(3) (3)1378124 本發明者爲達成上述目的，進行精密硏討後結果發現 ’於含有下述一般式（1)所示之二有機聚矽氧烷與1分 子中玉少具有3個可水解基之有機矽化合物所成之室溫硬 化性有機聚矽氧烷組成物中以含有 (甲）熔點或軟化點爲1 00°C以上之羧酸30〜70質量 %， (乙）CnH2n+1COOH(n爲10以上之數）所示之脂肪 酸1 0〜50質量％， (丙）CnHh-iCOOHCn爲10以上之數）或 CnH2n-3COOH(n爲10以上之數）所示之不飽和脂肪酸 5〜30質量％，之處理劑相對於碳酸鈣以2.5〜4.5質量％之 量所處理之碳酸鈣爲塡充材配合後，可取得與被覆材之黏 著性’特別是以氟樹脂、丙烯酸樹脂等對於表面處理之鋁 材之黏著性佳、溫水黏著性佳之硬化物，且組成物貯存時 之保存安定性良好之解決上述先行技術之問題點，進而完 成本發明。 【化1】 R1(3) (3) 1378124 In order to achieve the above object, the inventors of the present invention found that the two organic polyoxoxanes represented by the following general formula (1) and the one molecule have three The composition of the room temperature curable organopolyoxane formed by the hydrolyzable organic ruthenium compound is 30 to 70% by mass of a carboxylic acid having a (meth) melting point or a softening point of 100 ° C or more, (B) CnH2n 0-1COOH (n is a number of 10 or more) of fatty acids 10 to 50% by mass, (C) CnHh-iCOOHCn is 10 or more) or CnH2n-3COOH (n is 10 or more) of unsaturated 5 to 30% by mass of the fatty acid, and the calcium carbonate treated with calcium carbonate in an amount of 2.5 to 4.5% by mass based on the calcium carbonate is blended with the crucible, and the adhesion to the coated material can be obtained, particularly fluororesin or acrylic acid. The present invention has been accomplished by solving the problems of the above-mentioned prior art, such as a resin having good adhesion to a surface-treated aluminum material and a cured product having good warm water adhesion, and good storage stability at the time of storage of the composition. [1] R1
I ΗΟ-ίδΙΟ^Η (1) (其中，式中R1爲取代或非取代之1價烴基，m爲正之 整數。） ^ 亦即，本發明係提供—種其特徵爲含有 (1)上述一般式（1)所示之二有機聚矽氧烷100質 (4) 1378124 量份， • (2) 1分子中至少具有3個可水解基之有機矽化合物 • 0.2~20質量份， (3 )以含有（甲）熔點或軟化點爲100°C以上之羧酸 3 0 ~ 7 0 質量 ％， (乙）CnH2n+1COOH ( η爲10以上之數）所示之飽和 脂肪酸1〇~50質量％， • (丙）CnH2n- 〖COOH ( η爲1 0以上之數）或CnH2n. 3COOH(n爲1〇以上之數）所示之不飽和脂肪酸5~30質 量％，之處理劑相對於碳酸鈣以2.5~4.5質量％之量所處理 之膠質碳酸鈣20〜200質量份所成之室溫硬化性有機聚矽 氧烷組成物。 _ 本發明之室溫硬化性有機聚矽氧烷組成物，賦予與被 - 覆材之黏著性，特別是對於表面處理之鋁材等之黏著性佳 ’浸水及耐熱黏著性良好之硬化物，因此，可適用於黏著 ® 材料、塗層材料、電氣絕緣密封材、建築用密封材等。 • 【實施方式】 •[發明實施之最佳形態] . 以下’針對本發明進行更詳細說明，本發明室溫硬化 性有機聚矽氧烷組成物係使用下述一般式（1)所示之二 有機聚矽氧烷做爲基劑聚合物， 【化2】 R1 HO-ffiiOjrH R1I ΗΟ-ίδΙΟ^Η (1) (wherein R1 is a substituted or unsubstituted monovalent hydrocarbon group, and m is a positive integer.) ^ That is, the present invention provides a feature characterized by containing (1) the above general a compound of the formula (1): (1) 1378,124 parts by weight, (2) an organic ruthenium compound having at least three hydrolyzable groups in one molecule, 0.2 to 20 parts by mass, (3) a saturated fatty acid having a (a) melting point or a softening point of 100 ° C or more and a carboxylic acid of 100 ° C or more, (B) CnH 2 n + 1 COOH ( η is 10 or more), 1 to 50% by mass , (C)CnH2n- 〖COOH (η is more than 10) or CnH2n. 3COOH (n is 1〇 or more) 5 to 30% by mass of unsaturated fatty acid, the treatment agent is relative to calcium carbonate A room temperature curable organopolyoxane composition formed by using 20 to 200 parts by mass of colloidal calcium carbonate treated in an amount of 2.5 to 4.5% by mass. _ The room-temperature-curable organopolysiloxane composition of the present invention imparts adhesion to the coating material, particularly to the surface-treated aluminum material, and the like, which is excellent in water immersion and heat-resistant adhesion. Therefore, it can be applied to adhesive® materials, coating materials, electrical insulating sealing materials, building sealing materials, and the like. [Embodiment] [The best mode for carrying out the invention] The following description of the present invention will be described in more detail. The room temperature curable organopolysiloxane composition of the present invention is represented by the following general formula (1). Diorganopolyoxyalkylene as a base polymer, [Chemical 2] R1 HO-ffiiOjrH R1
I (1) -8 - (5) (5)1378124 (其中，式中R1爲取代或非取代之1價烴基，m爲正之 整數。） 上述一般式（1)中，R1爲取代或非取代之1價烴基 ’較佳者爲碳原子數1〜10，更佳者爲1〜8之非取代或取 代之1價烴基，如：甲基、乙基、丙基、丁基、己基等之 烷基、苯基、甲苯基等之芳基、乙烯基、烯丙基、丁烯基 、己烯基等之烯基、環己基等之環烷基、苄基、2-苯基乙 基等之芳烷基或使鍵結於此等基一部份或全部之碳原子之 氫原子被鹵素原子、氰基等取代之基，如：氯甲基、三氟 丙基、氰乙基等例，特別以甲基 '苯基、乙烯基、三氟丙 基者宜。 又，該式（1)中，m相當於聚合度之數，正之整數 ’其中，式（1)所示之二有機聚矽氧烷於25 °C之黏度爲 50~100萬mPa.s，特別以700〜10萬mpa. s爲最佳，調 整η値於上述範圍之黏度者宜。又，此黏度係藉由旋轉黏 度計之値者。 此式（1)之二有機聚矽氧烷之具體例如下述化合物 例。 【化3】 Me Me 1 Ph 1 HO-iSiO^H Me Me Ph Me Me 1 1 Me 1 Me 1 H〇-(SiO)p-(SiO)q-H Me CjH^CF, Me ch=ch2 (6) 1378124 (上述式中，Me爲甲基、Ph爲苯基、m與上述相同，p • 及q分別爲正之整數，且p + q相當於m之整數。） 接著’第2成份之1分子中至少具3個可水解基（水 解性基）之有機矽化合物係做爲硬化劑之作用者，本發明 組成物係於濕氣存在下，爲進行室溫硬化之必須成份者。 做爲此有機矽化合物者可使用做爲室溫硬化性之縮合型有 機聚矽氧烷組成物之公知硬化劑（有機矽化合物）。 其中，做爲該有機矽化合物中之水解性基例者如：甲 氧基、乙氧基、丙氧基、丁氧基、甲氧乙氧基等烷氧基、 二甲基酮肟基、丁酮肟基、二乙基酮肟基、環戊酮肟基、 環己酮肟基等酮肟基例，特別又以甲氧基、二甲基酮肟基 、二乙基酮肟基爲最佳。 又’做爲鍵結於此有機矽化合物之矽原子所得水解性 基以外之基者，以與上述第1成份之R1相同之取代或非 取代之1價烴基者宜，特別由易於合成之面觀之，又以碳 原子數爲之院基，碳原子數爲2〜10之嫌基及苯基爲 更佳。 做爲此第2成份之有機矽化合物之具體例者如：甲基 三甲氧基矽烷、乙烯基三甲氧基矽烷、苯基三甲氧基矽烷 、甲基三乙氧基矽烷、四甲氧基矽烷、四乙氧基矽烷、四 丙氧基矽烷、3-氯丙基三甲氧基矽烷等之烷氧基矽烷、甲 基三（丁酮肟）矽烷、乙烯基三（丁酮肟）矽烷、四（丁 酮肟）矽烷等酮肟矽烷、此等化合物之部份水解物等例。 -10- (7) 1378124 該第2成份之有機矽化合物配合量對於第1成份之式 (1)之二有機聚矽氧烷100質量份爲0.2〜2 0質量份者宜 - ’較佳者爲1.0〜18質量份，更佳者爲5.0〜15質量份。當 配合量未達0.2質量份則組成物之硬化將不足，反之，超 出20質量份則深部硬化速度變慢，同時所得硬化物變硬 變脆，損及密封材料之性能。 本發明做爲第3成份者係配合含有 ® (甲）熔點或軟化點爲l〇〇°C以上之羧酸30〜70質量 %， (乙）CnH2n+1COOH(n爲10以上之數）所示之飽和 脂肪酸1 0 ~ 5 0質量％， (丙）CnH^^COOHCn爲10以上之數）或 CnH2n.3COOH(n爲10以上之數）所示之不飽和脂肪酸 - 5〜30質量％相對於碳酸鈣以2.5〜4.5質量％之量進行處理 之膠質碳酸鈣。 ® 其中，碳酸鈣之必須條件係藉由含有 . (甲）熔點或軟化點爲l〇〇°C以上之羧酸 ，(乙）CnH2n+1COOH(n爲10以上之數）所示之飽和 脂肪酸， (丙）C^HhdCOOH (η爲10以上之數）或 CnH2n-3COOH(n爲10以上之數）所示之不飽和脂肪酸 之處理劑所處理者，而，特別是滿足以下條件時，將更具 充份之黏著性與耐久性之實現化。 (1 )平均粒徑使用0.2 μπι以下之碳酸鈣。 -11 - (12) (12)1378124 .I (1) -8 - (5) (5) 1378124 (wherein R1 is a substituted or unsubstituted monovalent hydrocarbon group, and m is a positive integer.) In the above general formula (1), R1 is a substituted or unsubstituted The monovalent hydrocarbon group is preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 8, such as methyl, ethyl, propyl, butyl, hexyl or the like. An alkyl group such as an alkyl group, a phenyl group or a tolyl group; an alkenyl group such as a vinyl group, an allyl group, a butenyl group or a hexenyl group; a cycloalkyl group such as a cyclohexyl group; a benzyl group; a 2-phenylethyl group; An aralkyl group or a group in which a hydrogen atom of a carbon atom to which a part or all of a group such as a bond is bonded is substituted with a halogen atom, a cyano group or the like, such as a chloromethyl group, a trifluoropropyl group or a cyanoethyl group; Particularly suitable for methyl 'phenyl, vinyl, trifluoropropyl. Further, in the formula (1), m corresponds to the number of polymerization degrees, and the positive integer 'wherein the viscosity of the diorganopolyoxyalkylene represented by the formula (1) at 25 ° C is 50 to 1,000,000 mPa·s, In particular, 700 to 100,000 mpa.s is the best, and it is preferable to adjust the viscosity of η to the above range. Again, this viscosity is achieved by rotating the viscometer. Specific examples of the organopolyoxane of the formula (1) are, for example, the following compounds. [Me 3] Me Me 1 Ph 1 HO-iSiO^H Me Me Ph Me Me 1 1 Me 1 Me 1 H〇-(SiO)p-(SiO)qH Me CjH^CF, Me ch=ch2 (6) 1378124 (In the above formula, Me is a methyl group, Ph is a phenyl group, m is the same as above, p and q are each a positive integer, and p + q corresponds to an integer of m.) Next, at least one molecule of the second component is at least The organic hydrazine compound having three hydrolyzable groups (hydrolyzable groups) functions as a hardener, and the composition of the present invention is in the presence of moisture and is an essential component for room temperature hardening. As the organic ruthenium compound, a known hardener (organo ruthenium compound) which is a room temperature curable condensed organic polyoxane composition can be used. Among them, as a hydrolyzable group in the organic hydrazine compound, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group or a methoxyethoxy group, or a dimethyl ketoximino group, a ketone oxime group such as butanone oxime, diethyl ketone oxime, cyclopentan oxime, cyclohexanone fluorenyl, and the like, in particular, a methoxy group, a dimethyl ketone oxime group, and a diethyl ketone fluorenyl group. optimal. Further, as the base other than the hydrolyzable group derived from the ruthenium atom of the organic ruthenium compound, it is preferably the same as the substituted or unsubstituted monovalent hydrocarbon group of R1 of the above first component, particularly from the surface which is easy to synthesize. It is better to use the carbon atom number as the base, the carbon number of 2 to 10, and the phenyl group. Specific examples of the organic ruthenium compound which is the second component are methyl trimethoxy decane, vinyl trimethoxy decane, phenyl trimethoxy decane, methyl triethoxy decane, tetramethoxy decane. , alkoxy decane such as tetraethoxy decane, tetrapropoxy decane, 3-chloropropyltrimethoxydecane, methyl tris(butanone oxime) decane, vinyl tris(butanone oxime) decane, four (butanone oxime) ketone decane such as decane, a partial hydrolyzate of these compounds, and the like. -10- (7) 1378124 The amount of the organic ruthenium compound of the second component is preferably 0.2 to 20 parts by mass based on 100 parts by mass of the formula (1) bis organopolyoxane of the first component - 'better It is 1.0 to 18 parts by mass, more preferably 5.0 to 15 parts by mass. When the blending amount is less than 0.2 part by mass, the hardening of the composition will be insufficient. On the contrary, if it exceeds 20 parts by mass, the deep hardening rate becomes slow, and at the same time, the obtained hardened material becomes hard and brittle, and the performance of the sealing material is impaired. The third component of the present invention is formulated to contain 30 to 70% by mass of a carboxylic acid having a melting point or a softening point of 10 ° C or more, and (b) CnH 2 n + 1 COOH (n is 10 or more) The saturated fatty acid is 10 to 50% by mass, (C) CnH^^COOHCn is 10 or more) or CnH2n.3COOH (n is 10 or more), and the unsaturated fatty acid is 5 to 30% by mass. A colloidal calcium carbonate treated with calcium carbonate in an amount of 2.5 to 4.5% by mass. ® Among them, the necessary conditions for calcium carbonate are saturated fatty acids represented by (a) a carboxylic acid having a melting point or a softening point of 10 ° C or higher, and (b) CnH 2 n + 1 COOH (n is 10 or more) , (C) is treated with a treatment agent of unsaturated fatty acid represented by C^HhdCOOH (η is 10 or more) or CnH2n-3COOH (n is 10 or more), and particularly, when the following conditions are satisfied, More complete adhesion and durability. (1) The average particle diameter is calcium carbonate of 0.2 μm or less. -11 - (12) (12) 1378124 .
[實施例1] 於萬能混合器中置入黏度5萬mPa.s之α ，ω-二經 基二甲基聚矽氧烷50質量份’表1之Α所示之處理碳酸 鈣50質量份、（丁酮肟）矽烷6質量份、二辛錫二月桂 酸酯0.1質量份、r-胺基丙基三乙氧基矽烷1質量份，進 行脫泡混合後，取得室溫硬化性有機聚矽氧烷組成物。 [實施例2] 以表1B所示之碳酸鈣取代表ία所示之碳酸鈣使用之 外’與實施例1同法取得室溫硬化性有機聚矽氧烷組成物 [比較例1 ] 以表1C所示之碳酸鈣取代表1A所示之碳酸鈣使用之 外’與實施例1同法取得室溫硬化性有機聚矽氧烷組成物 [比較例2 ] 以表1D所示之碳酸鈣取代表ία所示之碳酸鈣使用 以外，與實施例1同法取得室溫硬化性有機聚矽氧烷組成 物0 [比較例3] -16- (13) (13)1378124 以表1E所示之碳酸鈣取代表ία所示之碳酸鈣使用之 外，與實施例1同法取得室溫硬化性有機聚矽氧烷組成物 [比較例4] 以表1F所示之碳酸鈣取代表ία所示之碳酸鈣使用之 外’與實施例1同法取得室溫硬化性有機聚矽氧烷組成物 [比較例5] 以表1G所示之碳酸鈣取代表ία所示之碳酸鈣使用 之外’與實施例1同法取得室溫硬化性有機聚矽氧烷組成 物。 [比較例6] 以表1Η所示之碳酸鈣取代表1Α所示之碳酸鈣使用 之外’與實施例1同法取得室溫硬化性有機聚矽氧烷組成 物。 [比較例7] 以表II所不之碳酸銘取代表1Α所示之碳酸鈣使用之 外，與實施例1同法取得室溫硬化性有機聚砂氧院組成物 -17- (14) (14)1378124.[Example 1] 50 parts by mass of α,ω-dimercaptodimethylpolyoxane having a viscosity of 50,000 mPa·s was placed in a universal mixer, and 50 parts by mass of the treated calcium carbonate shown in Table 1 was placed. 6 parts by mass of (butanone oxime) decane, 0.1 parts by mass of dioctyltin dilaurate, and 1 part by mass of r-aminopropyltriethoxy decane, and after defoaming and mixing, room temperature hardening organic polymerization is obtained. A siloxane composition. [Example 2] The room temperature curable organopolyoxane composition was obtained by the same method as in Example 1 except that the calcium carbonate shown in Table 1B was used to represent the calcium carbonate represented by ία [Comparative Example 1] The calcium carbonate represented by 1C was taken to represent the calcium carbonate represented by 1A. In the same manner as in Example 1, the room temperature curable organopolyoxane composition was obtained [Comparative Example 2] The calcium carbonate shown in Table 1D was taken. The room temperature curable organopolyoxane composition was obtained in the same manner as in Example 1 except that calcium carbonate represented by ία was used. [Comparative Example 3] -16- (13) (13) 1378124 The room temperature curable organopolyoxane composition was obtained in the same manner as in Example 1 except that calcium carbonate was used to represent calcium carbonate represented by ία [Comparative Example 4] The calcium carbonate shown in Table 1F was represented by ία. In addition to the use of calcium carbonate, the room temperature curable organopolyoxane composition was obtained in the same manner as in Example 1 [Comparative Example 5] The calcium carbonate shown in Table 1G was taken as the calcium carbonate represented by ία. The room temperature curable organopolyoxane composition was obtained in the same manner as in Example 1. [Comparative Example 6] The room temperature curable organopolyoxane composition was obtained in the same manner as in Example 1 except that the calcium carbonate shown in Table 1A was used to represent the calcium carbonate represented by 1 。. [Comparative Example 7] A room temperature curable organic polyoxo composition -17-(14) was obtained in the same manner as in Example 1 except that the carbonic acid represented by Table II was used. 14) 1378124.
[比較例8 ] 以表1J所示之碳酸鈣取代表1A所示之碳酸鈣使用之 外’與實施例1同法取得室溫硬化性有機聚矽氧烷組成物 [比較例9] 以表1K所示之碳酸鈣取代表ία所示之碳酸鈣使用 之外’與實施例1同法取得室溫硬化性有機聚矽氧烷組成 物。 [比較例10] 以表1L·所示之碳酸鈣取代表ία所示之碳酸鈣使用之 外’與實施例1同法取得室溫硬化性有機聚矽氧烷組成物 [比較例1 1] 以表1M所示之碳酸鈣取代表1A所示之碳酸鈣使用 之外’與實施例1同法取得室溫硬化性有機聚矽氧烷組成 物。 針對上述實施例1〜2、比較例1〜1 1所得之室溫硬化 性有機聚矽氧烷組成物於聚丙烯製3 3 0ml筒中，23。(：， 5 0%RH之環境下，保存2年後’進行確其開封後之作業性 、硬化性。結果示於表2。 針對上述實施例1 ~2、比較例1〜1 1所得之室溫硬化 -18- 9 (15) 1378124. 性有機聚矽氧烷組成物，依JIS-A (5758)爲基 • 述方法進行嵌段H-1型黏著試驗。結果示於表2 . 使用凱納系氟塗裝鋁做爲被覆材料，使用上 化性有機聚矽氧烷組成物做爲密封材料，於溫度 度5〇%RH進行硬化7天後脫模，30艺下熟化7 做成初期之黏著試驗。 又，製成試料嵌段後，於5 0 °C之溫水中使浸 • 嵌段做成浸水後，進行黏著試驗。 使用（股份）東洋精機製作所製Strograph 嵌段之測定試驗機，於張力速度50mm/min下進:{ CF係以目視觀察張力試驗後之被覆材料與 . 之剪切面狀態，使密封材料殘留比例以％示之。 - 由表2結果證明，本發明室溫硬化性有機聚 成物具有與表面處理鋁材之黏著性良好，特別具 水黏著性、室溫下保存性亦良好。 準，以下 述室溫硬 23〇C、濕 天之嵌段 漬7天之 R-2做爲 ί測定。 密封材料 砂氧院組 良好的溫 -19- (16) 1378124.[Comparative Example 8] A room temperature curable organopolyoxane composition was obtained in the same manner as in Example 1 except that calcium carbonate represented by Table 1J was used to represent calcium carbonate represented by 1A [Comparative Example 9] The room temperature curable organopolyoxane composition was obtained in the same manner as in Example 1 except that the calcium carbonate represented by 1K was used to represent the calcium carbonate represented by ία. [Comparative Example 10] The room temperature curable organopolyoxane composition was obtained in the same manner as in Example 1 except that the calcium carbonate shown in Table 1L· was used to represent the calcium carbonate represented by ία [Comparative Example 1 1] The room temperature curable organopolyoxane composition was obtained in the same manner as in Example 1 except that the calcium carbonate shown in Table 1M was used to represent the calcium carbonate represented by 1A. The room temperature curable organopolyoxane compositions obtained in the above Examples 1 to 2 and Comparative Examples 1 to 1 were made into a 300 ml cylinder made of polypropylene, 23. (:, in the environment of 50% RH, after 2 years of storage, 'workability and hardenability after the opening was confirmed. The results are shown in Table 2. For the above Examples 1 to 2 and Comparative Examples 1 to 1 1 Room temperature hardening -18- 9 (15) 1378124. The composition of the organopolyaluminoxane was tested according to JIS-A (5758). The block H-1 type adhesion test was carried out. The results are shown in Table 2. Kina fluorinated aluminum is used as the coating material, and the composition of the superplastic organic polysiloxane is used as a sealing material. After curing at a temperature of 5〇% RH for 7 days, the mold is released, and 30 is matured. In the initial adhesion test, after the sample block was prepared, the immersion block was immersed in warm water at 50 ° C, and the adhesion test was carried out. The test of the Strograph block manufactured by Toyo Seiki Co., Ltd. was used. Machine, at a tension speed of 50mm/min: { CF is to visually observe the state of the sheared surface of the coated material after the tensile test, so that the residual ratio of the sealing material is shown in %. - The results of Table 2 prove that the present invention Room temperature hardening organic polymer has good adhesion to surface treated aluminum, especially water adhesion The storage stability at room temperature is also good. Precisely, the following room temperature is hard 23〇C, and the block of wet days is 7 days of R-2 as the ί. Sealing material sand oxygen group good temperature-19- ( 16) 1378124.
[表2] 實 實 比 比 比 比 比 比 比 比 比 比 比 施 施 較 較 較 較 較 較 較 較 較 較 較 例 例 例 例 例 例 例 例 例 例 例 例 例 1 2 1 2 3 4 5 6 7 8 9 10 11 碳酸鈣 A B C D E F G Η I J Κ L Μ 保存性 〇 Δ X X X X X X 〇 〇 X X X 對於Dickfro-metalic之Η型張力黏著性試驗結果 初期 CF(°/〇) 100 100 100 100 100 100 100 100 60 60 100 80 100 浸水後 CF(%) 100 100 100 100 0 0 50 100 40 40 100 10 0[Table 2] The actual ratio is more than the ratio of the specific example. The example is 1 2 1 2 3 4 5 6 7 8 9 10 11 Calcium carbonate ABCDEFG Η IJ Κ L Μ Preservation 〇 Δ XXXXXX 〇〇 XXX For Dickfro-metalic Η type tensile adhesion test results Initial CF (° / 〇) 100 100 100 100 100 100 100 100 60 60 100 80 100 Immersion After CF (%) 100 100 100 100 0 0 50 100 40 40 100 10 0
(注1 )於23°C，5 0%RH下保存2年後，相較於初期 其外觀、作業性、硬化性無差異者爲〇、稍出現不良者爲 △、明顯不良者爲X。(Note 1) After storage for 2 years at 23 ° C and 50% RH, it is 〇 if there is no difference in appearance, workability, and hardenability at the initial stage, △ is slightly worse, and X is obviously bad.
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