other Additives> In the composition of the present invention, in addition to the above components (A) to (C), other additives may be blended. (Component (D): Hardening retarder) As another additive, for example, in order to improve storage stability and handling workability of the composition, it is possible to adjust the hydrogenation reactivity during curing, etc., in the composition of the present invention. A hardening retarder (hereinafter sometimes referred to as a component (D)) is formulated. The composition of the present invention can be used as a cured product at a relatively low temperature, and thus can be preferably used for coating and sealing a heat-resistant optical semiconductor member. On the other hand, from the viewpoint of the storage stability and handling workability of the composition of the present invention, it is preferred to adjust the hardening retarder to adjust the curing rate depending on the working environment for coating and sealing. The type of the component (D) is not particularly limited as long as it has a curing retardation effect on the component (C). A conventionally known hardening retarder can be used, and examples thereof include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, a nitrogen-containing compound, an organic sulfur compound, an organic peroxide, and the like. These compounds may be used in a single type or in combination of plural kinds. The content of the component (D) in the composition of the present invention is not particularly limited. Usually, the hardening retarder may be added in an amount of 20 to 200 equivalents per equivalent of the platinum atom in the component (C) contained in the composition. The degree of hardening retardation effect by the hardening retarder varies depending on the chemical structure of the hardening retarder. Therefore, it is preferred to adjust the blending amount to the most suitable amount depending on the type of the hardening retarder to be used. By adding the most suitable amount of hardening retarder, the composition of the present invention can be used for long-term storage stability at room temperature (especially at ambient temperature of unheated or cooled, usually 15 to 30 ° C; the same below) And excellent in heat hardenability. (Component (E): Substance-imparting agent) In the composition of the present invention, in addition to the above components (A) to (C), in order to improve the adhesion, a subsequent application agent may be formulated (hereinafter, sometimes referred to as ( E) ingredients). As the type of the component (E), a conventionally known decane coupling agent or a hydrolysis-condensation product thereof can be used, and examples thereof include an epoxy group-containing decane coupling agent, a (meth) acrylonitrile-containing decane coupling agent, and the like. An isocyanate group decane coupling agent, an isocyanurate group-containing decane coupling agent, an amine group-containing decane coupling agent, a mercapto group-containing decane coupling agent, and the like. These may be used in a single type or in combination. The content of the component (E) in the composition of the present invention is not particularly limited. The total mass of the components (A) to (C) is preferably from 1 to 20% by mass, particularly preferably from 5 to 15% by mass. (Component (F): Antioxidant) An antioxidant (hereinafter sometimes referred to as a component (F)) may be added to the composition of the present invention in order to suppress the occurrence of coloration or oxidative degradation of the cured product. As the kind of the component (F), a conventionally known antioxidant can be used, and examples thereof include a phenol-based antioxidant, a thioether-based antioxidant, and a phosphorus-based antioxidant. Among them, a phenol-based antioxidant or a thioether-based antioxidant is preferred, and a thioether-based antioxidant is particularly preferred. These antioxidants may be used alone or in combination of two or more. The content of the component (F) in the composition of the present invention is not particularly limited as long as it does not impair the range of characteristics such as transparency of the cured product of the present invention and is an effective amount as an antioxidant. The amount of the components (A) to (C) is 0.001 to 2% by mass, preferably 0.01 to 1% by mass. When it is in this range, the antioxidant ability is fully exhibited, and it is possible to suppress the occurrence of coloring, white turbidity, oxidative degradation, and the like, and to obtain a cured product excellent in engineering properties. ((G) component: light stabilizer) A light stabilizer can be added to the composition of the present invention in order to impart resistance to light deterioration due to light energy such as sunlight or a fluorescent lamp (hereinafter sometimes referred to as (G) component). As the kind of the component (G), a previously known light stabilizer can be used. Among them, a hindered amine-based stabilizer that captures a radical generated by photooxidation (photodegradation) can be preferably used, and the antioxidant effect can be further enhanced by using the component (F) in combination. The amount of the component (G) in the composition of the present invention is not particularly limited as long as it does not impair the range of characteristics such as transparency of the cured product of the present invention and is an effective amount as a light stabilizer. The total mass of the components (A) to (C) may be adjusted to 0.01 to 5% by mass, preferably 0.05 to 0.5% by mass. (Component (H): Phosphor) A phosphor which is an optional component (hereinafter sometimes referred to as a component (H)) can be blended in the composition of the present invention. As the kind of the (H) component, a previously known one can be used. For example, an oxide-based phosphor, an oxynitride-based phosphor, a nitride-based phosphor, a sulfide-based phosphor, or an oxysulfide-based fluorite is widely used for a light-emitting diode (LED). Yellow, red, green, and blue luminescent phosphors such as light bodies. The amount of the component (H) is not particularly limited as long as it does not impair the range of characteristics such as transparency of the cured product of the present invention and is an effective amount as a phosphor. The total mass of the components (A) to (C) is preferably 10 to 70% by mass, particularly preferably 20 to 50% by mass. (Component (I): Inorganic Particles) In the composition of the present invention, in order to improve the optical properties, workability, mechanical properties, and physicochemical properties of the cured product, inorganic particles may be formulated (hereinafter, sometimes referred to as (I) ingredient). The type of the (I) component can be selected according to the purpose, and a single type can be added, and a plurality of types can be combined. Further, in order to improve the dispersibility, the inorganic particles may be surface-treated by a surface treatment agent such as a decane coupling agent. Examples of the type of the component (I) include inorganic oxide particles such as cerium oxide, barium titanate, titanium oxide, zirconium oxide, cerium oxide, aluminum oxide, cerium oxide, and cerium oxide, or cerium nitride or boron nitride. Nitride particles such as tantalum carbide or aluminum nitride, carbon compound particles, diamond particles, and the like may be selected depending on the purpose, and are not limited thereto. The form of the component (I) may be in any form such as a powder form or a slurry form depending on the purpose. The composition of the present invention is formulated in such a manner that the refractive index is as much as possible in the same manner as the cured product of the present invention, depending on the desired transparency. Further, it is preferably formulated into a composition of the present invention as a water-based or solvent-based transparent sol. The average particle diameter of the component (I) to be blended is not particularly limited, and those having an average particle diameter according to the purpose are used. Usually, it is about 1/10 or less of the particle diameter of the above-mentioned phosphor. Further, the particle diameter was measured by SEM (scanning electron microscope), and the short diameter and the long diameter of the particles were measured, and the value obtained by (short diameter + long diameter) / 2 was calculated. This operation is performed on the particles in a certain section in the SEM image, and the arithmetic mean value of each of the obtained particle diameters is taken as the average particle diameter of the component (I). The amount of the component (I) is optional unless it is inferior to the heat-resistant transparency of the cured product of the present invention. When the amount of the component (I) is too small, the desired effect may not be obtained, and if it is too large, the properties such as heat-resistant transparency, adhesion, transparency, moldability, and hardness of the cured product may be brought about. Bad effects. The total mass of the components (A) to (C) may be adjusted to about 1 to 50% by mass, preferably about 5 to 35% by mass. In addition to the components (D) to (I), the release agent, the resin modifier, the colorant, the diluent, and the like may be formulated in the composition of the present invention within a range not impairing the transparency of the cured product or the like. Antibacterial agent, anti-fungal agent, leveling agent, anti-sagging agent, etc. <Preparation Ratio of (A) Component, (B) Component, and (C) Component> The compounding ratio of the component (A) to the component (B) in the composition of the present invention is not particularly limited. It is basically formulated based on the molar ratio of the H-Si group contained in the component (A) and the Vi-Si group contained in the component (B). Specifically, the number of moles of the Vi-Si group included in the number of moles of the H-Si group contained in the component (A)/(B) is preferably in the range of 1 to 4, and more preferably 1 to 4; 3. If it is within this range, the composition of the present invention exhibits good formability, and the cured product of the present invention has excellent heat-resistant transparency. The compounding amount of the component (C) in the composition of the present invention is not particularly limited. It is preferable that the metal atom in the component (C) is in an amount of 0.003 to 30 ppm in mass units based on the total mass of the component (A) and the components (B) and (C). Among them, the obtained cured product tends to have excellent heat-resistant transparency, and is more preferably 0.003 to 5.0 ppm, still more preferably 0.003 to 3.0 ppm, and particularly preferably 0.003 to 2.0 ppm. When the amount of the component (C) is 0.003 to 30 ppm, the hydrogenation reaction of the component (A) and the component (B) proceeds smoothly. The viscosity of the composition of the present invention is not particularly limited as long as it is 10,000 cP (centipoise) or less in a standard state (25 ° C, 1 atm). If it is 10,000 cP or less, it is preferably 7,000 cP or less. The lower limit value is not particularly limited, and the lower the viscosity, the easier the sealing operation of the semiconductor device becomes, which is preferable. The viscosity of the composition of the present invention may be more than 0 cP and less than 10,000 cP in a standard state (25 ° C, 1 atm), preferably more than 0 cP and less than 7,000. Here, the viscosity of the composition of the present invention is determined by the same method as the viscosity of the component (A). Since the composition of the present invention is a low-viscosity resin composition, it has good fluidity, and particularly in the sealing operation of a semiconductor device, it is difficult to cause breakage of the resin composition or entrapment of air bubbles, and it is easy to apply. Therefore, the sealing work can be performed efficiently. Further, the cured product obtained from the composition of the present invention has sufficient durability in the use of a sealing material for a semiconductor device. Therefore, the composition of the present invention is suitable for use as a sealing material for semiconductor devices. The total content of the HO-Si group in the component (A) and the component (B) in the composition of the present invention is not particularly limited. It may be from 0.5 to 5.0 mmol/g, preferably from 1.0 to 4.5 mmol/g, particularly preferably from 1.5 to 4.5 mmol/g. If it is in this range, the hardening of the composition proceeds sufficiently, and the desired cured product can be easily obtained. <Preparation of Curable Polyoxyxyl Resin Composition> The composition of the present invention can be prepared by blending the component (A), the component (B) and the component (C), and optionally blending other additives as needed. It is preferred to uniformly disperse these substances by mixing the components (A), (B), (C), and additives as needed. The mixing method is not particularly limited, and a previously known mixing method can be employed. For example, a mixing method using a mixing device such as a universal kneader or a kneader can be employed. Further, the component (C) may be mixed with the component (A) and/or the component (B) in advance. Further, in order to stably store for a long period of time, the component (B) and the component (C) are stored in separate containers. For example, the first component containing the component (A) and the component (C) may be previously prepared, and The second composition containing the remaining portion of the component (A) and the component (B) is separately stored in a different container, and is mixed immediately before use to prepare the composition of the present invention, and the composition can be used. Further, it is degassed by depressurization and then supplied for use. (Manufacturing Method of Component (A)) As an example of the production method of the component (A), the component (A) can be produced by a method including at least the following first to third steps. The first step: a step of reacting a dialkoxy decane represented by the following formula [3] with a trialkoxy decane represented by the following formula [4] to obtain a first hydrolysis polycondensate; a step of reacting a first hydrolyzed polycondensate with a tetraalkoxydecane represented by the following formula [5] under a strong acid condition to obtain a second hydrolyzed polycondensate; and a third step: a second hydrolyzed polycondensate a step of reacting a decane compound represented by the general formula [6], [7] or [8] under a strong acid condition, thereby obtaining a component (A); 2 Si (OR 5 ) 2 [3] PhSi (OR 6 ) 3 [4] Si (OR 7 ) 4 [5] H-SiMe 2 (OH) [6] H-SiMe 2 (OR 8 ) [7] (H-SiMe 2 ) 2 O [8] In the formula [3], R 5 Indicates an alkyl group having 1 to 3 carbon atoms, and two R 5 They may be the same or different types from each other. In the formula [4], R 6 Indicates an alkyl group having 1 to 3 carbon atoms, and three R 6 They may be the same or different types from each other. In the formula [5], R 7 Indicates an alkyl group having 1 to 3 carbon atoms, and four R 7 They may be the same or different types from each other. In the formula [7], R 8 It represents an alkyl group having 1 to 3 carbon atoms. Hereinafter, the first to third steps will be described. "First Step" In the first step, first, a certain amount of dialkoxy decane represented by the general formula [3] (hereinafter sometimes referred to as "dialkoxydecane [3]") The trialkoxy decane (hereinafter sometimes referred to as "trialkoxydecane [4]") represented by the formula [4] is put into a reaction vessel at room temperature, and then water for hydrolysis and polycondensation is added, according to A reaction solvent is added as needed, and a catalyst for smoothly conducting the condensation reaction is added as needed to prepare a reaction solution. The order of the reaction materials to be introduced at this time is not particularly limited, and can be prepared as a reaction solution in any order. Then, while stirring the reaction solution, the reaction is carried out for a specific time and at a specific temperature, whereby the first hydrolyzed polycondensate can be obtained. In this case, in order to prevent the alkoxydecane compound, water, reaction solvent and/or catalyst which are unreacted raw materials in the reaction system from being distilled out of the reaction system, it is preferred to provide a reflux apparatus in the reaction vessel. In the first step, the amount of the dialkoxydecane [3] and the trialkoxydecane [4] is not particularly limited. Preferably, the dialkoxy decane [3]: trialkoxy decane [4] is formulated in a molar ratio of 85: 15 to 15: 85, and more preferably 85: 15 to 30: 70. When the molar ratio of the dialkoxysilane [3] is less than 15, the molecular weight may be higher than the desired molecular weight. If it exceeds 85, the hydrolysis polycondensation reaction may be difficult to proceed, and may be lower than the desired molecular weight. In the first step, the amount of water used is not particularly limited. From the viewpoint of the reaction efficiency, the alkoxy group contained in the alkoxydecane compound relative to the reaction raw material, that is, the alkoxy group contained in the dialkoxy decane [3], the trialkoxy decane [4] The total molar equivalent is preferably 1.5 times or more and 5 times or less. When it is 1.5 times the molar equivalent or more, the hydrolysis of the dialkoxy decane [3] and the trialkoxy decane [4] proceeds efficiently, and it is not necessary to add more than 5 times the molar equivalent. In the first step, the reaction can be carried out without a solvent, but a reaction solvent can also be used. The type of the reaction solvent is not particularly limited as long as it does not inhibit the reaction for obtaining the first hydrolysis polycondensate. Among them, a hydrophilic organic solvent such as an alcohol is preferred. Specific examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, butanol, and the like, but are not limited thereto. The amount of the reaction solvent used is preferably from 0.1 to 1,000% by mass, particularly preferably from 1 to 300% by mass, based on the total amount of the alkoxydecane compound of the reaction raw material. Further, the alcohol formed from the alkoxysilane compound of the reaction raw material during the reaction can function as a reaction solvent, and thus it is not necessary to add it. In the first step, in the case of using a catalyst, an acidic catalyst or an alkaline catalyst can be used. Among them, since the molecular weight of the obtained first hydrolyzed polycondensate is easily controlled, it is preferred to use an acidic catalyst. The type of the acidic catalyst is not particularly limited. For example, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, trifluoroacetic acid, etc. are mentioned. Among them, acetic acid, hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and more preferably acetic acid are preferred because the removal of the acid catalyst after the completion of the reaction is relatively easy. Further, the type of the alkaline catalyst is not particularly limited. For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, pyridine, etc. are mentioned. The amount of the catalyst used is preferably 0.001 to 5% by mass, particularly preferably 0.005 to 1% by mass, based on the total amount of the alkoxydecane compound, water and solvent of the reaction raw material. In the first step, the reaction time and the reaction temperature are not particularly limited. The reaction time is usually from 3 to 15 hours. The reaction temperature is usually 60 to 120 ° C, preferably 80 to 100 ° C. After the reaction, from the viewpoint of the rationality of the first hydrolysis polycondensate, it is preferred to separate and purify the first hydrolysis polycondensate from the reaction system. This separation method is not particularly limited. As a separation method, the extraction method is mentioned, for example. Specifically, after the reaction solution after the above reaction is cooled to room temperature, it is contacted with a water-insoluble organic solvent as an extraction solvent, whereby the first hydrolyzed polycondensate present in the reaction system is extracted. Then, the removal of the catalyst contained in the extracted solution is performed. The method of removing the catalyst is not particularly limited. For example, if the catalyst (e.g., acetic acid) used is water soluble, the catalyst can be removed by washing the extracted solution with water. Then, a desiccant is added to the solution after removing the catalyst to remove the dissolved water in the system. Further, the removal of the desiccant and the removal of the extraction solvent are carried out under reduced pressure, whereby the first hydrolyzed polycondensate of high purity can be separated. At this time, it is also possible to remove the water under reduced pressure while the extraction solvent is removed under reduced pressure from the solution after removing the catalyst without using a desiccant. As the above extraction solvent, a water-insoluble organic solvent can be used. The type of the water-insoluble organic solvent is not particularly limited. For example, an aromatic hydrocarbon, an ether, etc. are mentioned. Specific examples thereof include toluene, diethyl ether, isopropyl ether, and dibutyl ether, but are not limited thereto. The desiccant is not particularly limited as long as it can remove water from the system and is separated from the first hydrolyzed polycondensate. As such a desiccant, a solid desiccant is preferably used, and specific examples thereof include magnesium sulfate and the like, but are not limited thereto. The separated and purified first hydrolyzed polycondensate can be further subjected to a condensation reaction by heating under reflux in a solvent or heating and stirring without a solvent. Thereby, the molecular weight of the first hydrolysis polycondensate can be increased. When a solvent is used, the first hydrolyzed polycondensate and the solvent are introduced into a reaction vessel which can be heated to reflux to prepare a solution. The solution was heated under reflux to carry out condensation while azeotroping with water formed in the system. In this case, p-toluenesulfonic acid or the like may be added to the solution to be heated and refluxed. The type of the solvent to be used is not particularly limited as long as it is a solvent which can dissolve the first hydrolyzed polycondensate and can be heated to reflux. Specific examples thereof include aromatic hydrocarbons, ethers, and esters. Examples of the aromatic hydrocarbons include toluene, xylene, and benzene. Examples of the ethers include diethyl ether and diisopropyl ether. Examples of the esters include ethyl acetate. Further, in the case of no solvent, the first hydrolyzed polycondensate is placed in a reaction vessel which can be heated and stirred, and heated to 100 to 150 ° C for 6 to 18 hours. In this case, in order to suppress the change in the composition ratio of the first hydrolysis polycondensate, it is preferred to provide a reflux device (for example, a condenser) in the reaction container. After heating and stirring, the content liquid was cooled to room temperature. These series of operations can be repeated, and the number of repetitions is not particularly limited. It is preferably carried out 1 to 4 times. "Second Step" In the second step, the first hydrolyzed polycondensate obtained in the first step and the tetraalkoxydecane represented by the general formula [5] (hereinafter sometimes referred to as "tetraalkoxydecane"[5]") The reaction is carried out in the presence of a strong acid to obtain a second hydrolyzed polycondensate. Specifically, after a specific amount of the first hydrolyzed polycondensate and the tetraalkoxydecane [5] are introduced into the reaction vessel at room temperature, a reaction solvent is added as needed, and a strong acid is added as a catalyst for performing a condensation reaction. , made into a reaction solution. The order of the input at this time is not limited to this, and it can be set as a reaction solution in arbitrary order. Then, while stirring the reaction liquid, the reaction is carried out for a specific time and at a specific temperature, whereby the second hydrolysis polycondensate can be obtained. In this case, in order to prevent the alkoxydecane compound, the reaction solvent, and/or the catalyst of the unreacted raw material in the reaction system from being distilled out of the reaction system, it is preferred to provide a reflux apparatus in the reaction vessel. In the second step, the amount of the first hydrolyzed polycondensate and the tetraalkoxydecane [5] is not particularly limited. From the viewpoint of the reactivity, the tetraalkoxydecane [5] is preferably 0.001 to 600% by mass, and more preferably 0.01 to 400% by mass, based on the first hydrolysis polycondensate. In the second step, a small amount of water may be contained in the reaction liquid. However, if a large amount of water is contained, cerium oxide may be formed during the reaction, and the desired second hydrolysis polycondensate may not be obtained. The content of the water in the reaction liquid is not particularly limited as long as the desired second hydrolyzed polycondensate can be obtained, and is preferably 1% by mass or less, and particularly preferably 0.001% by mass based on the tetraalkoxydecane [5]. the following. The water content also includes water which is sometimes contained in a strong acid such as nitric acid or hydrochloric acid. In the second step, the reaction may be carried out in the absence of a solvent, but a reaction solvent may also be used, and it is preferably used. The type of the reaction solvent is not particularly limited as long as it does not inhibit the reaction for obtaining the second hydrolysis polycondensate. Among them, a hydrophilic organic solvent such as an alcohol is preferred. Specific examples of the alcohol include methanol, ethanol, n-propanol, isopropanol, butanol, and the like, but are not limited thereto. The amount of the reaction solvent to be used is preferably from 0.1 to 1,000% by mass, particularly preferably from 1 to 300% by mass, based on the total amount of the first hydrolysis condensate and the tetraalkoxydecane [5]. Further, the alcohol formed from the alkoxysilane compound of the reaction raw material during the reaction can function as a reaction solvent, and thus it is not necessary to add it. In the second step, the strong acid to be used is preferably an acid having an acid dissociation constant pKa of 3 or less. Specific examples thereof include nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. Among them, nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, and more preferably nitric acid are preferred because the acid removal treatment after the completion of the reaction is relatively easy. The amount of the strong acid to be used is preferably 0.0001 to 5% by mass, and particularly preferably 0.001 to 1% by mass, based on the total amount of the first hydrolyzed polycondensate and the tetraalkoxydecane [5] and the reaction solvent. In the second step, the reaction time and the reaction temperature are not particularly limited. The reaction time is usually from 1 to 48 hours. The reaction temperature is usually 60 to 120 ° C, preferably 80 to 100 ° C. After the reaction, the second hydrolysis polycondensate can be separated from the reaction system and purified. This separation method is not particularly limited. As the separation method, for example, the same method as the separation method described in the above first step can be mentioned, and the second hydrolysis polycondensate can be separated and purified in the same manner as in the first step. "3rd step" In the third step, the second hydrolyzed polycondensate is reacted with a decane compound represented by the above formula [6], [7] or [8] under strong acid conditions to obtain a component (A). The second hydrolysis polycondensate may be separated from the reaction system in the second step to be supplied to the reaction, or may be directly supplied to the reaction without being separated from the reaction system. Specifically, a specific amount of the second hydrolysis polycondensate, a decane compound represented by the general formula [6], a decane compound represented by the general formula [7], or a decane compound represented by the general formula [8], as needed After the reaction solvent was added to the reaction vessel at room temperature, a strong acid was added as a catalyst for carrying out the condensation reaction to prepare a reaction liquid. The order of the input at this time is not limited to this, and it can be prepared as a reaction liquid in any order, but it is preferable that the catalyst is finally supplied. Then, while stirring the reaction liquid, the reaction is carried out at a specific temperature and a specific temperature, whereby the component (A) can be obtained. At this time, in order to prevent the unreacted raw materials, the reaction solvent, and/or the catalyst in the reaction system from being distilled out of the reaction system, it is preferred to provide a reflux device in the reaction container. In the third step, the second hydrolysis polycondensate, the decane compound represented by the general formula [6], the decane compound represented by the general formula [7] or the decane compound represented by the general formula [8] are not particularly used. limited. From the viewpoint of the physical properties of the component (A), it is preferably a decane compound represented by the general formula [6] and a decane compound represented by the general formula [7] with respect to 1 g of the second hydrolysis polycondensate. The total amount of the H-Si group in the decane compound represented by the general formula [8] is used in the range of 0.2 to 10 mmol. The strong acid used in the third step is preferably an acid having an acid dissociation constant pKa of 3 or less. Specific examples thereof include nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. Among them, nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, and more preferably nitric acid are preferred because the acid removal treatment after the completion of the reaction is relatively easy. The amount of the strong acid used is preferably from 0.0001 to 10 mmol%, particularly preferably from 0.005 to 5 mmol%, based on 1 g of the second hydrolysis polycondensate. When the reaction solvent is used in the third step, the type thereof is not particularly limited as long as it does not inhibit the reaction for obtaining the component (A). As the reaction solvent used in the third step, a water-soluble organic solvent or a water-insoluble organic solvent can be used. By using these reaction solvents, the viscosity of the reaction solution can be lowered. Among them, a water-soluble organic solvent is preferred. By using a water-soluble organic solvent, the viscosity of the reaction solution can be lowered, and the second hydrolysis polycondensate can be uniformly dispersed in the reaction system with the strong acid used in the third step. Specific examples of the water-soluble organic solvent include alcohols and the like, and more specifically, methanol, ethanol, n-propanol, isopropanol, butanol, and the like are exemplified, but are not limited thereto. Specific examples of the water-insoluble organic solvent include aromatic hydrocarbons and ethers, and more specifically, toluene, diethyl ether, tetrahydrofuran, diisopropyl ether, etc., but are not limited thereto. . The amount of the reaction solvent used in the third step is preferably more than 0% by mass and not more than 1000% by mass, and more preferably from 50 to 500% by mass, based on 1 g of the second hydrolyzed polycondensate. When the second hydrolysis-condensation product obtained in the second step is not separated from the reaction system and supplied to the third step, the reaction solvent is not particularly limited. When the reaction solvent is used, the total amount of the reaction solvent used in the second step is preferably more than 0% by mass and not more than 1000% by mass, particularly preferably from 10 to 500% by mass based on 1 g of the second hydrolyzed polycondensate. %. Further, the use of the reaction solvent in the third step is arbitrary, and the target (A) component can also be obtained when it is not used. In the third step, the method of completing the reaction is not particularly limited. For example, the reaction can be terminated by the addition of water (preferably ion-exchanged water) to the reaction system. After the reaction, from the viewpoint of the rationality of the component (A), it is preferred to separate the component (A) from the reaction system and purify it. This separation method is not particularly limited. For example, a method of extraction may be mentioned, and specifically, an organic layer is obtained by the solution after the above reaction. Then, the organic layer is washed with water (preferably ion-exchanged water), and an acid scavenger and a desiccant are added to remove dissolved acid and water in the system. Thereafter, the acid scavenger is removed from the organic layer and the desiccant and the water-insoluble organic solvent are removed under reduced pressure, whereby the component (A) can be separated in high purity. At this time, it is also possible to remove the water while removing the water-insoluble organic solvent without using a desiccant. The component (A) after the separation is preferably removed by heating the water contained in the component (A) by heating without a solvent and under reduced pressure. The heating temperature at this time is not particularly limited, and is usually from 100 to 190 °C. As the above extraction solvent, a water-insoluble organic solvent can be used. The type of the non-aqueous aqueous organic solvent is not particularly limited. For example, an aromatic hydrocarbon, an ether, etc. are mentioned. Specific examples thereof include toluene, diethyl ether, isopropyl ether, and dibutyl ether, but are not limited thereto. The type of the acid scavenger is not particularly limited as long as the strong acid can be removed from the system. As such an acid scavenger, a solid acid scavenger can be preferably used. Further, a commercially available acid scavenger can be used as needed. As a commercial item, Kyoword 500 manufactured by Kyowa Chemical Industry Co., Ltd. may be cited, but is not limited thereto. The desiccant is not particularly limited as long as it can remove water from the system. As such a desiccant, a solid desiccant can be preferably used. Specific examples thereof include magnesium sulfate and the like, but are not limited thereto. (Manufacturing Method of Component (B)) As an example of the production method of the component (B), the component (B) can be produced by a method including at least the following fourth step. Step 4: a step of obtaining a component (B) by reacting a second hydrolysis polycondensate with a decane compound represented by the following general formula [9], [10] or [11] under strong acid conditions. [化16] Vi-SiMe 2 (OH) [9] Vi-SiMe 2 (OR 9 ) [10] (Vi-SiMe 2 ) 2 O [11] In the formula [10], R 9 It represents an alkyl group having 1 to 3 carbon atoms. Hereinafter, the fourth step will be described. "Step 4" In the fourth step, the second hydrolyzed polycondensate is reacted with the decane compound represented by the above formula [9], [10] or [11] under strong acid conditions, thereby obtaining (B) ingredient. As the second hydrolysis polycondensate, a second hydrolysis polycondensate obtained when the component (A) is produced can be used, and a second hydrolysis polycondensate separately prepared can also be used. The reaction conditions, the separation operation, and the like of the above third step can be applied to the reaction conditions, the separation operation of the component (B), and the like. In other words, the decane compound represented by the general formula [6] in the third step, the decane compound represented by the general formula [7], the decane compound represented by the general formula [8], and the H-Si group can be used. The component A) is replaced by a decane compound represented by the general formula [9], a decane compound represented by the general formula [10], a decane compound represented by the general formula [11], a Vi-Si group, and (B) component, respectively. Explain the fourth step. [2. The cured product of the curable polyoxyxene resin composition] The cured product of the curable polyoxyxene resin composition of the present invention (hereinafter sometimes referred to as "the cured product of the present invention") may be a combination of the present invention. Obtained by heating. The cured product of the present invention can be used as a sealing material for a semiconductor device, and is preferably used as a sealing material for an optical semiconductor device or a power semiconductor device. The sealing material for an optical semiconductor device can be preferably used as a sealing material for an optical member for an LED or a sealing member for an optical member for a semiconductor laser. Among them, a sealing material for an optical member for an LED is particularly preferable. In general, an optical semiconductor device is improved in light extraction efficiency by various techniques. However, if the transparency of the sealing material of the optical semiconductor element is low, the sealing material absorbs light, and the light extraction efficiency of the optical semiconductor device using the same is lowered. As a result, there is a tendency that it is difficult to obtain a high-intensity optical semiconductor device product. Further, energy equivalent to a decrease in light extraction efficiency is converted into heat, which is a cause of thermal deterioration of the optical semiconductor device, which is not preferable. The cured product of the present invention is excellent in transparency. Specifically, the cured product of the present invention has a good light transmittance at a wavelength of usually 300 nm or more, preferably 350 nm or more, and usually 900 nm or less, preferably 500 nm or less. Therefore, when the cured product of the present invention is used as the sealing material in an optical semiconductor device having an emission wavelength in the region, an optical semiconductor device having high luminance can be obtained, which is preferable. Further, the cured product of the present invention may be used as a sealing material in an optical semiconductor device having an emission wavelength outside the above region. Furthermore, the above light transmittance can be measured by transmittance measurement using an ultraviolet/visible spectrophotometer. The method of hardening the composition of the present invention is not particularly limited. For example, the composition of the present invention is formed by injection, dripping, casting, injection molding, extrusion from a container, or the like by means of transfer molding or injection molding, such as an LED. The combination of the sealing objects is usually heated at 45 to 300 ° C, preferably 60 to 200 ° C, whereby the composition is cured to be a cured product, and the object to be sealed can be sealed. When the heating temperature is 45° C. or more, adhesion is hard to be observed in the obtained cured product, and when it is 300° C. or less, it is difficult to observe foaming in the obtained cured product, which is practical. The heating time is not particularly limited. It is usually about 0.5 to 12 hours, preferably about 1 to 10 hours. When the heating time is 0.5 hours or more, the hardening is sufficiently performed. However, in the case where the precision for LED sealing or the like is required, the curing time is preferably extended. [3. Sealing material] The cured product of the present invention can be used as a sealing material for a semiconductor device, and is particularly preferably used as a sealing material for an optical semiconductor device or a power semiconductor device. The sealing material containing the cured product of the present invention is excellent in transparency as described above. Moreover, it is excellent in heat resistance, cold resistance, and electrical insulation similarly to the cured product of the conventional addition-hardening polyoxyxylene resin composition. [4. Optical semiconductor device] The optical semiconductor device of the present invention is an optical semiconductor device including at least an optical semiconductor element, and at least the optical semiconductor device is sealed by the cured product of the present invention. The other configuration of the optical semiconductor device of the present invention is not particularly limited, and a member other than the optical semiconductor element may be provided. Examples of such a member include a base substrate, a lead wiring, a lead wiring, a control element, an insulating substrate, a reflective material, a heat sink, a conductive member, a die bonding material, and a bonding pad. Further, in addition to the optical semiconductor element, part or all of the member may be sealed by the cured product of the present invention. Specific examples of the optical semiconductor device of the present invention include a light-emitting diode (LED) device, a semiconductor laser device, and a photocoupler, but are not limited thereto. The optical semiconductor device of the present invention can be preferably used, for example, as a backlight for a liquid crystal display or the like, illumination, various light sources such as a sensor, a printer, and a photocopying machine, a vehicle light source, a signal lamp, a display lamp, and a display device. Light source, display, decoration, various lamps, switching elements, etc. of the planar illuminator. Fig. 1 shows an example of an optical semiconductor device of the present invention. As illustrated in FIG. 1 , the optical semiconductor device 10 includes at least the sealing material 1 , the optical semiconductor element 2 , and the bonding wires 3 on the optical semiconductor substrate 6 . The optical semiconductor substrate 6 has a concave portion including a bottom surface of the lead frame 5 and an inner peripheral side surface including the reflective material 4. The optical semiconductor element 2 is connected to the lead frame 5 by using a die bond (not shown). A bonding pad (not shown) provided on the optical semiconductor element 2 and the lead frame 5 are electrically connected by a bonding wire 3. The reflective material 4 has a function of reflecting light from the optical semiconductor element 2 in a specific direction. The sealing material 1 is filled in the region of the above-mentioned concave portion of the optical semiconductor substrate 6 so as to at least seal the optical semiconductor element 2. At this time, the sealing material 1 may be filled also in such a manner as to seal the bonding wires 3. The sealing material 1 contains the cured product of the present invention. The inside of the sealing material 1 may contain the above-mentioned phosphor (not shown). By the sealing material 1, the optical semiconductor element 2 can be protected from moisture, dust, and the like, and the reliability for a long period of time can be maintained. Further, by sealing the bonding wire 3 also with the sealing material 1, it is possible to simultaneously prevent electrical adverse effects due to dropping, breaking, and short-circuiting of the bonding wire 3. The cured product of the present invention can be used as an adhesive for semiconductors as described below. Therefore, it can also be used as the above-mentioned cement crystal material or the like. In the optical semiconductor device 10, examples of the optical semiconductor element 2 sealed by the sealing material 1 including the cured product of the present invention include an LED, a semiconductor laser, a photodiode, a photoelectric crystal, a solar cell, and a CCD ( Charge couple device, charge coupler, etc. In addition, the structure shown in FIG. 1 is only an example of the optical semiconductor device of the present invention, and the structure of the reflective material, the structure of the lead frame, the mounting structure of the optical semiconductor element, and the like can be suitably changed. The method of manufacturing the optical semiconductor device 10 shown in FIG. 1 is not particularly limited. For example, a method in which the optical semiconductor element 2 is bonded to the lead frame 5 including the reflective material 4, and the optical semiconductor element 2 and the lead frame 5 are bonded by a bonding wire 3, and then to the optical semiconductor element The inside of the surrounding reflective material (including the recessed portion of the lead frame and the reflective material) is filled with the composition of the present invention, and then heated at 50 to 250 ° C to be cured to form the sealing material 1 . [5. Adhesive for Semiconductor Device] The composition of the present invention has good adhesion and can be used as an adhesive for a semiconductor device. Specifically, for example, in the case of the semiconductor element and the package, in the case of the semiconductor element and the sub-mount substrate, and then in the case where the package constitutes the elements, in the case of the semiconductor device and the external optical member The composition of the present invention can be used by coating, printing, potting, and the like. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by the examples. 1. Evaluation method of physical properties of raw materials [determination of composition ratio and quantification of HO-Si group] 0.5 mL of ruthenium chloroform was added to 200 mg of polyoxyxylene resin, and acetonitrile acetonate (III) was added as a moderator. ) The complex is 10 mg. Take 29 The solution thus prepared was determined by Si-NMR. The detected signals are classified as peaks (a) to (k) as shown in Table 1, and the respective peaks are calculated from the sum of the total integral values in percentage (integral ratio). Furthermore, polyoxyl resin 29 The Si-NMR measurement was performed using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., model: JNM-AL400) having a resonance frequency of 400 MHz. [Table 1] [化17] (H-SiMe 2 O 1/2 ) a (Me 2 SiO 2/2 ) b (PhSiO 3/2 ) c (SiO 4/2 ) d [1] The values of a, b, c, and d in the above formula [1] can be determined by calculating from the following formula: a = (peak (a) area + peak (b) area) / total peak area sum , b = (peak (c) area + peak (d) area + peak (e) area) / total peak area sum, c = (peak (f) area + peak (g) area + peak (h) area + Peak (i) area) / total peak area sum, d = peak (j) area / total peak area sum. [化18] (Vi-SiMe 2 O 1/2 ) e (Me 2 SiO 2/2 ) f (PhSiO 3/2 ) g (SiO 4/2 ) h [2] The values of e, f, g, and h in the above formula [2] can be determined by calculating from the following equation: e = (peak (a) area + peak (b) area) / total peak area sum , f = (peak (c) area + peak (d) area + peak (e) area) / total peak area sum, g = (peak (f) area + peak (g) area + peak (h) area + Peak (i) area) / total peak area sum, h = peak (k) area / total peak area sum. to 29 In Si-NMR, Me-Si group, Ph-Si group, H-Si group, CH 2 When the CH-Si group (Vi-Si group) or other base peaks overlap, based on 1 Me-Si group, Ph-Si group, H-Si group, CH in H-NMR 2 Calculated by the integrated area of the peak of the CH-Si group or other base. The content of the HO-Si group (mmol/g) can be determined from the integral ratio calculated by the above method according to the following formula: [A] = peak (a) integral ratio + 2 × peak (c) integral ratio + peak (d) Integral ratio +3 × peak (f) integral ratio +2 × peak (g) integral ratio + peak (h) integral ratio, [B] = peak (a) integral ratio × 83.16 + peak (b) integral ratio × 74.15 + peak ( c) integral ratio × 147.2+ peak (d) integral ratio × 138.2+ peak (e) integral ratio × 129.2+ peak (f) integral ratio × 87.9 + 2 peak (g) integral ratio × 78.10 + peak (h) integral ratio × 69.09+Crest (i) integral ratio ×60.08+peak (j) integral ratio×67.16+peak (k) integral ratio×93.20, HO-Si base content (mmol/g)=([A]/[B]) ×1000. [Quantification of H-Si based and Vi-Si based] 20 to 30 mg of polyfluorene oxide resin was weighed in a 6 mL sample tube, and 0.8 mL of deuterated dichloromethane was added to dissolve the polyoxynoxy resin. To the solution, 2.0 μL of dimethyl hydrazine (0.0282 mmol) was added in a micro syringe, the sample tube was closed, and the solution was stirred to make a uniform sample. Take 1 The sample was measured by H-NMR, and the proton ratio of dimethyl fluorene to the proton ratio of the H-Si group or the Vi-Si group was calculated, and the number of moles of the H-Si group or the Vi-Si group in the measurement sample was determined. Then, the content of each functional group in 1 g of the measurement sample was calculated according to the following formula: Moir number (mmol) of the functional group in the polyoxyl resin/measurement sample amount (mg) × 1000 = 1 g in the measurement sample The amount of functional groups (mmol/g). Furthermore, polyoxyl resin 1 The H-NMR measurement was performed using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd., model: ECA-400) having a resonance frequency of 400 MHz. The chemical shifts of the functional groups in the polyoxyxene resin are as follows: Me-Si: 0.0 to 0.5 ppm (3H), H-Si: 4.0 to 5.0 ppm (1H), Vi-Si: 5.5 to 6.5 ppm (3H) ), Ph-Si: 7.0 to 8.0 ppm (5H). [Measurement of Mass Average Molecular Weight (Mw)] The mass average molecular weight (Mw) of the polyoxyxene resin is a gel permeation chromatography (abbreviation: GPC) under the following conditions, and a calibration curve is prepared using polystyrene as a reference material. Calculated value: Device: manufactured by Tosoh Co., Ltd., product name: HLC-8320GPC, column: manufactured by Tosoh Co., Ltd., product name: TSK Gel Super HZ 2000×4, 3000×2, dissolving solution: tetrahydrofuran. [Refractive Index] The refractive index of the polyoxyxene resin was measured using a refractometer (manufactured by Kyoto Electronics Manufacturing Co., Ltd., type: RA-600). [Viscosity measurement] The viscosity of the polyoxyxene resin is based on "The viscosity measurement method by a cone-plate-shaped rotational viscometer" in JIS Z8803 (2011), using a rotational viscometer (manufactured by ANTON PAAR, trade name: PHYSICA MCR51, The measurement range is 200 to 1,000,000 cP) and the temperature control unit (manufactured by ANTON PAAR, trade name: P-PTD200) is measured at a shear rate of 30 [1/s] in a standard state (25 ° C, 1 atm). The value obtained after 1 minute from the start of the measurement. The case of a low viscosity that does not reach the measurement range is referred to as "<200". [Transparency] The transmittance of the resin in the wavelength region of 405 nm and 365 nm was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV-3150). The measurement unit was made of quartz and the thickness of the unit was 1 cm. 2. Raw material synthesis example and comparative synthesis example [Starting material synthesis example 1-1] The synthesis of the polyfluorene oxide resin (I) was carried out in a glass reaction vessel having a volume of 10 L of a stirring blade made of a fluororesin and a Dairy reflux apparatus. 961.6 g (8.0 mol) of Me 2 Si(OMe) 2 1586.4 g (8.0 mol) of PhSi (OMe) 3 . Then, 1440 g of water and 0.96 g of acetic acid were added to the reaction vessel, and the reaction vessel was continuously heated at 75 ° C for 6 hours to carry out hydrolysis and condensation reaction. Thereafter, the reaction liquid was returned to room temperature, and only the water layer was removed. To the reaction vessel of the residual organic layer, 3520 g of toluene and 1440 g of water were added to carry out a liquid separation operation, and then the aqueous layer was removed. The organic layer was then washed four times with 1440 g of water. Thereafter, the organic layer was recovered, and toluene was distilled off under reduced pressure by an evaporator to obtain a polyoxyalkylene resin (I) as a colorless viscous liquid. The yield of the polyoxyloxy resin (I) was 1388.0 g, the mass average molecular weight (Mw) was 900, and the composition ratio was (Me). 2 SiO 2/2 ) 0.49 (PhSiO 3/2 ) 0.51 The content of the HO-Si group was 7.2 mmol/g (12% by mass). [Starting Material Synthesis Example 1-2] Synthesis of Polyxanthene Resin (A1) In a 100 mL flask, 20.00 g of polyoxyl resin (I) and 14.96 g of Si (OEt) were used. 4 . Then, 8.74 g of 2-propanol was added, and 1.84 μL of 70% concentrated nitric acid was added, and the mixture was stirred at 100 °C. After 6 hours, the temperature in the flask was set to room temperature, and 4.82 g of 1,1,3,3-tetramethyldioxane and 0.12 mL of 70% concentrated nitric acid were added, and the mixture was stirred at room temperature. After 17 hours, the reaction solution was transferred to a separatory funnel, and 50 mL of toluene and 80 mL of water were added to carry out an extraction operation, and the organic layer was recovered. Further, 80 mL of water and 20 mL of 2-propanol were added to carry out an extraction operation, and the organic layer was recovered. This same operation was repeated three times, thereby washing the organic layer. To the organic layer, 1 g of an acid scavenger (manufactured by Kyowa Chemical Industry Co., Ltd., product name: Kyoword 500) was added and stirred, and a filter paper made of fluororesin after 1 hour (PORE SIZE: 1 μm) )filter. After removing the toluene from the organic phase by the evaporator, the filtrate was distilled off under reduced pressure at 150 ° C for 1 hour, and further distilled under reduced pressure by heating at 170 ° C for 1 hour. A colorless transparent viscous liquid polyoxyl resin (A1). The yield of polyoxyxylene resin (A1) is 28.58 g, the mass average molecular weight (Mw) is 1400, the viscosity is less than 200 cP, and the composition ratio is (H-SiMe). 2 O 1/2 ) 0.18 (Me 2 SiO 2/2 ) 0.32 (PhSiO 3/2 ) 0.43 (SiO 4/2 ) 0.07 The content of the H-Si group was 1.36 mmol/g, and the content of the HO-Si group was 4.8 mmol/g (8.2% by mass). [Starting Material Synthesis Example 1-3] Synthesis of Polyxanthoxy Resin (B1) In a 100 mL flask, 20.00 g of polyoxyl resin (I) and 14.96 g of Si (OEt) were used. 4 . Then, 8.74 g of 2-propanol was added, and 1.84 μL of 70% concentrated nitric acid was added, and the mixture was stirred at 100 °C. After 6 hours, the temperature in the flask was set to room temperature, and 6.69 g of 1,3-divinyl-1,1,3,3-tetramethyldioxane and 2.30 mL of 70% concentrated nitric acid were added. Stir at room temperature. After 15 hours, the reaction solution was transferred to a separatory funnel, and 80 mL of toluene, 50 mL of water, and 40 mL of 2-propanol were added to carry out an extraction operation, and the organic layer was recovered. Further, 80 mL of water and 20 mL of 2-propanol were added to carry out an extraction operation, and the organic layer was recovered. This same operation was repeated three times, thereby washing the organic layer. Then, 1 g of an acid scavenger (manufactured by Kyowa Chemical Industry Co., Ltd., product name: Kyoword 500) was added to the organic layer and stirred, and a filter paper made of fluororesin (PORE SIZE: 1 μm) was used 1 hour later. filter. After removing the toluene from the organic phase by the evaporator, the filtrate was distilled off under reduced pressure at 150 ° C for 1 hour, and further distilled under reduced pressure by heating at 170 ° C for 1 hour. A colorless transparent viscous liquid polyoxyl resin (B1). The yield of polyoxyxylene resin (B1) was 29.67 g, the mass average molecular weight (Mw) was 2000, the viscosity was 410 cP, and the composition ratio was (Vi-SiMe). 2 O 1/2 ) 0.25 (Me 2 SiO 2/2 ) 0.25 (PhSiO 3/2 ) 0.32 (SiO 4/2 ) 0.18 The content of the Vi-Si group was 2.23 mmol/g, and the content of the HO-Si group was 3.1 mmol/g (5.3% by mass). [Starting Material Synthesis Example 2-1] Synthesis of Polyxanthoxy Resin (II) In a 300 mL flask, 100.00 g of polyoxyl resin (I) and 74.78 g of Si (OEt) were used. 4 . Then, 43.69 g of 2-propanol was added, and 9.21 μL of 70% concentrated nitric acid was added, and the mixture was stirred at 100 °C. After 6 hours, the reaction solution was transferred to a separatory funnel, and 100 mL of toluene, 200 mL of water, and 50 mL of 2-propanol were added to carry out an extraction operation, and the organic layer was recovered. Further, 200 mL of water and 100 mL of 2-propanol were added to carry out an extraction operation, and the organic layer was recovered. This same operation is repeated again, thereby washing the organic layer. Thereafter, toluene was removed from the organic phase by an evaporator to obtain a polyoxyl resin (II) as a colorless transparent viscous liquid. The yield of polyoxyloxy resin (II) is 132.01 g, the mass average molecular weight (Mw) is 1600, the viscosity is less than 200 cP, and the composition ratio is (Me). 2 SiO 2/2 ) 0.40 (PhSiO 3/2 ) 0.51 (SiO 4/2 ) 0.09 The content of the HO-Si group was 7.36 mmol/g (13% by mass). [Starting Material Synthesis Example 2-2] Synthesis of Polydecane Oxygen Resin (A2) 20.00 g of polyfluorene oxide resin (II), 60.00 g of toluene, 20.00 g of methanol, 4.94 g of 1,1,3,3- Tetramethyldioxane and 0.12 mL of 70% concentrated nitric acid were added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 60 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. The toluene was distilled off from the organic layer by an evaporator, and the mixture was distilled off under reduced pressure at 150 ° C for one hour, and then distilled under reduced pressure at 170 ° C for one hour to obtain colorlessness. Transparent viscous liquid polyoxyl resin (A2). The yield of polyoxyxylene resin (A2) is 16.05 g, the mass average molecular weight (Mw) is 1500, the viscosity is less than 200 cP, and the composition ratio is (H-SiMe). 2 O 1/2 ) 0.24 (Me 2 SiO 2/2 ) 0.30 (PhSiO 3/2 ) 0.45 (SiO 4/2 ) 0.01 The content of the H-Si group was 2.19 mmol/g, and the content of the HO-Si group was 2.9 mmol/g (4.9% by mass). [Starting Material Synthesis Example 2-3] Synthesis of Polydecane Oxygen Resin (B2) 20.00 g of polyfluorene oxide resin (II), 60.00 g of toluene, 20.00 g of methanol, and 6.86 g of 1,3-divinyl- 1,1,3,3-Tetramethyldioxane and 2.36 mL of 70% concentrated nitric acid were added to the flask and stirred at room temperature. After 4 hours, the reaction solution was transferred to a separatory funnel, and 60 g of water was added thereto, and after the extraction operation, the organic layer was recovered. The same operation was repeated 4 times, thereby washing the organic layer. The toluene was distilled off from the organic layer by an evaporator, and the mixture was distilled off under reduced pressure at 150 ° C for one hour, and then distilled under reduced pressure at 170 ° C for one hour to obtain colorlessness. Transparent viscous liquid polyoxyl resin (B2). The yield of polyoxyxylene resin (B2) was 19.38 g, the mass average molecular weight (Mw) was 1500, the viscosity was 210 cP, and the composition ratio was (Vi-SiMe). 2 O 1/2 ) 0.32 (Me 2 SiO 2/2 ) 0.25 (PhSiO 3/2 ) 0.33 (SiO 4/2 ) 0.10 The content of the Vi-Si group was 2.19 mmol/g, and the content of the HO-Si group was 3.2 mmol/g (3.0% by mass). [Comparative Synthesis Example 1] 96.16 g (0.80 mol) of Me was taken in a 3-liter flask having a volume of 2 L of a stirring blade made of a fluororesin and a Dairy reflux apparatus. 2 Si(OMe) 2 158.64 g (0.80 mol) of PhSi(OMe) 3 . Then, 180.15 g of water and 0.12 g of acetic acid were added to the flask, and the flask was continuously heated at 100 ° C for 6 hours to carry out hydrolysis and condensation reaction. Thereafter, the reaction solution was returned to room temperature, and 52.08 g of Si(OEt) was added. 4 The flask was placed in the flask, and the flask was continuously heated at 100 ° C for 6 hours to carry out hydrolysis and condensation reaction. As a result, a white solid was obtained but not obtained (Me 2 SiO 2/2 ) the structural unit represented, (PhSiO 3/2 ) the structural unit represented and (SiO 4/2 The target of the structural unit represented by the polyoxyl resin. [Comparative Synthesis Example 2] 20.00 g of a polyoxyxylene resin (I) was taken in a flask having a volume of 200 mL of a stirring blade made of a fluororesin and a Dy's reflux. Then, 7.64 g of Si(OEt) 4 5.29 g of an 11 mmol/L aqueous acetic acid solution was added to the flask, and the flask was continuously heated at 100 ° C for 6 hours to carry out hydrolysis and condensation reaction. As a result, a white solid and a gel-like substance were obtained, but not obtained (Me 2 SiO 2/2 ) the structural unit represented, (PhSiO 3/2 ) the structural unit represented and (SiO 4/2 The target of the structural unit represented by the polyoxyl resin. [Comparative Synthesis Example 3] Hydrolysis and condensation reactions were carried out in the same manner as in Comparative Synthesis Example 2 except that 3.4 μL of acetic acid was used instead of the aqueous acetic acid solution. As a result, a white solid was obtained in the flask, but it was not obtained (Me 2 SiO 2/2 ) the structural unit represented, (PhSiO 3/2 ) the structural unit represented and (SiO 4/2 The target of the structural unit represented by the polyoxyl resin. [Comparative Synthesis Example 4] Hydrolysis and condensation reactions were carried out in the same manner as in Comparative Synthesis Example 2, except that 3.4 μL of acetic acid and 7.06 g of 2-propanol were used instead of the aqueous acetic acid solution. Thereafter, the reaction liquid was transferred to a separatory funnel, and 50 mL of toluene and 50 mL of water were added to carry out an extraction operation, and then the organic layer was recovered. The organic layer was then washed twice with 50 mL of water. Toluene was distilled off from the organic layer by means of an evaporator. As a result, a polyfluorene oxide resin which is a colorless transparent liquid was obtained, but it was not obtained (Me 2 SiO 2/2 ) the structural unit represented, (PhSiO 3/2 ) the structural unit represented and (SiO 4/2 The target of the structural unit represented by the polyoxyl resin. [Comparative Synthesis Example 5-1] Synthesis of polyfluorene oxide resin (PI) except 96.16 g (0.8 mol) of Me 2 Si(OMe) 2 And 158.64 g (0.8 mol) of PhSi (OMe) 3 In addition, take 52.08 g (0.25 mol) of Si (OEt) 4 Further, hydrolysis and condensation reactions were carried out in the same manner as in Comparative Synthesis Example 1 except for the above. Thereafter, the reaction solution was returned to room temperature, transferred to a 2 L separatory funnel, and 400 mL of toluene and 400 mL of water were added to carry out a liquid separation operation, and then the aqueous layer was removed. The organic layer was washed twice with 400 mL of water. Thereafter, the organic layer was recovered, and toluene was distilled off under reduced pressure by an evaporator. As a result, a polyfluorene oxide resin (PI) as a colorless viscous liquid was obtained. The yield of polyoxynene resin (PI) is 288.82 g, the mass average molecular weight (Mw) is 1200, and the composition ratio is (Me). 2 SiO 2/2 ) 0.36 (PhSiO 3/2 ) 0.48 (SiO 4/2 ) 0.16 The content of the HO-Si group was 8.4 mmol/g (14% by mass). [Comparative Synthesis Example 5-2] Synthesis of polyfluorene oxide resin (PA1) except that 179.22 g of polyoxynoxy resin (PI), 537.66 g of toluene, 179.22 g of methanol, and 35.30 g of 1,1,3,3 were used. -Tetramethyldioxane and 0.84 mL of 70% concentrated nitric acid instead of 20.00 g of polyoxyl resin (II), 60.00 g of toluene, 20.00 g of methanol, 4.94 g of 1,1,3,3-four The reaction was carried out in the same manner as in the raw material Synthesis Example 2-2 except for methyl dioxane and 0.12 mL of 70% concentrated nitric acid. Thereafter, the same operation as in the raw material Synthesis Example 2-2 was carried out, except that 540 g of water was used instead of 60 g of water. As a result, a polyfluorene oxide resin (PA1) which is a colorless transparent viscous liquid was obtained. The yield of polyoxyphthalocene resin (PA1) is 159.76 g, the mass average molecular weight (Mw) is 2400, the viscosity is 42000 cP, and the composition ratio is (H-SiMe). 2 O 1/2 ) 0.23 (Me 2 SiO 2/2 ) 0.14 (PhSiO 3/2 ) 0.52 (SiO 4/2 ) 0.11 The content of the H-Si group was 2.1 mmol/g, and the content of the HO-Si group was 3.2 mmol/g (6% by mass). [Comparative Synthesis Example 5-3] Synthesis of polyfluorene oxide resin (PB1) except that 89.61 g of polyoxynoxy resin (PI), 268.83 g of toluene, 89.61 g of methanol, and 24.56 g of 1,3-divinyl were used. -1,1,3,3-tetramethyldioxane and 24.50 mL of 70% concentrated nitric acid instead of 20.00 g of polyoxyl resin (II), 60.00 g of toluene, 20.00 g of methanol, 6.86 g of 1 The reaction was carried out in the same manner as in the raw material Synthesis Example 2-3 except that 3-divinyl-1,1,3,3-tetramethyldioxane and 2.36 mL of 70% concentrated nitric acid were used. Thereafter, the same operation as in the raw material Synthesis Example 2-3 was carried out, except that 270 g of water was used instead of 60 g of water. As a result, a polyfluorene oxide resin (PB1) as a colorless transparent viscous liquid was obtained. The yield of polyoxyphthalocene resin (PB1) was 92.52 g, the mass average molecular weight (Mw) was 1700, the viscosity was 11000 cP, and the composition ratio was (Vi-SiMe). 2 O 1/2 ) 0.22 (Me 2 SiO 2/2 ) 0.21 (PhSiO 3/2 ) 0.44 (SiO 4/2 ) 0.13 The content of the Vi-Si group was 2.0 mmol/g, and the content of the HO-Si group was 2.1 mmol/g (4% by mass). [Comparative Synthesis Example 6-1] Synthesis of Polyoxyxylene Resin (QI) In the same manner as in Comparative Synthesis Example 5, except that water and acetic acid were added to the flask, 239.6 g of 2-propanol was further added. Hydrolysis and condensation reactions are carried out. Thereafter, the same operation as in Comparative Synthesis Example 5 was carried out, and as a result, a polyoxyxylene resin (QI) as a colorless viscous liquid was obtained. The yield of polyoxyxylene resin (QI) is 143.4 g, the mass average molecular weight (Mw) is 1,100, and the composition ratio is (Me). 2 SiO 2/2 ) 0.36 (PhSiO 3/2 ) 0.50 (SiO 4/2 ) 0.14 The content of the HO-Si group was 7.9 mmol/g (14% by mass). [Comparative Synthesis Example 6-2] Synthesis of polyfluorene oxide resin (QA1) except that 173.7 g of polyoxynoxy resin (QI), 521.1 g of toluene, 173.7 g of methanol, and 32.3 g of 1,1,3,3 were used. -Tetramethyldioxane and 0.77 mL of 70% concentrated nitric acid instead of 20.00 g of polyoxyl resin (II), 60.00 g of toluene, 20.00 g of methanol, 4.94 g of 1,1,3,3-four The reaction was carried out in the same manner as in the raw material Synthesis Example 2-2 except for methyl dioxane and 0.12 mL of 70% concentrated nitric acid. Thereafter, the same operation as in the raw material Synthesis Example 2-2 was carried out except that 521.1 g of water was used instead of 60 g of water. As a result, a polyfluorene oxide resin (QA1) which is a colorless transparent viscous liquid was obtained. The yield of polyoxyxylene resin (QA1) is 165.7 g, the mass average molecular weight (Mw) is 3300, the viscosity is 94000 cP, and the composition ratio is (H-SiMe). 2 O 1/2 ) 0.24 (Me 2 SiO 2/2 ) 0.15 (PhSiO 3/2 ) 0.48 (SiO 4/2 ) 0.13 The content of the H-Si group was 2.3 mmol/g, and the content of the HO-Si group was 3.1 mmol/g (5 mass%). [Comparative Synthesis Example 6-3] Synthesis of polyoxyxylene resin (QB1) except that 91.4 g of polyoxynoxy resin (QI), 274.2 g of toluene, 91.4 g of methanol, and 23.6 g of 1,3-divinyl were used. -1,1,3,3-tetramethyldioxane and 8.10 mL of 70% concentrated nitric acid instead of 20.00 g of polyoxyl resin (II), 60.00 g of toluene, 20.00 g of methanol, 6.86 g of 1 The reaction was carried out in the same manner as in the raw material Synthesis Example 2-3 except that 3-divinyl-1,1,3,3-tetramethyldioxane and 2.36 mL of 70% concentrated nitric acid were used. Thereafter, the same operation as in the raw material Synthesis Example 2-3 was carried out except that 274.2 g of water was used instead of 60 g of water. As a result, a polyoxynoxy resin (QB1) as a colorless transparent viscous liquid was obtained. The yield of polyoxyxylene resin (QB1) is 99.2 g, the mass average molecular weight (Mw) is 1900, the viscosity is 9600 cP, and the composition ratio is (Vi-SiMe). 2 O 1/2 ) 0.23 (Me 2 SiO 2/2 ) 0.19 (PhSiO 3/2 ) 0.43 (SiO 4/2 ) 0.15 The content of the Vi-Si group was 2.2 mmol/g, and the content of the HO-Si group was 1.7 mmol/g (3 mass%). [Comparative Synthesis Example 7-2] Synthesis of polyfluorene oxide resin (RA1) except that 39.7 g of polyoxyl resin (I), 119 g of toluene, 39.7 g of methanol, and 8.3 g of 1,1,3,3 were used. - tetramethyldioxane and 0.20 mL of 70% concentrated nitric acid instead of 20.00 g of polyoxyl resin (II), 60.00 g of toluene, 20.00 g of methanol, 4.94 g of 1,1,3,3-tetra The reaction was carried out in the same manner as in the raw material Synthesis Example 2-2 except for methyl dioxane and 0.12 mL of 70% concentrated nitric acid. Thereafter, the same operation as in the raw material Synthesis Example 2-2 was carried out except that 119 g of water was used instead of 60 g of water. As a result, a polyfluorene oxide resin (RA1) which is a colorless transparent viscous liquid was obtained. The yield of polyoxyphthalocene resin (RA1) is 42.5 g, the mass average molecular weight (Mw) is 1900, the viscosity is 200 cP, and the composition ratio is (H-SiMe). 2 O 1/2 ) 0.27 (Me 2 SiO 2/2 ) 0.31 (PhSiO 3/2 ) 0.42 The content of the H-Si group was 2.8 mmol/g, and the content of the HO-Si group was 2.0 mmol/g (3.4% by mass). [Comparative Synthesis Example 7-3] Synthesis of polyfluorene oxide resin (RB1) except that 19.9 g of polyoxyl resin (I), 59.7 g of toluene, 19.9 g of methanol, and 5.76 g of 1,3-divinyl were used. -1,1,3,3-tetramethyldioxane and 1.98 mL of 70% concentrated nitric acid instead of 20.00 g of polyoxyl resin (II), 60.00 g of toluene, 20.00 g of methanol, 6.86 g of 1 The reaction was carried out in the same manner as in the raw material Synthesis Example 2-3 except that 3-divinyl-1,1,3,3-tetramethyldioxane and 2.36 mL of 70% concentrated nitric acid were used. Thereafter, the same operation as in the raw material Synthesis Example 2-3 was carried out, except that 59.7 g of water was used instead of 60 g of water. As a result, a polyfluorene oxide resin (RB1) which is a colorless transparent viscous liquid was obtained. The yield of polyoxyxylene resin (RB1) was 20.6 g, the mass average molecular weight (Mw) was 1800, the viscosity was 350 cP, and the composition ratio was (Vi-SiMe). 2 O 1/2 ) 0.23 (Me 2 SiO 2/2 ) 0.32 (PhSiO 3/2 ) 0.45 The content of the Vi-Si group was 2.3 mmol/g, and the content of the HO-Si group was 2.1 mmol/g (3.6% by mass). Regarding the synthesized polyoxyloxy resins (A1), (B1), (A2), (B2), (PA1), (PB1), (QA1), (QB1), (RA1), (RB1), the composition ratio The physical property values (the content of the HO-Si group, the content of the H-Si group or the Vi-Si group, the mass average molecular weight, the viscosity, the refractive index, and the transparency) are shown in Table 2. [Table 2] As shown in Table 2, the polyfluorene oxide resins (A1), (B1), (A2), and (B2) obtained in the raw material synthesis examples and the polyoxyxylene resins (PA1) and (PB1) obtained in the comparative synthesis examples, (QA1) and (QB1) comparisons show extremely low viscosity. Also, as compared with the comparative synthesis example, it has no (SiO 4/2 The polyoxynoxy resin (RA1) and (RB1) of the polyoxyl resin represented by the structural unit shown also showed the same or lower viscosity. The polyfluorene oxide resins (A1), (B1), (A2), and (B2) obtained in the raw material synthesis examples all have (SiO 4/2 ) the structural unit represented, and therefore does not have (SiO 4/2 The crosslinking density of the structural unit represented by the structural unit becomes higher. As described above, although the crosslinking density is generally higher, the viscosity becomes higher, but the polyoxynoxy resins (A1), (B1), (A2), and (B2) all exhibit low viscosity. Further, as shown in Comparative Synthesis Examples 1 to 4, when acetic acid is used as a catalyst for hydrolysis polycondensation, when acetic acid aqueous solution is used, or when acetic acid and 2-propanol as a solvent are used, Unable to synthesize with (Me 2 SiO 2/2 ) the structural unit represented, (PhSiO 3/2 ) the structural unit represented and (SiO 4/2 The target of the structural unit represented by the polyoxyl resin. On the other hand, as shown in the raw material synthesis example, when using a strong acid catalyst such as nitric acid, it can be synthesized at least (Me 2 SiO 2/2 ) the structural unit represented, (PhSiO 3/2 ) the structural unit represented and (SiO 4/2 The target of the structural unit represented by the polyoxyl resin. 3. Preparation of the curable polyoxyxene resin composition In the following Examples 1 to 2 and Comparative Examples 1 to 3, it is selected from the group consisting of polyoxyxylene resins (A1), (A2), (PA1), and (QA1). And one of the groups consisting of (RA1) as the component (A), which is selected from the group consisting of polyoxyxylene resins (B1), (B2), (PB1), (QB1), and (RB1). As the component (B), the component (A) and the component (B) are prepared such that the mass of the component (A): the mass of the component (B) is 2:1, and further, the platinum contact as the component (C) The mixture was mixed to prepare compositions 1 to 5. Here, as the platinum catalyst, a platinum-divinyltetramethyldioxane complex is used in such a manner that the content of the platinum atom is 0.03 ppm by mass based on the total amount of the composition. The compositions of the compositions 1 to 5 prepared are shown in Table 3. 4. Evaluation method of physical properties of composition and cured product The viscosity of the prepared composition, the content of HO-Si group, and the physical properties of the cured product obtained from the composition (hardness, adhesion, transparency, and the like) were measured by the following methods. Linear thermal expansion coefficient, subsequent strength), appearance at the time of hardening, and press formability. [Viscosity of the composition] The viscosity of the prepared composition is based on "Measurement of viscosity by a cone-plate-shaped rotational viscometer" in JIS Z8803 (2011), using a rotational viscometer (manufactured by ANTON PAAR, trade name: PHYSICA) MCR51, measuring range 200 to 1,000,000 cP) and temperature control unit (manufactured by ANTON PAAR, trade name: P-PTD200), measured at a shear rate of 30 [1/s] in a standard state (25 ° C, 1 atm) The value obtained after 1 minute from the start of the measurement was used. When the low viscosity liquid is not in the measurement range, it is marked as "<200". [HO-Si group content of composition] The HO-Si group content of the prepared composition was calculated by the following calculation formula. [HO-Si group content of composition]={(HO-Si group content of (A) component)×2+ (HO-Si group content of (B) component)}/2 [hardness of hardened material] Combined logistics into the mold (25 mm The mixture was heated in air at 90 ° C for 1 hour, and further heated at 150 ° C for 4 hours to prepare a cured product having a thickness of 4 to 5 mm. Using a Durometer (manufactured by Teclock Co., Ltd., model: GS-719R, GS-720R), the cured product was measured by the method specified in JIS K 7215 "Plastic Hardness Test Method for Plastics". A or the hardness of Xiao's D. [Adhesion test of cured product (SMD3528 type PPA resin package)] The prepared mixture was transferred into SMD3528 type PPA resin package (surface mount part 3528 type polyphthalamide resin package) (3.5 mm× 2.8 mm × 0.9 mm), heated at 90 ° C for 1 hour in the air, and further heated at 150 ° C for 4 hours to prepare 24 specimens as a cured product. These samples were confirmed by an optical microscope (optical magnification: 3 times to 30 times), and the cured product was evaluated as "peeling" from the package, and the unpeeled person was evaluated as "closed". Among the 24 samples, the number of samples evaluated as "closed" was counted as "qualified number". [Adhesion test of cured product (SMD6050 type PPA resin package)] The prepared composition was transferred into an SMD6050 type PPA resin package (6.0 mm × 5.0 mm × 2.0 mm), and heated at 90 ° C for 1 hour in the air. Further, the mixture was heated at 150 ° C for 4 hours to prepare 12 specimens as a cured product. These samples were confirmed by an optical microscope (optical magnification: 3 times to 30 times), and the cured product was evaluated as "peeling" from the package, and the unpeeled person was evaluated as "closed". Among the 12 samples, the number of samples evaluated as "closed" was counted as "qualified number". [Transparency of hardened material] The prepared mixture was transferred into a mold (22 mm) ), heated at 90 ° C for 1 hour in air, and further heated at 150 ° C for 4 hours to make 22 mm 2 mm thick hardened material. The transmittance of the cured product at a wavelength of 405 nm and 365 nm was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV-3150). [Heat-resistant transparency of hardened material] The prepared mixture was transferred into a mold (22 mm ), heated at 90 ° C for 1 hour in air, and further heated at 150 ° C for 4 hours to make 22 mm 2 mm thick hardened material. After the cured product was heated at 200 ° C for 100 hours, the transmittance of the cured product at a wavelength of 405 nm and 365 nm was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, model: UV-3150). [Linear thermal expansion coefficient of hardened material] 0.7 g of the prepared composition was added to a fluororesin tube (inner diameter: 5.8 mm) In the height: 1.8 mm), it was heated at 90 ° C for 1 hour in the air, and further heated at 150 ° C for 4 hours to prepare a cured product. The cured product was heated from 25 ° C to 200 ° C in a temperature of 5 ° C / min using a ThermoPlusTM A8310 (manufactured by RIGAKU Co., Ltd.), and the linear thermal expansion coefficient was measured. The measurement was performed twice, and the measured value was the second time. [Continuation strength of hardened material] The prepared composition was mixed with a zirconia ball having a diameter of 50 μm, and was applied to a glass piece (5.0 mm × 5.0 mm × 1.1 mm) and a glass substrate (50 mm × 50 mm × 3.0 mm). In the state between them, it was heated at 90 ° C for 1 hour in the air, and further heated at 150 ° C for 4 hours to be hardened. The adhesion (adequate strength) of the produced sample was measured by a adhesion tester (manufactured by DAGE JAPAN Co., Ltd., model: Dage 4000 Plus). The strength of the hardened material is weak, and the hardened material is destroyed at the time of measurement, and the value of the subsequent strength cannot be obtained as "aggregation damage". [Appearance of hardened material] 1 g of the prepared composition was developed on a glass mold (22 mm) ), heated at 90 ° C for 1 hour in air, and further heated at 150 ° C for 4 hours to make 22 mm 2 mm thick hardened material. Three test pieces were produced, and the appearance of the test piece was visually confirmed. In all of the test pieces, the state in which no foaming and cracking were observed in the cured product was rated as "good". The situation other than it is rated as "bad". [Press Formability Test] The prepared composition was poured into a mold (90 mm × 90 mm × 2 mm), heated in air at 90 ° C for 1 hour, and further heated at 150 ° C for 4 hours to prepare a plate-like cured product. The plate-like cured product was press-formed into a dumbbell-shaped No. 8 shape in accordance with JIS K6251. When the hardened body was pressed, no cracking or resin leakage occurred, and the press-formed product was evaluated as "good". The situation other than this was evaluated as "bad". 5. Examples and Comparative Examples [Examples 1 to 2 and Comparative Examples 1 to 3] The above physical property evaluation tests (Examples 1 and 2) were carried out using the prepared compositions 1 and 2. Similarly, the above physical property evaluation test (Comparative Examples 1 to 3) was carried out using the prepared compositions 3 to 5. These results are shown in Table 3. [table 3] As shown in Table 3, the compositions 1 to 2 prepared in Examples 1 and 2 had extremely low viscosities as compared with the compositions 3 to 4 prepared in Comparative Examples 1 and 2. Further, the cured product obtained from the compositions 1 to 2 exhibited a good appearance and press formability, and had the same physical properties in terms of adhesion and transparency. Further, compared with the cured product obtained from the low viscosity composition 5 of Comparative Example 3, it has excellent physical properties in terms of adhesion and resin strength. The above indicates that the compositions 1 to 2 prepared in Examples 1 to 2 belonging to the scope of the present invention have extremely low viscosity, and the cured product has good physical properties.