200948837 六、發明說明： 【發明所屬之技術領域】 本發明係有關聚異氰酸酯組成物及使用其之二液型塗 料組成物。 【先前技術】 以聚異氰酸酯作爲一種成份使用之二液型之胺基甲酸 Φ 酯系塗料因具有良好的耐氣候性、耐磨損性之塗膜，故先 行技術中被利用於建築物、土木架構物等之室外基材的塗 裝、汽車的修補、塑膠之塗裝等。 該塗料中，由聚異氰酸酯之極性的高度，通常使用甲 苯、二甲苯等之芳香族烴溶劑、乙酸丁酯等之酯系溶劑等 之強溶劑，亦即使用溶解力強之溶劑。 此等強溶劑由於臭氣強，故由其作業環境改善面，減 少地球環境負荷面觀之，近年來有避開的傾向。進一步， ® 由舊塗膜上重新塗佈修補，進行塗佈更新時，含有修補用 塗料中具有高度溶解力之強溶劑時，舊塗膜膨潤或溶解， 務必修補至舊塗膜。其結果造成塗佈作業的擴大化、煩雜 化、塗佈費用增加、工期延長等問題的產生。 有鑑於上述，近年被提倡開發一種易溶於低極性有機 溶劑之聚異氰酸酯。 如：專利文獻1 (特開平8-1 98928號公報）中，作爲 經由低極性溶劑稀釋性良好之聚異氰酸酯者，被揭示有： 使脂環式二異氰酸酯與經由低極性溶劑之稀釋性爲1 〇〇% 200948837 以上之多元醇進行反應後得到聚異氰酸酯。 又，專利文獻2 (特開20〇8-24828號公報）中，作爲 對於低極性有機溶劑之溶解性及矽酸酯化合物之互溶性良 好之聚異氰酸酯者，被揭示有：由脂肪族及/或脂環二異 氰酸酯以及碳數1〜20之單醇所得之具有特定之脲基甲酸 酯基/三聚異氰酸酯基之莫耳比及特定分子量分佈之聚異 氰酸酯化合物。 該專利文獻1及專利文獻2之聚異氰酸酯對於低極性 有機溶劑而言，溶解性均良好，惟，與主劑之多元醇化合 物之互溶性，所得塗膜之表面硬度等之各種物性面中，卻 有進一步改善的空間，且低極性溶劑之選擇亦有改善的空 間。 專利文獻1 :特開平8- 1 9 8928號 專利文獻2:特開2008-24828號 【發明內容】 本發明係鑑於上述問題，提供一種可溶於低極性有機 溶劑’同時與多元醇化合物之互溶性良好，可賦予表面硬 度爲首之各種物性良好之塗膜之聚異氰酸酯組成物及使用 其之二液型塗料組成物者爲其目的。 本發明者爲達成該目的，進行精密硏討後結果發現， 使六甲撐二異氰酸酯與碳數11〜20之脂肪族單醇進行反 應而得到之聚異氰酸酯之脲基甲酸酯基/三聚異氰酸酯基 之莫耳比作成特定範圍後’可提昇對於低極性有機溶劑之 -6 - 200948837 溶解性，同時’由含此之聚異氰酸酯與多元醇之塗料所得 之塗膜中，提昇始於表面硬度之各種物性，進而完成本發 明。 亦即，本發明係提供： 1. 含有使六甲撐二異氰酸酯與碳數1 1〜20之脂肪 族單醇經由反應而得到之聚異氰酸酯及苯胺點爲10〜70 °C 之低極性有機溶劑或混合苯胺點爲5〜5 0 °C之低極性有機 〇 溶劑，該聚異氰酸酯於分子內具有脲基甲酸酯基、三聚異 氰酸酯基及胺基甲酸酯基，同時，該脲基甲酸酯基與三聚 異氰酸酯基之莫耳比爲脲基甲酸酯基/三聚異氰酸酯基 = 7 0/30〜3 0/7 0者爲其特徵之聚異氰酸酯組成物。 2. 該反應係使脲基甲酸酯化反應與三聚異氰酸酯化 反應同時進行之1項之聚異氰酸酯組成物。 3- 該脲基甲酸酯化反應與三聚異氰酸酯化反應之觸 媒爲辛酸錫之2項之聚異氰酸酯組成物。 ® 4. 使六甲撐二異氰酸酯與碳數1 1〜20之脂肪族單 醇於辛酸錫觸媒之存在下進行脲基甲酸酯化反應與三聚異 氰酸酯化反應者爲其特徵之聚異氰酸酯之製造方法。 5. 含有1項至3項中任意之聚異氰酸酯組成物與多 元醇化合物之二液型塗料組成物。 含於本發明組成物中之聚異氰酸酯係對於低極性有機 溶劑（弱溶劑）之溶解性良好，同時與二液型塗料所使用 之氟系、丙烯酸系之多元醇之互溶性良好。 該聚異氰酸酯其三聚異氰酸酯含量高，故將此作成二 200948837 液型塗料組成物之硬化劑使用後，可提昇表面硬度爲首之 各種塗膜物性。 又，本發明之二液型塗料組成物，由於可溶於低極性 有機溶劑（弱溶劑），故於重覆塗佈時，不會侵蝕底層， 具良好的再度塗層性。 【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的說明。 本發明之聚異氰酸酯組成物係含有使六甲撐二異氰酸 酯與碳數11〜20之脂肪族單醇反應所得之聚異氰酸酯， 及苯胺點爲10〜70°C之低極性有機溶劑，或混合苯胺點爲 5〜50 °C之低極性有機溶劑，聚異氰酸酯於分子內具有脲 基甲酸酯基、三聚異氰酸酯基及胺基甲酸酯基’同時此等 脲基甲酸酯基與三聚異氰酸酯基之莫耳比爲滿足脲基甲酸 酯基/三聚異氰酸酯基=70/30〜30/70者。 本發明中，當脲基甲酸酯基/三聚異氰酸酯基（莫耳 比）不在上述範圍時，則對於取得之聚異氰酸酯對低極性 有機溶劑之溶解性將降低，同時使用該組成物得到之塗膜 物性亦降低。 較佳者，脲基甲酸酯基/三聚異氰酸酯基（莫耳比） = 60/40 〜30/70，更佳者爲 40/60 〜30/70 ° 又，胺基甲酸酯基之含量未特別受限’ 一般本發明之 聚異氰酸酯中，對於脲基甲酸酯基與三聚異氰酸酯基之總 -8- 200948837 莫耳量而言’爲G.1莫耳％〜2莫耳％者宜，更佳者爲0.5 〜2吴耳％。 另外’上述各官能基之莫耳比可藉由1H_NMR測定算 出。 作爲六甲撐二異氰酸酯反應之碳數n〜20之脂肪族 單醇者，如：異十三醇、1-十一醇、；!·十二醇、丨_二十醇 、1-十七醇、1-十九醇、：!-十三醇、〗_十四醇、〗_十五醇 ❹ 、硬脂醇、異硬脂醇、3 -乙基-4,5,6-三甲基辛醇、4,5,6,7-四甲基壬醇、4,5,8-三甲基癸醇、4,7,8-三甲基癸醇、2-己 基十二醇、2-辛基十二醇、2-十二烷基癸醇、2_十六烷基 十八醇等例。此等可單獨使用，亦可組合2種以上使用。 此等醇中，考量更提高對於得到聚異氰酸酯組成物對 低極性有機溶劑之溶解性後，又以1 _十三醇、異十三醇、 1·月桂醇、1-二十醇、1-庚癸醇、1·壬癸醇、1-十四醇、 1-十五醇、硬脂烯醇、異硬脂烯醇、2 -辛基月桂醇爲較佳 ® ，更佳者爲1-十三醇、異十三醇、2 -辛基月桂醇。 六甲撐二異氰酸酯與單醇之反應可於有機溶劑之存在 或不存在下，加熱5 0〜1 5 0 °C後進行之。 脲基甲酸酯化可與胺基甲酸酯化同時進行，亦可於胺 基甲酸酯化後進行之，而本發明中最好於胺基甲酸酯化之 後進行者宜。胺基甲酸酯化與脲基甲酸酯化同時進行時， 可於脲基甲酸酯化觸媒之存在下進行反應，於胺基甲酸酯 化之後進行脲基甲酸酯化時，於脲基甲酸酯化觸媒之不存 在下，進行特定時間之胺基甲酸酯化反應後，添加脲基甲 -9- 200948837 酸酯化觸媒後，進行脲基甲酸酯化反應即可。200948837 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a polyisocyanate composition and a two-liquid type coating composition using the same. [Prior Art] The two-liquid type methic acid Φ ester coating using polyisocyanate as a component is used in buildings and civil engineering because of its good weather resistance and abrasion resistance. Painting of outdoor substrates such as structures, repair of automobiles, painting of plastics, etc. In the coating material, a strong solvent such as an aromatic hydrocarbon solvent such as toluene or xylene or an ester solvent such as butyl acetate is used as the height of the polyisocyanate, that is, a solvent having a strong dissolving power is used. Since these strong solvents are strong in odor, the surface of the working environment is improved, and the global environmental load is reduced. In recent years, there has been a tendency to avoid. Further, when the old coating film is recoated and repaired, and the coating is renewed, the old coating film is swollen or dissolved when it contains a strong solvent having a high dissolving power in the coating material, and it is necessary to repair the old coating film. As a result, problems such as enlargement and cumbersome coating work, increase in coating cost, and prolonged construction period have occurred. In view of the above, in recent years, it has been advocated to develop a polyisocyanate which is easily soluble in a low polar organic solvent. In the case of a polyisocyanate having a low solubility in a low-polarity solvent, it is disclosed that the dilution of the alicyclic diisocyanate with a low-polar solvent is 1 in the patent document 1 (Japanese Laid-Open Patent Publication No. Hei No. Hei 8-1 98928). 〇〇% 200948837 The above polyol is reacted to obtain a polyisocyanate. Further, in the case of the polyisocyanate which is excellent in the solubility of a low-polar organic solvent and the mutual solubility of a phthalic acid ester compound, it is disclosed by the aliphatic group and/or Or a polyisocyanate compound having a specific allophanate group/trimeric isocyanate group molar ratio and a specific molecular weight distribution obtained from an alicyclic diisocyanate and a monohydric alcohol having 1 to 20 carbon atoms. The polyisocyanate of Patent Document 1 and Patent Document 2 has good solubility in a low-polarity organic solvent, and is compatible with various other physical properties such as the mutual solubility of the polyol compound of the main component and the surface hardness of the obtained coating film. There is room for further improvement, and there is room for improvement in the choice of low-polarity solvents. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. No. 2008-24828. SUMMARY OF THE INVENTION The present invention provides a solution of a low-polarity organic solvent in combination with a polyol compound in view of the above problems. The polyisocyanate composition of the coating film having good surface properties and the two-liquid type coating composition using the same can be provided for the purpose of imparting good solubility. In order to achieve the object, the inventors of the present invention found that the allophanate/polyisocyanate of the polyisocyanate obtained by reacting hexamethylene diisocyanate with an aliphatic monoalcohol having 11 to 20 carbon atoms was obtained. After the molar ratio of the molar ratio is made to a specific range, the solubility of the low-polar organic solvent -6 - 200948837 can be improved, and in the coating film obtained from the coating containing the polyisocyanate and the polyol, the lifting starts from the surface hardness. Various physical properties have been completed to complete the present invention. That is, the present invention provides: 1. a polyisocyanate obtained by reacting hexamethylene diisocyanate with an aliphatic monool having a carbon number of 1 to 20 and a low polar organic solvent having an aniline point of 10 to 70 ° C or a low polarity organic hydrazine solvent having a mixed aniline point of 5 to 50 ° C, the polyisocyanate having an allophanate group, a trimeric isocyanate group and a urethane group in the molecule, and the ureido formic acid The polyisocyanate composition characterized by an allophanate group and a trimeric isocyanate group is an allophanate group/trimeric isocyanate group = 7 0/30 to 3 0/7 0 . 2. This reaction is a polyisocyanate composition of the above-mentioned item in which the allophanation reaction and the isocyanation reaction are carried out simultaneously. 3- The catalyst for the allophanation reaction and the trimeric isocyanation reaction is a polyisocyanate composition of 2 parts of tin octylate. ® 4. The polyisocyanate characterized by the allophanation reaction and the trimerization reaction of the hexamethylene diisocyanate with the aliphatic monoalcohol having a carbon number of 1 to 20 in the presence of a tin octanoate catalyst Production method. 5. A two-component coating composition comprising a polyisocyanate composition of any one of items 1 to 3 and a polyol compound. The polyisocyanate contained in the composition of the present invention is excellent in solubility in a low-polar organic solvent (weak solvent), and is excellent in miscibility with a fluorine-based or acrylic-based polyol used in a two-component type coating. Since the polyisocyanate has a high content of the trimeric isocyanate, it can be used as a hardener for the liquid coating composition of 200948837, and the surface hardness can be improved by the surface hardness. Further, since the two-liquid type coating composition of the present invention is soluble in a low-polar organic solvent (weak solvent), it does not attack the underlayer at the time of repeated coating, and has good recoatability. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in more detail. The polyisocyanate composition of the present invention contains a polyisocyanate obtained by reacting hexamethylene diisocyanate with an aliphatic monool having a carbon number of 11 to 20, and a low polar organic solvent having an aniline point of 10 to 70 ° C, or a mixed aniline point. A low polar organic solvent of 5 to 50 ° C, the polyisocyanate has an allophanate group, a trimeric isocyanate group and a urethane group in the molecule, and these allophanate groups and trimer isocyanates The molar ratio of the base is such that the allophanate group/trimeric isocyanate group is 70/30 to 30/70. In the present invention, when the allophanate group/trimeric isocyanate group (mole ratio) is out of the above range, the solubility of the obtained polyisocyanate to the low polar organic solvent is lowered, and the composition is obtained by using the composition. The physical properties of the coating film are also lowered. Preferably, the allophanate group/trimeric isocyanate group (mole ratio) = 60/40 to 30/70, more preferably 40/60 to 30/70 °, and the urethane group The content is not particularly limited. Generally, in the polyisocyanate of the present invention, the total amount of the allophanate group and the trimeric isocyanate group is -8 - 200948837, and the amount is 'G.1 mol% to 2 mol%. Preferably, the better one is 0.5 to 2 mils. Further, the molar ratio of each of the above functional groups can be calculated by 1H_NMR. As an aliphatic monoalcohol having a carbon number of n to 20 as a reaction of hexamethylene diisocyanate, such as: isotridecyl alcohol, 1-undecyl alcohol, ;··dodecanol, oxime-eicosanol, 1-heptadecanol , 1-nonadecanol, :!-tridecyl alcohol, __tetradecyl alcohol, 〗 _ pentadecanol oxime, stearyl alcohol, isostearyl alcohol, 3-ethyl-4,5,6-trimethyl Octanol, 4,5,6,7-tetramethylnonanol, 4,5,8-trimethylnonanol, 4,7,8-trimethylnonanol, 2-hexyldodecanol, 2- Examples of octyldodecanol, 2-dodecyl decyl alcohol, and 2-hexadecyl octadecyl alcohol. These may be used alone or in combination of two or more. In these alcohols, the consideration is further improved. After obtaining the solubility of the polyisocyanate composition to the low-polar organic solvent, 1 -tridecyl alcohol, isotridecyl alcohol, lauryl alcohol, 1-eicosanol, 1- Hexanol, l-nonanol, 1-tetradecanol, 1-pentadecanol, stearyl enol, isostearyl alcohol, 2-octyl lauryl alcohol is preferably ®, more preferably 1- Tridecyl alcohol, isotridecyl alcohol, 2-octyl lauryl alcohol. The reaction of hexamethylene diisocyanate with a monool can be carried out after heating at 50 to 150 ° C in the presence or absence of an organic solvent. The allophanation can be carried out simultaneously with the urethanization, or after the urethanization, and it is preferred in the present invention to carry out the post-urementation. When the urethanation is carried out simultaneously with the allophanation, the reaction can be carried out in the presence of an allophanate catalyst, and when the allophanation is carried out after the ureidolation, After the ureidolation reaction for a specific period of time in the absence of the allophanate catalyst, the allophanate reaction is carried out after the addition of the urea-formamide-9-200948837 acid esterification catalyst. Just fine.
作爲脲基甲酸酯化觸媒者，可由公知觸媒中適當選用 之，例如羧酸的金屬鹽。上述羧酸可使用例如乙酸、丙酸 、酪酸、己酸、辛酸、月桂酸、肉豆蔻酸、棕櫚酸、硬脂 酸、2·乙基己酸等之飽和脂肪族羧酸、環己烷羧酸、環戊 烷羧酸等之飽和單環羧酸、雙環（4.4.0)癸烷-2-羧酸等 之飽和複環羧酸、環烷酸等之上述之羧酸混合物、油酸、 亞油酸、亞麻酸、大豆油脂肪酸、妥爾油脂肪酸等之不飽 和脂肪族羧酸、二苯乙酸等之芳香脂肪族羧酸、苯甲酸、 甲苯酸等之芳香族羧酸等之單羧酸類；鄰苯二甲酸、異苯As the allophanate catalyst, a suitable one of known catalysts such as a metal salt of a carboxylic acid can be suitably used. As the carboxylic acid, for example, a saturated aliphatic carboxylic acid such as acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid or diethylhexanoic acid, or cyclohexanecarboxylic acid can be used. a saturated monocyclic carboxylic acid such as an acid or a cyclopentanecarboxylic acid; a saturated cyclic carboxylic acid such as a bicyclo (4.4.0) decane-2-carboxylic acid; or a carboxylic acid mixture of a naphthenic acid or the like; a monocarboxylic acid such as an unsaturated aliphatic carboxylic acid such as linoleic acid, linolenic acid, soybean oil fatty acid or tall oil fatty acid, an aromatic aliphatic carboxylic acid such as diphenylacetic acid, or an aromatic carboxylic acid such as benzoic acid or toluic acid. Acids; phthalic acid, isophthalic acid
、丙二酸、戊二酸、己二酸、庚二酸、辛二酸、戊烯二酸 、壬二酸、癸二酸、1,4-環己二羧酸、α-氫化黏康酸、 冷-氫化黏康酸、α-丁基-α-乙基戊二酸、α，/3-二乙基琥 珀酸、馬來酸、延胡索酸、偏苯三甲酸、均苯四甲酸等之 聚羧酸類之例。 又，作爲構成羧酸金屬鹽之金屬例者，如：鋰、鈉、 鉀等鹼金屬；鎂、鈣、鋇等之鹼土類金屬；錫、鉛等之其 他典型之金屬；錳、鐵、鈷、鎳、銅、鋅、锆等之過渡金 屬等例。 此等羧酸金屬鹽可單獨或組合2種以上使用之，另外 ，脲基甲酸酯化觸媒之使用量對於聚異氟酸酯與醇之合計 質量而言，爲0.0005〜1質量％者宜，更佳者爲0.001〜 〇. 1質量％。 -10- 200948837 於有機溶媒之存在下，進行反應時，可使 應之各種有機溶媒，其具體例如：η-己烷、辛 族烴類；環己烷、甲基環己烷等之脂環族烴類 基乙基酮、甲基異丁酮、環己酮等之酮類；乙 酸乙酯、乙酸丁酯、乙酸異丁酯等之酯類；乙 酸酯、丙二醇甲醚乙酸酯、3-甲基-3-甲氧基丁 乙基-3-乙氧基丙酸酯等之二醇醚酯類；二乙醚 〇 、二氧陸圜等之醚類；甲基氯、二氯甲烷、氯 碳、甲基溴、二碘甲烷、二氯乙烷等之鹵化烴 吡咯烷酮、二甲基甲醯胺、二甲基乙醯胺、二 甲基膦酸醯胺等之極性非質子溶媒等例。此等 、或組合2種以上使用之。 反應結束後，於反應系內加入磷酸、磷酸 停止劑，於3 0〜1 00°C下進行停止反應1〜2小 甲酸酯化反應進行停止。 ® 反應停止後，藉由薄膜蒸餾等公知之方法 應成份，可取得脲基甲酸酯改性聚異氰酸酯。 所得之脲基甲酸酯改性聚異氰酸酯係（上 基甲酸酯基/三聚異氰酸酯基之範圍時）可直 氰酸酯組成物。 另外，如上述所得到之脲基甲酸酯基改性 係具有以脲基甲酸酯基爲主者，而於異氰酸酯 在之條件下，經由反應等之進行產生副反應， 氰酸酯。 用不影響反 烷等之脂肪 :丙酮、甲 酸甲酯、乙 二醇乙醚乙 基乙酸酯、 、四氫呋喃 仿、四氯化 類；N-甲基 甲亞颯、六 溶媒可單獨 酯等之反應 時，使脲基 ，去除未反 述之滿足脲 接作成聚異 聚異氰酸酯 基爲過剩存 生成三聚異 -11 - 200948837 因此，適度調整脲基甲酸酯化中[nco]/[oh]之比等各 種條件後，可將所得到聚異氰酸酯中之脲基甲酸酯基與三 聚異氰酸酯基之莫耳比適度調整於70/30〜30/70之範圍。 又，依以上之方法，使脲基甲酸酯化之聚異氰酸酯進 一步作成三聚異氰酸酯化，亦可調整脲基甲酸酯基/三聚 異氰酸酯基之莫耳比。 作爲三聚異氰酸酯化反應者，如：於三聚異氰酸酯化 觸媒之存在下，使聚異氰酸酯進行改性（三聚物化）之方 @ 法例。作爲該改性方法者，可使用如：專利第3 3 7 1 4 8 0號 公報、特開2002-241458號公報所載之方法。 作爲三聚異氰酸酯化觸媒者，可使用如：脂肪族羧酸 之金屬鹽、鉀苯酚鹽等之苯酚鹽、2,4,6-三（二甲基胺基 甲基）苯酚、2,4-雙（二甲基胺基甲基）苯酚、2,6-二-第 三丁基-4-二甲基胺基三甲基矽烷苯酚、三乙胺' N，n，，N，，-二（一·甲基胺基丙基）六氨-S-二曉、二氮雜雙環十一嫌 等之胺系化合物。其中又以脂肪族羧酸之金屬鹽爲較佳， β 如：乙酸、丙酸、十一酸、己酸、辛酸、肉豆蔻酸等之羧 酸之鈉鹽、鉀鹽、錫鹽等爲理想者。又，作爲市售品者， 亦可使用2-羥基丙基三甲銨、辛酸鹽（DABCO TMR、air products Japan (股份）製）、辛酸鉀（DABCO K-15、air products Japan (股份）製）。 如上述’本發明聚異氰酸酯可藉由：同時進行脲基甲 酸酯化與三聚異氰酸酯化之方法，或階段性進行脲基甲酸 酯化與三聚異氰酸酯化之方法製造之，而本發明中最理想 -12- 200948837 方法爲同時進行脲基甲酸酯化與三聚異氰酸酯化之方法。 此時，作爲觸媒者，由容易進行反應控制之面視之， 上述各種觸媒中又以辛酸錫爲理想使用者。 此外，聚異氰酸酯可混合2種以上使用，此時，混合 物在滿足上述的脲基甲酸酯基與三聚異氰酸酯基的莫耳比 下，可一部份使用不滿足上述脲基甲酸酯基與三聚異氰酸 酯基的莫耳比之聚異氰酸酯。 〇 本發明所使用之聚異氰酸酯黏度並未特別限定，一般 爲25°C下2,000mPa· s以下者宜，較佳者爲l，500mPa· s 以下’更佳者爲l，000mPa· s以下。當聚異氰酸酯之黏度 超出2,OOOmPa · s時，則塗料組成物之黏度變高，導致不 易使用之情況產生。另外，黏度之下限値並未特別限定， 一般由使用上之觀點視之，爲50mPa· s以上者宜。 本發明之塗料組成物於上述之聚異氰酸酯中具有特徵 ，因此，作爲與此進行反應硬化之另一成份者，只要適度 © 選自該用途所使用之多元醇化合物即可。 具體例如：丙烯酸系多元醇、氟系多元醇等例，此等 中又考量耐氣候性後，又以氟系多元醇爲較佳，考量耐氣 候性與成本面之均衡性，又以丙烯酸系多元醇者宜。 又，本發明中，由其對於低極性有機溶劑之良好溶解 性的上述聚異氰酸酯之特性面視之，多元醇化合物亦可溶 於低極性有機溶劑爲理想者。 作爲可溶於低極性有機溶劑之丙烯酸系多元醇者，並 未特別限定，一般可使用公知之弱溶劑可溶型丙烯酸系多 -13- 200948837 元醇。作爲該具體例者’如：市售品之ACRYDIC HU-596 (大日本油墨化學工業（股份）製）、EXXELOR 410 (亞 細亞工業（股份）製）、希塔羅依德65 00 (日立化成工業 (股份）製）等例。 作爲可溶於低極性有機溶劑之氟系多元醇者，並未特 別限定，一般可使用公知之弱溶劑可溶型氟系多元醇。其 具體例如·氟乙烯一乙烯醚（乙烯酯）共聚物等例。市售 品如_· LumiflonLF800(旭硝子（股份）製）等例。 ❿ 該多元醇化合物之羥基價及酸價並未特別限定，而本 發明之塗料中’羥基價爲1〜3〇〇mgKOH/g者宜，更佳者 爲1〜25 0mgKOH/g。當羥基價未達1 mgKOH/g時，則塗 膜之交聯將不足’致使塗膜強度等之物性出現下降傾向， 超出300mgKOH/g則塗膜交聯密度太高變得太硬，致使對 於基材之追隨性與柔軟性降低。 又，多元醇化合物之數平均分子量考量所得塗膜之強 度，塗料之使用性等，爲5,000〜20,000者宜，更佳者爲 ❹ 7,00 0〜15,000。數平均分子量係經由掃描折射率計檢出之 凝膠滲透色譜法（GPC )測定之測定値（聚苯乙烯換算値 )。 本發明塗料組成物中聚異氰酸酯組成物與多元醇化合 物之配合比例，對於100質量份多元醇而言，爲1〜150 質量份之聚異氰酸酯組成物者宜，較佳者爲1〜130質量 份，更佳者爲1〜100質量份。 用於本發明塗料組成物之聚異氰酸酯組成物係含有苯 -14- 200948837 胺點爲10〜70 °c之低極性有機溶劑或混合苯胺點爲5〜50 t之低極性有機溶劑。此等低極性有機溶劑可預先添加於 聚異氰酸酯中放置之’亦可爲於聚異氰酸酯與多元醇之混 合前調整黏度之目的下’添加於聚異氰酸酯。 又，低極性有機溶劑於必要時，亦可添加於多元醇組 成物之調製時，更可添加於聚異氰酸酯組成物與多元醇之 混合時。 〇 其中，「苯胺點」係指使等容量之苯胺與試料（有機 溶劑）作爲均勻混合溶液存在之最低溫度者。又，「混合 苯胺點」係指使苯胺2容量’試料1容量及丨_庚垸丨容量 作成均勻混合溶液存在之最低溫度者。苯胺點及混合苯胺 點可依JIS K 2256所載之苯胺點及混合苯胺點試驗方法爲 基準進行測定。 另外’苯胺之凝固點爲-6 °C ’故其以下之溫度時，將 無法測定苯胺點。因此’於苯胺中混合庚烷，爲使有機溶 ® 劑之溶解力於更廣範圍進行測定，而使用混合苯胺點。 該本胺點爲10〜70°c者宜，較佳者爲1〇〜6〇t>c，更 佳者爲10〜5(TC。又，混合苯胺點爲5〜5(rc者宜。當苯 胺點未達1 〇°c，或混合苯胺點未達5t時，則容易侵蝕基 底，苯胺點超出7(TC，或混合苯胺點超出5〇t則不易溶 解本發明之聚異氰酸酯。 作爲該有機溶劑例者’如：甲基環己烷（苯胺點：4〇 °C)、乙基環己院（苯胺點：44t)、石油溶劑（苯胺點 • 56 c )、松節油（苯胺點：44t )之例，又，作成石油 -15- 200948837 系烴被市售之商品名，High Aromatic White Spirit ( HAWS) ( Shellchemicals Japan 製，苯胺點：17°C )、 Low Aromatic White Spirit ( LAWS ) ( Shellchemicals, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, α-hydrogenated fatty acid , cold-hydrogenated muconic acid, α-butyl-α-ethylglutaric acid, α,/3-diethyl succinic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid, etc. Examples of carboxylic acids. Further, examples of the metal constituting the metal carboxylate include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as magnesium, calcium, and barium; and other typical metals such as tin and lead; manganese, iron, and cobalt. Examples of transition metals such as nickel, copper, zinc, and zirconium. These carboxylic acid metal salts may be used singly or in combination of two or more kinds, and the amount of the allophanate catalyst used is 0.0005 to 1% by mass based on the total mass of the polyisocyanate and the alcohol. Preferably, the better is 0.001~ 〇. 1% by mass. -10- 200948837 When the reaction is carried out in the presence of an organic solvent, various organic solvents can be used, such as η-hexane, octane hydrocarbons, and alicyclic rings such as cyclohexane and methylcyclohexane. a ketone of a hydrocarbon group such as ethyl ketone, methyl isobutyl ketone or cyclohexanone; an ester of ethyl acetate, butyl acetate or isobutyl acetate; acetate, propylene glycol methyl ether acetate, Glycol ether esters such as 3-methyl-3-methoxybutylethyl-3-ethoxypropionate; ethers such as diethyl ether, dioxane, etc.; methyl chloride, dichloromethane, chlorine Examples of a polar aprotic solvent such as a halogenated hydrocarbon pyrrolidone such as carbon, methyl bromide, diiodomethane or dichloroethane, dimethylformamide, dimethylacetamide or dimethylphosphonium phthalate. These or two or more combinations are used. After the completion of the reaction, a phosphoric acid or a phosphoric acid stopping agent was added to the reaction system, and the reaction was stopped at 30 to 100 ° C for 1 to 2 small formic acidification reaction. ® After the reaction is stopped, the allophanate-modified polyisocyanate can be obtained by a known method such as thin film distillation. The obtained allophanate-modified polyisocyanate type (when it is in the range of a perflate group/trimeric isocyanate group) can be a straight cyanate composition. Further, the allophanate-based modified system obtained as described above has an allophanate group as a main component, and a side reaction, a cyanate ester, is generated by a reaction or the like under the conditions of an isocyanate. It does not affect the fat of trans-alkane, etc.: acetone, methyl formate, ethylene glycol ethyl acetate, tetrahydrofuran, tetrachlorinated; N-methylformamidine, hexasolvent, ester alone, etc. When the urea group is removed, the unreported one is satisfied, and the urea is formed into a polyisocyanate group to form a trimeric iso-11 - 200948837. Therefore, moderately adjusting the [nco]/[oh] in the allophanation The molar ratio of the allophanate group to the trimeric isocyanate group in the obtained polyisocyanate can be appropriately adjusted to a range of 70/30 to 30/70, depending on various conditions. Further, according to the above method, the allophanate-forming polyisocyanate is further subjected to trimerization, and the allyl group of the allophanate group/trimeric isocyanate group can also be adjusted. As a trimeric isocyanation reactor, for example, in the presence of a trimeric isocyanate catalyst, the polyisocyanate is modified (trimerization) @法例. As the method of the modification, a method as disclosed in Japanese Patent Publication No. 3 3 7 1 4 8 0 and JP-A-2002-241458 can be used. As the trimeric isocyanate catalyst, for example, a metal salt of an aliphatic carboxylic acid, a phenolate such as potassium phenate, or a 2,4,6-tris(dimethylaminomethyl)phenol, 2, 4 may be used. - bis(dimethylaminomethyl)phenol, 2,6-di-t-butyl-4-dimethylaminotrimethyldecanephenol, triethylamine 'N,n,,N,,- An amine compound of bis(monomethylaminopropyl) hexaamino-S-dioxa, diazabicycloheptene and the like. Among them, a metal salt of an aliphatic carboxylic acid is preferable, and a sodium salt, a potassium salt or a tin salt of a carboxylic acid such as acetic acid, propionic acid, undecanoic acid, caproic acid, caprylic acid or myristic acid is preferable. By. In addition, as a commercial product, 2-hydroxypropyltrimethylammonium, octanoate (DABCO TMR, manufactured by Air Products Japan), and potassium octoate (DABCO K-15, manufactured by Air Products Japan) can also be used. . As described above, the polyisocyanate of the present invention can be produced by a method of simultaneously performing allophanation and trimerization, or a stepwise process of allophanation and trimerization, and the present invention The most desirable method -12- 200948837 is a method of simultaneously performing allophanation and trimerization. At this time, as a catalyst, it is easy to carry out reaction control, and among the above various catalysts, tin octylate is an ideal user. Further, the polyisocyanate may be used in combination of two or more kinds. In this case, the mixture may be partially used to satisfy the above allophanate group at a molar ratio satisfying the above allophanate group and the trimer isocyanate group. Polyisocyanate with a molar ratio of a trimeric isocyanate group. The viscosity of the polyisocyanate used in the present invention is not particularly limited, and is generally 2,000 mPa·s or less at 25 ° C, preferably 1,500 mPa·s or less, and more preferably 1,000 mPa·s or less. When the viscosity of the polyisocyanate exceeds 2,000 mPa · s, the viscosity of the coating composition becomes high, resulting in an unusable condition. Further, the lower limit of the viscosity is not particularly limited, and it is generally preferably 50 mPa·s or more from the viewpoint of use. The coating composition of the present invention is characterized by the above-mentioned polyisocyanate. Therefore, as another component which is reactively cured by this reaction, it is sufficient to use a polyol compound selected from the above-mentioned applications. Specifically, for example, an acrylic polyol or a fluorine-based polyol, and in consideration of weather resistance, a fluorine-based polyol is preferable, and a balance between weather resistance and cost is considered, and acrylic acid is used. Polyol is suitable. Further, in the present invention, it is preferable that the polyol compound is soluble in a low-polar organic solvent from the viewpoint of the properties of the polyisocyanate which is excellent in solubility in a low-polar organic solvent. The acrylic polyol which is soluble in the low-polar organic solvent is not particularly limited, and generally, a known weak solvent-soluble acrylic type poly-13-200948837-alcohol can be used. As a specific example, such as: ACRYDIC HU-596 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.), EXXELOR 410 (Asian Industrial Co., Ltd.), and Hita Royde 65 00 (Hitachi Chemical Industry Co., Ltd.) (Shares) system and other examples. The fluorine-based polyol which is soluble in the low-polar organic solvent is not particularly limited, and a known weak solvent-soluble fluorine-based polyol can be generally used. Specific examples thereof include a fluoroethylene-vinyl ether (vinyl ester) copolymer. Commercial products such as _· Lumiflon LF800 (Asahi Glass Co., Ltd.) and the like. The hydroxyl value and the acid value of the polyol compound are not particularly limited, and the coating material of the present invention preferably has a hydroxyl group value of 1 to 3 〇〇 mgKOH/g, more preferably 1 to 25 mg KOH/g. When the valence of the hydroxyl group is less than 1 mgKOH/g, the cross-linking of the coating film will be insufficient to cause the physical properties such as the strength of the coating film to decrease, and if the molecular weight exceeds 300 mgKOH/g, the cross-linking density of the coating film becomes too high, resulting in The followability and softness of the substrate are reduced. Further, the number average molecular weight of the polyol compound is preferably from 5,000 to 20,000, more preferably from ❹, 00 0 to 15,000, in consideration of the strength of the obtained coating film and the usability of the coating material. The number average molecular weight is measured by gel permeation chromatography (GPC) detected by a scanning refractometer (polystyrene-converted 値). The compounding ratio of the polyisocyanate composition to the polyol compound in the coating composition of the present invention is preferably from 1 to 150 parts by mass, preferably from 1 to 130 parts by mass, per 100 parts by mass of the polyol. More preferably, it is 1 to 100 parts by mass. The polyisocyanate composition used in the coating composition of the present invention contains a benzene-14-200948837 low-polar organic solvent having an amine point of 10 to 70 ° C or a low-polar organic solvent having a mixed aniline point of 5 to 50 t. These low-polarity organic solvents may be previously added to the polyisocyanate, and may be added to the polyisocyanate for the purpose of adjusting the viscosity before mixing the polyisocyanate with the polyol. Further, the low-polarity organic solvent may be added to the polyol composition as needed, and may be added to the mixture of the polyisocyanate composition and the polyol. 〇 In the above, "aniline point" means the lowest temperature at which an equal volume of aniline and a sample (organic solvent) are present as a homogeneous mixed solution. Further, "mixed aniline point" means the volume of the aniline 2 capacity' sample 1 and the 丨_g垸丨 capacity to be the lowest temperature at which the homogeneous mixed solution is present. The aniline point and the mixed aniline point can be determined based on the aniline point and mixed aniline point test method contained in JIS K 2256. In addition, when the freezing point of aniline is -6 °C, the aniline point cannot be measured. Therefore, heptane is mixed with aniline, and the mixed aniline point is used in order to measure the solubility of the organic solvent in a wider range. The amine point is preferably from 10 to 70 ° C, preferably from 1 to 6 〇 t > c, and more preferably from 10 to 5 (TC. Further, the mixed aniline point is 5 to 5 (rc is preferred). When the aniline point is less than 1 〇 ° C, or the mixed aniline point is less than 5 t, the substrate is easily eroded, and the aniline point exceeds 7 (TC, or the mixed aniline point exceeds 5 〇 t, so that the polyisocyanate of the present invention is not easily dissolved. Examples of organic solvents such as methylcyclohexane (aniline point: 4 ° C), ethylcyclohexan (aniline point: 44 t), petroleum solvent (aniline point • 56 c ), turpentine (aniline point: 44 t) ), in addition, made a petroleum--15- 200948837 hydrocarbon product under the trade name, High Aromatic White Spirit (HAWS) (manufactured by Shellchemicals Japan, aniline point: 17 ° C), Low Aromatic White Spirit ( LAWS ) ( Shellchemicals
Japan 製，苯胺點：44。。) 、Esso naphtha No.6 ( exxon mobile 公司製，苯胺點：43°C ) 、Pegasol 3040 (exxon mobile公司製，苯胺點：55 °C ) 、A溶媒（新日本石油公 司製，苯胺點：45 °C) 、Cleans〇l(新日本石油公司製， 苯胺點：64°C)、石油溶劑A (新日本石油公司製’苯胺 點：43°C ) 、HIAROM 2S (新日本石油公司製，苯胺點： 44 °C )、Solvesso 100 (exxon mobile 公司製，混合苯胺 點：14 °C )、Solvesso 150 (exxon mobile 公司製，混合 苯胺點：1 8.3 °C ) 、Swasol 100 (九善石油化學公司製’ 混合苯胺點·· 24.6°C ) 、Swasol 200 (九善石油化學公司 製，混合苯胺點：23.8°C) 、Swasol 1000 (九善石油化學 公司製，混合苯胺點：12.7 °C) 、Swasol 1 5 00 (九善石油 化學公司製，混合苯胺點：16.5 °C) 、Swasol 1 800 (九善Made by Japan, aniline point: 44. . ), Esso naphtha No. 6 (manufactured by exxon mobile, aniline point: 43 ° C), Pegasol 3040 (manufactured by exxon mobile, aniline point: 55 ° C), A solvent (manufactured by Nippon Oil Co., Ltd., aniline point: 45 °C), Cleans〇l (manufactured by Nippon Oil Co., Ltd., aniline point: 64 ° C), petroleum solvent A (Nippon Oil Co., Ltd. 'aniline point: 43 ° C), HIAROM 2S (manufactured by Nippon Oil Corporation, aniline) Point: 44 °C), Solvesso 100 (exxon mobile company, mixed aniline point: 14 °C), Solvesso 150 (exxon mobile company, mixed aniline point: 1 8.3 °C), Swasol 100 (Jiushan Petrochemical Company) 'mixed aniline point · · 24.6 ° C ), Swasol 200 (made by Jiushan Petrochemical Co., Ltd., mixed aniline point: 23.8 ° C), Swasol 1000 (made by Jiushan Petrochemical Co., Ltd., mixed aniline point: 12.7 ° C), Swasol 1 5 00 (made by Jiushan Petrochemical Company, mixed aniline point: 16.5 °C), Swasol 1 800 (Jiushan
石油化學公司製，混合苯胺點：15.7°C )、出光IPZOLE 100(出光興產公司製，混合苯胺點：13.5°C ) 、IPZOLE 150(出光興產公司製，混合苯胺點：15.2 °C )、Pegasol ARO-80 ( exxon mobile 公司製，混合苯胺點：25 °C )、 Pegasol R-l〇〇( exxon mobile 公司製，混合苯胺點：14 °C )、昭石特 Hysol( Shellchemicals Japan 公司製，混合苯 胺點：12.6°C )、日石Hysol (新日本石油公司製，混合 苯胺點：1 71以下）等例。此等有機溶劑可單獨使用1種 -16- 200948837 、或混合2種以上使用之。 苯胺點爲10°c以上或混合苯胺點爲5°c以上之有機溶 劑有臭氣少之特徵。因此’含有該低極性有機溶劑之本發 明塗料組成物由其耐環境性之觀點視之，亦爲理想者。 又，該低極性有機溶劑其溶解力低，不易侵鈾基底， 故可重覆塗佈塗料用組成物，亦適用於修補用塗料。 另外，該塗料組成物亦可含有一般用於塗料之各種添 〇 加劑。作爲添加劑例者，如，可塑劑、防腐劑、防黴劑、 防藻劑、消泡劑、塗平劑、顏料分散劑 '沈降防止劑、防 滴垂劑、觸媒、硬化促進劑、脫水劑、去光劑、紫外線吸 收劑、抗氧化劑、顏料、界面活性劑等例。 由本發明之塗料組成物製作塗膜時，可於混凝土、砂 漿、塗膠板（siding board)、擠壓成形板、磁磚、金屬 、玻璃、木材、塑膠等適當之基材上，經由刷塗、輥塗、 噴霧塗佈等方法，進行塗佈，以適當方法乾燥、硬化即可 ❹ 又，於乾式建材進行塗裝時，亦可經由流動塗層或滾 輥塗層，於工場等進行預塗層。 另外，塗料用組成物亦可直接塗佈於基材，由塡縫、 電沈積、底塗（底漆塗佈）、中塗（著色等）之上進行塗 佈。又，基材爲金屬時，亦可塗佈於施予磷酸鐵處理或磷 酸鋅處理等之表面處理之上面。 以下以實施例及比較例爲例，進行本發明更具體的說 明，惟本發明並未受限於下述實施例。另外，以下，黏度 -17- 200948837 係由B型旋轉黏度計之測定値。 [1]聚異氰酸酯之製造 [實施例1] 於具備攪拌器、溫度計、冷卻管及氮氣體導入管之容 量1升之四口燒瓶中，置入880g之六甲撐二異氰酸酯（ 曰本聚胺基甲酸酯工業（股份）製、NCO含量：49.9質量 %，以下稱HDI)，及120g之十三醇（協和發酵工業（股 0 份）製），將此等進行攪拌，同時加熱至85 °C，進行胺基 甲酸酯化反應3個小時。 之後，於此反應液中，添加〇.lg之脲基甲酸酯化及 三聚異氰酸酯化觸媒之辛酸錫（日本化學產業（股份）製 )，以1 1 〇°C到達特定之NCO含量爲止進行反應後，添加 〇.4g之反應停止劑之酸性磷酸酯（JP-508，城北化學工業 (股份）製），於50°C下進行停止反應1個小時。 由此反應生成物，去除經由薄膜蒸餾（條件：140 °C 〇 ，0.04kPa)之過剩HDI，得到NCO含量15.8質量％，黏 度（25°C ) 320mPa · s，游離HDI含量0.1質量％之改性 聚異氰酸酯S-1 )。 [實施例2〜4] 除變更表1所示之觸媒等之置入量，NCO含量之外 與實施例1同法’得到改性聚異氰酸酯S - 2〜S - 4。 -18- 200948837 [實施例5] 於具備攪拌器、溫度計、冷卻管、及氮氣導入管之容 量1升之四口燒瓶中，置入850g之HDI(日本聚胺基甲 酸酯工業（股份）製’NCO含量：49.9質量％ ) ’及150g 之KALCOL 200GD(2-辛基十二醇，花王（股份）製）’ 將此進行攪拌，同時加熱至85 °C ’進行胺基甲酸酯化3個 小時。 〇 之後，於此反應中，添加〇_2g之脲基甲酸酯化及三 聚異氰酸酯化觸媒之辛酸錫（日本化學產業（股份）製） ，以110 °C到達特定之NCO含量爲止進行反應後’添加 〇.8g之反應停止劑之酸性磷酸酯（JP-508 ’城北化學工業 (股份）製），於50°C下進行停止反應1個小時。 由此反應生成物去除經由薄膜蒸餾（條件：140 °C ’ 0.04kPa)之過剩HDI，得到NCO含量15.7質量％，黏度 (25°C ) 560mPa . s，游離HDI含量0_2質量％之改性聚 ® 異氰酸酯S-5。 [實施例6] 除變更表1所示之觸媒等之置入量，NCO含量之外 與實施例5同法，得到改性聚異氰酸酯S-6。 [比較例1 ] 於具備攪拌器、溫度計、冷卻管、及氮氣導入管之容 量1升之四口燒瓶中，置入850g之HDI’及15〇g之 -19- 200948837 KALCOL 200GD(2-辛基十二醇，花王（股份）製），將 此進行攪拌，同時加熱至85 °C，進行胺基甲酸酯化3個小 時。 之後，於該反應液中，添加〇.4g之脲基甲酸酯化及 三聚異氰酸酯化觸媒之辛酸錫（日本化學產業（股份）製 )，以110°C，達到特定之NCO含量爲止進行反應後，添 加2.0g之反應停止劑之酸性磷酸酯（JP-508，城北化學工 業（股份）製），於50°C下進行停止反應1個小時。 0 由該反應生成物，去除經由薄膜蒸餾（條件：140 °C ，0.04kPa )之過剩HDI，得到NCO含量15.3質量％，黏 度（25°C ) 2,500 mPa · s，游離HDI含量0.1質量％之改 性聚異氰酸酯H-1。 [比較例2] 於具備攪拌器、溫度計、冷卻管、及氮氣導入管之容 量1升之四口燒瓶中，置入880g之HDI，及120g之三癸 © 醇（協和發酵工業（股份）製），將此進行攪拌，同時加 熱至8 5 °C，進行胺基甲酸酯化3個小時。 之後，於該反應液中，添加〇.lg之脲基甲酸酯化觸 媒辛酸锆（第1稀元素化學工業（股份）製），以ll〇°C 達到特定之NCO含量爲止進行反應後，添加0.2g之反應 停止劑之酸性磷酸酯（JP-5 08，城北化學工業（股份）製 )，於50 °C下進行停止反應1個小時。Petrochemical company, mixed aniline point: 15.7 ° C), light IPZOLE 100 (made by Idemitsu Kosan Co., Ltd., mixed aniline point: 13.5 ° C), IPZOLE 150 (made by Idemitsu Kosan Co., Ltd., mixed aniline point: 15.2 °C) , Pegasol ARO-80 (manufactured by exxon mobile, mixed aniline point: 25 °C), Pegasol Rl〇〇 (manufactured by exxon mobile, mixed aniline point: 14 °C), Hydra (made by Shellchemicals Japan), mixed Anthracene point: 12.6 ° C), Nikko Hysol (manufactured by Shin Nippon Oil Co., mixed aniline point: 1 71 or less) and the like. These organic solvents may be used alone or in combination of two or more kinds from -16 to 200948837. An organic solvent having an aniline point of 10 ° C or more or a mixed aniline point of 5 ° C or more has a characteristic of low odor. Therefore, the coating composition of the present invention containing the low-polarity organic solvent is also desirable from the viewpoint of environmental resistance. Further, the low-polarity organic solvent has a low dissolving power and is less likely to invade the uranium base, so that the coating composition can be repeatedly applied, and is also suitable for a coating for repair. Further, the coating composition may contain various additives for coatings. As an additive, for example, a plasticizer, a preservative, an antifungal agent, an anti-algae agent, an antifoaming agent, a leveling agent, a pigment dispersing agent, a sedimentation preventing agent, an anti-dripping agent, a catalyst, a hardening accelerator, and dehydration Examples of agents, deluters, ultraviolet absorbers, antioxidants, pigments, surfactants, and the like. When the coating film is prepared from the coating composition of the present invention, it can be applied to a suitable substrate such as concrete, mortar, siding board, extruded sheet, tile, metal, glass, wood, plastic, etc. Coating by roll coating, spray coating, etc., drying and hardening by an appropriate method, and drying in a dry building material, or by coating with a flowing coating or a roll coating in a factory. coating. Further, the coating composition may be directly applied to a substrate and coated by quilting, electrodeposition, primer (primer coating), or intermediate coating (coloring, etc.). Further, when the substrate is a metal, it may be applied to a surface treatment such as an iron phosphate treatment or a zinc phosphate treatment. Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited by the following examples. In addition, below, the viscosity -17-200948837 is measured by a B-type rotational viscometer. [1] Manufacture of polyisocyanate [Example 1] 880 g of hexamethylene diisocyanate was placed in a four-liter four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction tube. Formate system (stock), NCO content: 49.9 mass%, hereinafter referred to as HDI), and 120 g of tridecyl alcohol (Kyowa fermentation industry (share 0)), stir these while heating to 85 ° C, the urethanization reaction was carried out for 3 hours. Then, in the reaction liquid, urethane-based and trimeric isocyanate-catalyzed tin octylate (manufactured by Nippon Chemical Industry Co., Ltd.) was added to reach a specific NCO content at 1 1 〇 ° C. After the reaction was carried out, an acid phosphate (JP-508, manufactured by Seongbuk Chemical Industry Co., Ltd.) of 4 g of a reaction stopper was added, and the reaction was stopped at 50 ° C for 1 hour. Thus, the reaction product was removed, and excess HDI was removed by thin film distillation (condition: 140 ° C 0.0, 0.04 kPa) to obtain an NCO content of 15.8% by mass, a viscosity (25 ° C) of 320 mPa · s, and a free HDI content of 0.1% by mass. Polyisocyanate S-1). [Examples 2 to 4] Modified polyisocyanates S - 2 to S - 4 were obtained in the same manner as in Example 1 except that the amount of the catalyst or the like shown in Table 1 was changed and the NCO content was changed. -18- 200948837 [Example 5] 850 g of HDI (Japanese Polyurethane Industry Co., Ltd.) was placed in a four-liter four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction tube. 'NCO content: 49.9 mass%> ' and 150 g of KALCOL 200GD (2-octyldodecanol, manufactured by Kao Co., Ltd.)' This was stirred while heating to 85 ° C for urethane formation 3 hours. After the enthalpy, in the reaction, urethane diformate of 〇 2 g and tin octylate of a trimeric isocyanate catalyst (manufactured by Nippon Chemical Industry Co., Ltd.) were added, and the specific NCO content was reached at 110 ° C. After the reaction, an acid phosphate (JP-508 'Seibei Chemical Industry Co., Ltd.) of 8 g of a reaction stopper was added, and the reaction was stopped at 50 ° C for 1 hour. Thus, the reaction product was removed by excess HDI by thin film distillation (condition: 140 ° C '0.04 kPa) to obtain a modified polypolymer having an NCO content of 15.7 mass%, a viscosity (25 ° C) of 560 mPa·s, and a free HDI content of 0 to 2 mass%. ® Isocyanate S-5. [Example 6] A modified polyisocyanate S-6 was obtained in the same manner as in Example 5 except that the amount of the catalyst or the like shown in Table 1 was changed and the NCO content was changed. [Comparative Example 1] 850 g of HDI' and 15 g of -19-200948837 KALCOL 200GD (2-xin) were placed in a four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen introduction tube. Base dodecanol, manufactured by Kao (share), was stirred while heating to 85 ° C for urethanization for 3 hours. Then, 4 g of an allophanate and a trimeric isocyanate catalyst tin octylate (manufactured by Nippon Chemical Industry Co., Ltd.) were added to the reaction liquid to reach a specific NCO content at 110 ° C. After the reaction, 2.0 g of an acid phosphate (JP-508, manufactured by Seongbuk Chemical Industry Co., Ltd.) of a reaction stopper was added, and the reaction was stopped at 50 ° C for 1 hour. 0 From the reaction product, excess HDI was removed by thin film distillation (condition: 140 ° C, 0.04 kPa) to obtain an NCO content of 15.3% by mass, a viscosity (25 ° C) of 2,500 mPa · s, and a free HDI content of 0.1% by mass. Modified polyisocyanate H-1. [Comparative Example 2] 880 g of HDI and 120 g of triterpene alcohol were placed in a four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction tube (Kyowa Fermentation Co., Ltd.) This was stirred while heating to 85 ° C for urethane for 3 hours. Then, in the reaction liquid, zirconium octylate catalyst zirconium octoate (manufactured by the first dilute element chemical industry (manufactured by the company) was added, and the reaction was carried out at a specific NCO content at ll 〇 ° C. An acid phosphate (JP-5 08, manufactured by Seongbuk Chemical Industry Co., Ltd.) of 0.2 g of a reaction stopper was added, and the reaction was stopped at 50 ° C for 1 hour.
由該反應生成物，去除經由薄膜蒸餾（條件：140 °C -20- 200948837 ，0.04kPa)之過剩HDI，得到NCO含量14.8質量％，黏 度（25°C ) 130mPa · s，游離HDI含量0.1質量％之改性 聚異氰酸酯H-2。 [比較例3] 於具備攪拌器、溫度計、冷卻管、及氮氣導入管之容 量1升之四口燒瓶中，置入910g之HDI，90g之2-乙基 0 己醇，馬上加熱至80°C，進行胺基甲酸酯化2小時。 之後，添加0.1 g之三聚異氰酸酯化觸媒之2-羥丙基 三甲錢•辛酸鹽（D A B C Ο T M R、A i r p r 〇 d u c t s J a p a η (股 份）製），以8(TC，進行反應至達到特定之NCO含量後 ，添加〇.8g之反應停止劑之酸性磷酸酯（JP-508，城北化 學工業（股份）製），於50°C下進行停止反應1個小時。 由該反應生成物，去除經由薄膜蒸餾（條件：130 °C ，0.04kPa )之過剩HDI，得到NCO含量19.1質量％，黏 Φ 度（25°C ) 700mPa . s，游離之HDI含量0.2質量％之改 性聚異氰酸酯H-3。 [實施例7] 於具備攪拌器、溫度計、冷卻管、及氮氣導入管之容 量1升之四口燒瓶中，置入13 0g之該實施例4所得到之 聚異氰酸酯S-4、70g之該比較例2所得到之聚異氰酸酯 H-2，進行1小時攪拌、混合，得到NCO含量16.0質量％ ，黏度（25°C) 24 0mPa. s，游離HDI含量0.2質量％之 -21 - 200948837 改性聚異氰酸酯Η。。 [比較例4] 於具備攪拌器、溫度計、冷卻管、及氮氣導入管之容 量11之四口燒瓶中，置入100g之該實施例4所得到之聚 異氰酸酯S-4、100g之該比較例2所得到之聚異氰酸酯H-2，進行1小時攪拌、混合，得到NCO含量15.8質量％， 黏度（25°C) 210mPa.s，游離HDI含量0.2質量％之改 ❿ 性聚異氰酸酯H-4。 針對該實施例1〜7及比較例1〜4所得到之各聚異氰 酸酯，藉由下述方法，測定各自之脲基甲酸酯基、三聚異 氰酸酯基及胺基甲酸酯基之（生成）莫耳比。其結果示於 表1。 [測定法] 使用1 Η-N MR ( varian 製 Gem i ni2 000 ( 3 00MHz )，由 ◎ 鍵結於8_5ppm附近之脲基甲酸酯基之氮原子之氫原子的 記號，與鄰接於3.7PPm附近之三聚異氰酸酯基之氮原子 之甲撐基之氫原子的記號，以及鍵結於7. Oppm附近之胺 基甲酸酯之氮原子之氫原子的記號之面積比求出。具體的 測定條件如下。 測定溫度：23°C 試料濃度：〇.lg/lml 合計次數：3 2次 -22- 200948837 緩和時間：5秒 溶媒：重氫二甲亞楓 化學位移基準：重寥二甲亞楓之甲基的氫原子符號（ 2.5ppm ) 又，針對實施例1 ~ 7及比較例1〜4所得到之各聚異 氰酸酯，藉由以下方法，測定對於石油溶劑A (新日本石 油（股份）製）之20 °C下"的溶解性。其結果合倂示於表1 ❹ [測定法] 秤取lg聚異氰酸酯，於此中加入石油溶劑A ’混濁 時作成終點，求出此時所添加之石油溶劑A之量（g)。 利用該添加量，由下述式（1)算出容許度。 Ο) 容許度=有機溶劑之所要量（g)/採樣量（1 g) 200948837 [表l] 實施例 比麵 1 2 3 4 5 6 7 1 2 3 4 聚異氰酸醋 S-1 S-2 S-3 S-4 S-5 S-6 S-7 H-1 H-2 H-3 H-4 HDI(g) 880 880 880 880 850 850 850 880 910 • 十三醇ω 120 120 120 120 _ - 120 KALCOL 200GD(g) _ _ 150 150 - 150 2-乙基己醇(g) 90 - 辛酸錫(ppm) 100 100 100 150 200 300 400 - • • 辛酸锆(ppm) 100 DABCO TMR(ppm) 100 JP-508fg) 0.4 0.4 0.8 0.6 0.8 1.0 _ 2.0 0.2 0.8 _ S-4(g) . _ - • _ • 130 一 _ 100 H-2(g) - • • • _ _ 70 _ _ _ 100 停止NCO(質量％) 36.9 36.0 33.7 32.6 32.5 29.4 _ 25.0 38.9 30.5 • 蒸餾後NCO(質量％) 15.8 16.2 16.6 16.7 15.7 15.8 16.0 15.3 14.8 19.1 15.8 黏度(mPa . s) 320 400 710 890 560 1,200 240 2,500 130 700 210 容許度(_ >20.0 >20.0 6.0 2.2 40 1.2 >20.0 <0.1 >20.0 <0.1 >20.0 脲基甲酸醋比率(mol%) 69 63 52 48 45 36 65 28 96 48 72 三聚異氰酸酯比率(mol%) 31 37 48 52 55 64 35 72 4.0 52 28 胺基甲酸乙酯比率(mol%) 1.1 1.1 0.7 0.7 0.4 0.5 0.8 1.0 1.0 2.1 1.1 胺基甲酸乙酯比率：脲基甲酸酯基及三聚異氰酸酯基之總 量爲100時之比率 [2]二液型塗料組成物之製造 [實施例8〜14、比較例5〜8] 依表2所示比例’配合實施例1〜7及比較例1〜4所 得之各聚異氰酸酯與石油溶劑A(新日本石油（股份）製 )(聚異氰酸酯組成物）以及丙烯酸多元醇（ACRYDIC HU-5 96，大日本油墨化學工業（股份）製）、氧化鈦（ 200948837 CR-90、石原產業（股份）製），與石油溶劑A(新日本 石油（股份）製）’調製成二液型塗料組成物。 ❹ ❹ [表2] 實施例 比較例 8 9 10 11 12 13 14 5 6 7 8 聚異氰酸酯 S-l 2.9 S-2 2.8 S-3 2.7 S-4 2.7 S-5 2.9 S-6 2.9 S-7 2.8 H-l 2.6 H-2 3.1 H-3 2.2 H-4 2.8 石油溶劑A 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.1 1.3 0.9 1.2 NCO含量(％) 11.1 11.3 11.6 11.7 11.1 11.2 11.2 10.7 10.4 13.4 11.1 黏度(mPa · s，25〇C) 30 40 50 50 50 50 30 60 20 50 20 ACRYDIC HU-596 20 20 20 20 20 20 20 20 20 20 20 氧化欽CR-% 8.6 8.5 8.5 8.5 8.6 8.6 9.9 8.6 8.7 8.1 9.9 石油溶劑A 10.3 10.1 10.0 10.0 10.3 10.3 10.2 10.3 10.4 9.5 10.1 將該實施例8〜14及比較例6，8所調製之二液型塗 料組成物，各自以丁酮於脫脂之鋼板（JIS G 3 1 4 1商品名 SPCC-SB ' PF-1077處理，日本test pan el工業（股份）製 )中，利用薄層塗佈器，以濕式膜厚100μπι進行塗佈’於 溫度20 °C，相對濕度65 %之環境下，進行養成7天’形成 乾燥膜厚40〜50 μηι之塗膜。針對所得之塗膜，進行下述 各特性之評定。其結果示於表3。 -25- 200948837 另外，比較例5，7所調製之二液型塗料組成物’由 於對於低極性溶劑之容許度不足，故未能進行試驗。 (1 )耐彎曲性 依JIS K-5600-5-1: 1999之耐彎曲性試驗爲基準，利 用直徑2mm之圓筒形模蕊，進行評定是否經由圓筒形模 蕊彎曲時之塗膜的割裂、及由鋼板是否出現剝落。若無出 現塗膜割裂、剝落者判定爲合格者。 (2 )耐凹壓性 依JIS K-5600-5-2: 1999之耐凹壓試驗爲基準，利用 擠壓器，進行評定經由擠壓，是否出現部份變形時之塗膜 的割裂，及由鋼板是否出現剝落。經由擠壓器，塗膜的割 裂、剝落所產生之擠壓深度（mm)作爲耐凹壓性。 (3 )耐重錘掉落性 依JIS K-5600-5-3 : 1999之耐重錘掉落試驗爲基準， 利用直徑l〇_3mm、質量0.5 kg之砝碼，進行評定經由砝 碼掉落是否出現變形時之塗膜的割裂，及由鋼板是否出現 剝落。將塗膜的割裂、產生剝落之最低掉落高度（cm )作 爲耐重錘掉落性。 (4)塗膜硬度 依JIS K-5600-5-4: 1999之劃痕硬度試驗（鉛筆法） 200948837 爲基準，測定塗膜表面之硬度。於塗膜表面未產生痕跡之 最硬的鉛筆硬度作爲塗膜硬度。 (5 )密合性From the reaction product, excess HDI was removed by thin film distillation (condition: 140 ° C -20-200948837, 0.04 kPa) to obtain an NCO content of 14.8% by mass, a viscosity (25 ° C) of 130 mPa · s, and a free HDI content of 0.1 mass. % modified polyisocyanate H-2. [Comparative Example 3] 910 g of HDI and 90 g of 2-ethylhexyl alcohol were placed in a four-liter four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen introduction tube, and immediately heated to 80°. C, urethanization was carried out for 2 hours. Thereafter, 0.1 g of a 3-polypropyl isocyanate-catalyzed 2-hydroxypropyl triacetate octanoate (DABC Ο TMR, A irpr 〇ducts J apa η (manufactured by KK) was added, and the reaction was carried out at 8 (TC). After the specific NCO content, an acid phosphate (JP-508, manufactured by Seongbuk Chemical Industry Co., Ltd.) of 反应8 g of a reaction stopper was added, and the reaction was stopped at 50 ° C for 1 hour. Excess HDI by thin film distillation (condition: 130 ° C, 0.04 kPa) was removed to obtain a modified polyisocyanate H having an NCO content of 19.1% by mass, a viscosity of Φ (25 ° C) of 700 mPa·s, and a free HDI content of 0.2% by mass. -3. [Example 7] In a four-necked flask equipped with a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction tube, 130 g of the polyisocyanate S-4 obtained in Example 4 was placed. 70 g of the polyisocyanate H-2 obtained in Comparative Example 2 was stirred and mixed for 1 hour to obtain an NCO content of 16.0% by mass, a viscosity (25 ° C) of 24 0 mPa·s, and a free HDI content of 0.2% by mass - 21 - 200948837 Modified polyisocyanate Η. [Comparative Example 4] Into a four-necked flask of a stirrer, a thermometer, a cooling tube, and a nitrogen gas introduction tube, 100 g of the polyisocyanate S-4 obtained in Example 4 and 100 g of the polyisocyanate H obtained in Comparative Example 2 were placed. -2, the mixture was stirred and mixed for 1 hour to obtain a modified polyisocyanate H-4 having an NCO content of 15.8% by mass, a viscosity (25 ° C) of 210 mPa·s, and a free HDI content of 0.2% by mass. For Examples 1 to 7 And each of the polyisocyanates obtained in Comparative Examples 1 to 4 was measured for the molar ratio of each of the allophanate groups, the trimer isocyanate groups, and the urethane groups by the following method. It is shown in Table 1. [Measurement method] A mark of a hydrogen atom of a nitrogen atom of an allophanate group bonded to the vicinity of 8 to 5 ppm by a Η-N MR (Varian ig 2 ni (3 00 MHz )) was used. The area ratio of the sign of the hydrogen atom of the methylene group of the nitrogen atom adjacent to the trimeric isocyanate group in the vicinity of 3.7 ppm, and the sign of the hydrogen atom of the nitrogen atom of the urethane bonded to the vicinity of 7. Oppm The specific measurement conditions are as follows. Measurement temperature: 23 ° C Sample concentration: 〇.lg/lml Total number of times: 3 2 times-22- 200948837 Relaxation time: 5 seconds Solvent: Hydrogen dimethyl sulfoxide chemical shift reference: Hydrogen atom symbol (2.5ppm) of methyl dimethyl sulfoxide With respect to each of the polyisocyanates obtained in Examples 1 to 7 and Comparative Examples 1 to 4, the solubility in petroleum solvent A (manufactured by Nippon Oil Co., Ltd.) at 20 ° C was measured by the following method. The results are shown in Table 1. [Measurement Method] lg polyisocyanate was weighed, and the petroleum solvent A' was added to the turbidity to form an end point, and the amount (g) of the petroleum solvent A added at this time was determined. Using the added amount, the tolerance is calculated by the following formula (1). Ο) Tolerance = required amount of organic solvent (g) / sampled amount (1 g) 200948837 [Table 1] Example specific surface 1 2 3 4 5 6 7 1 2 3 4 Polyisocyanuric acid S-1 S- 2 S-3 S-4 S-5 S-6 S-7 H-1 H-2 H-3 H-4 HDI(g) 880 880 880 880 850 850 850 880 910 • Tridecyl alcohol ω 120 120 120 120 _ - 120 KALCOL 200GD(g) _ _ 150 150 - 150 2-Ethylhexanol (g) 90 - Tin octoate (ppm) 100 100 100 150 200 300 400 - • • Zirconium octoate (ppm) 100 DABCO TMR (ppm 100 JP-508fg) 0.4 0.4 0.8 0.6 0.8 1.0 _ 2.0 0.2 0.8 _ S-4(g) . _ - • _ • 130 _ 100 H-2(g) - • • • _ _ 70 _ _ _ 100 Stop NCO (% by mass) 36.9 36.0 33.7 32.6 32.5 29.4 _ 25.0 38.9 30.5 • NCO (% by mass) after distillation 15.8 16.2 16.6 16.7 15.7 15.8 16.0 15.3 14.8 19.1 15.8 Viscosity (mPa. s) 320 400 710 890 560 1,200 240 2,500 130 700 210 Tolerance (_ > 20.0 > 20.0 6.0 2.2 40 1.2 > 20.0 < 0.1 > 20.0 < 0.1 > 20.0 Urea carboxylic acid vinegar ratio (mol%) 69 63 52 48 45 36 65 28 96 48 72 Trimeric isocyanate ratio (mol%) 31 37 48 52 5 5 64 35 72 4.0 52 28 Ethyl carbamate ratio (mol%) 1.1 1.1 0.7 0.7 0.4 0.5 0.8 1.0 1.0 2.1 1.1 Ethyl carbamate ratio: The total amount of allophanate groups and trimeric isocyanate groups is Ratio of 100° [2] Production of two-component paint composition [Examples 8 to 14 and Comparative Examples 5 to 8] Each of Examples 1 to 7 and Comparative Examples 1 to 4 was obtained in accordance with the ratio shown in Table 2 Polyisocyanate and petroleum solvent A (manufactured by Nippon Oil Co., Ltd.) (polyisocyanate composition) and acrylic polyol (ACRYDIC HU-5 96, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), titanium oxide (200948837 CR-90) Ishihara Industry Co., Ltd., and a petroleum solvent A (Nippon Oil Co., Ltd.) are prepared into a two-component coating composition. ❹ ❹ [Table 2] Example Comparative Example 8 9 10 11 12 13 14 5 6 7 8 Polyisocyanate Sl 2.9 S-2 2.8 S-3 2.7 S-4 2.7 S-5 2.9 S-6 2.9 S-7 2.8 Hl 2.6 H-2 3.1 H-3 2.2 H-4 2.8 Petroleum solvent A 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.1 1.3 0.9 1.2 NCO content (%) 11.1 11.3 11.6 11.7 11.1 11.2 11.2 10.7 10.4 13.4 11.1 Viscosity (mPa · s, 25 〇C) 30 40 50 50 50 50 30 60 20 50 20 ACRYDIC HU-596 20 20 20 20 20 20 20 20 20 20 20 Oxidation CR-% 8.6 8.5 8.5 8.5 8.6 8.6 9.9 8.6 8.7 8.1 9.9 Petroleum Solvent A 10.3 10.1 10.0 10.0 10.3 10.3 10.2 10.3 10.4 9.5 10.1 The two-component paint compositions prepared in Examples 8 to 14 and Comparative Examples 6 and 8 were each subjected to methyl ethyl ketone on a degreased steel sheet (JIS G 3 1 4 1 trade name SPCC) -SB 'PF-1077 treatment, Japan test pan el industrial (stock) system, using a thin layer applicator, coating with a wet film thickness of 100μπι 'at a temperature of 20 ° C, relative humidity of 65% , to develop into 7 days' A dry film thickness of the coating film 40~50 μηι. The following characteristics were evaluated for the obtained coating film. The results are shown in Table 3. -25- 200948837 In addition, the two-component paint composition prepared in Comparative Examples 5 and 7 was not tested because of insufficient tolerance for a low-polar solvent. (1) Bending resistance According to the bending resistance test of JIS K-5600-5-1: 1999, a cylindrical mold core having a diameter of 2 mm was used to evaluate whether or not the coating film was bent through a cylindrical mold core. Split, and whether the steel sheet peeled off. If there is no film peeling or peeling, it is judged as qualified. (2) The dent resistance is determined by the squeezing pressure test according to JIS K-5600-5-2: 1999, and the squeezing is used to evaluate whether or not the film is split during the partial deformation by extrusion, and Whether the steel sheet peels off. The extrusion depth (mm) produced by the slitting and peeling of the coating film through the extruder was used as the recession resistance. (3) The weight drop resistance is based on the weight drop test of JIS K-5600-5-3: 1999. Using the weight of l〇_3mm and mass 0.5 kg, it is assessed whether the weight is dropped by the weight. The film is split when deformation occurs, and whether the steel sheet is peeled off. The minimum drop height (cm) at which the coating film is split and peeled off is used as the weight drop resistance. (4) Hardness of coating film The hardness of the surface of the coating film was measured in accordance with the scratch hardness test (pencil method) of JIS K-5600-5-4: 1999 on the basis of 200948837. The hardest pencil hardness at which no trace was formed on the surface of the coating film was taken as the hardness of the coating film. (5) Adhesion
實施例 比較例 8 9 10 11 12 13 14 6 8 耐彎曲性 合格 合格 合格 合格 合格 合格 合格 合格 合格 耐凹壓性 10 10 10 10 10 10 10 10 10 耐重錘掉落性 100 100 100 100 100 100 100 100 100 橫切(分類） 0 0 0 0 0 0 0 0 0 鉛筆硬度 HB F F F F F HB 2B B 使塗膜之密合性依JIS K-5600-5-6: 1999爲基準之棋 盤格膠帶剝離試驗，直角之格子圖案切入塗膜，對於由貫 穿至基底時之基底的剝離，評定（橫切法）塗膜之耐性。 ❹ .[表 3 ]____ 如表3所示，由實施例8〜1 4之塗料組成物所得到之 塗膜’其硬度爲良好者’同時亦顯示，其他各特性均爲良 好。 -27-EXAMPLES Comparative Example 8 9 10 11 12 13 14 6 8 Bending resistance Qualified Qualified Qualified Qualified Qualified Qualified dent resistance 10 10 10 10 10 10 10 10 10 10 Heavy hammer drop resistance 100 100 100 100 100 100 100 100 100 Transverse cut (classification) 0 0 0 0 0 0 0 0 0 Pencil hardness HB FFFFF HB 2B B The adhesion of the coating film is based on JIS K-5600-5-6: 1999. The grid pattern of the right angle was cut into the coating film, and the resistance of the coating film was evaluated (cross-cut method) for the peeling of the substrate from the time of penetration to the substrate. ❹. [Table 3] ____ As shown in Table 3, the coating film obtained by the coating compositions of Examples 8 to 14 had a good hardness, and it was also shown that all other characteristics were good. -27-