TW202003731A - Film coating agent - Google Patents
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- TW202003731A TW202003731A TW108114963A TW108114963A TW202003731A TW 202003731 A TW202003731 A TW 202003731A TW 108114963 A TW108114963 A TW 108114963A TW 108114963 A TW108114963 A TW 108114963A TW 202003731 A TW202003731 A TW 202003731A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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Abstract
Description
本發明涉及塗膜劑。 The present invention relates to a coating agent.
聚氨酯水分散體作為塗料、塗布劑的原料，例如作為飛機．汽車等的內外裝飾用、住宅的外牆面和地板材料等的塗料、塗布劑的原料被廣泛地利用。因此，對於聚氨酯水分散體，要求提供根據其使用的用途．目的等而具備各種特性(例如硬度、強度、耐久性等)的塗膜。 Aqueous polyurethane dispersions are used as raw materials for coatings and coating agents, such as airplanes. Raw materials for paints and coating agents for interior and exterior decoration of automobiles, exterior walls of houses, and floor materials are widely used. Therefore, for the polyurethane aqueous dispersion, it is required to provide the use according to its use. A coating film having various characteristics (for example, hardness, strength, durability, etc.) for purposes, etc.
例如，專利文獻1中，作為在基材上塗布後能夠容易進行重塗或除去多餘塗膜的塗布用組合物，公開了一種含有水性聚氨酯樹脂分散體的塗布用組合物，該水性聚氨酯樹脂分散體是使聚氨酯樹脂分散於水系介質中而得到的，上述聚氨酯樹脂是使(A)聚氨酯預聚物跟與異氰酸酯基具有反應性的(B)擴鏈劑反應而得到的，上述(A)聚氨酯預聚物是使(a)聚異氰酸酯化合物、(b)包含數均分子量為400~3000的聚碳酸酯多元醇的一種以上多元醇化合物、(c)含酸性基團的多元醇化合物和(d)在80~180℃解離的異氰酸酯基的封閉劑反應而得到的，氨基甲酸酯鍵的含有比例和脲鍵的含有比例的合計以固體成分基準計為7~18重量%，碳酸酯鍵的含有比例以固體成分基準計為15~40重量%，上述封閉劑進行鍵合的異氰酸酯基的含有比例以固體成分基準且以異氰酸酯基換算計為0.2~3重量%。 For example, Patent Literature 1 discloses a coating composition containing an aqueous polyurethane resin dispersion as a coating composition capable of easily recoating or removing excess coating film after coating on a substrate, the aqueous polyurethane resin dispersed The polyurethane resin is obtained by dispersing a polyurethane resin in an aqueous medium. The polyurethane resin is obtained by reacting (A) a polyurethane prepolymer with (B) a chain extender that is reactive with an isocyanate group. The above (A) polyurethane The prepolymer is made up of (a) a polyisocyanate compound, (b) one or more polyol compounds containing a polycarbonate polyol having a number average molecular weight of 400 to 3000, (c) an acid group-containing polyol compound and (d ) The isocyanate group dissociated at 80~180 ℃ obtained by the reaction, the total content of urethane bond content and urea bond content of 7-18% by weight based on solids, carbonate bond The content ratio is 15 to 40% by weight based on the solid content, and the content ratio of the isocyanate group to which the above-mentioned blocking agent is bonded is 0.2 to 3% by weight based on the solid content and converted to isocyanate groups.
(註：現有技術文獻：專利文獻1-日本特開2015-7239公報。) (Note: Prior Art Literature: Patent Literature 1-Japanese Unexamined Patent Publication No. 2015-7239.)
塗布用組合物，因其用途、目的要求耐熱性，特別是耐熱黃變性，但是以往的塗布用組合物，不具有充分的耐熱黃變性。 The coating composition requires heat resistance, especially heat yellowing due to its use and purpose, but the conventional coating composition does not have sufficient heat yellowing resistance.
本發明是基於以上情形而完成的發明，其目的在於提供硬度、耐熱黃變性和透明性優異的塗膜劑。 The present invention has been completed based on the above circumstances, and its object is to provide a coating agent excellent in hardness, heat yellowing resistance, and transparency.
本發明提供以下〔1〕~〔4〕的發明內容。 The present invention provides the following inventions [1] to [4].
〔1〕一種塗膜劑，含有使聚氨酯樹脂分散於水中而成的聚氨酯水分散體，所述聚氨酯樹脂是使(A)聚異氰酸酯、(B)含有聚酯多元醇和/或聚醚多元醇的多元醇化合物、(C)具有1個以上的酸性基團的多元醇以及(D)具有1個以上的氨基的化合物反應而得到的。 [1] A coating agent containing an aqueous polyurethane dispersion obtained by dispersing a polyurethane resin in water, wherein the polyurethane resin contains (A) polyisocyanate and (B) contains polyester polyol and/or polyether polyol It is obtained by reacting a polyol compound, (C) a polyol having one or more acidic groups, and (D) a compound having one or more amino groups.
〔2〕根據〔1〕記載的塗膜劑，其特徵在於，上述(C)具有1個以上的酸性基團的多元醇的中和劑為沸點為100℃以下的有機胺類。 [2] The coating agent according to [1], wherein the neutralizing agent of the polyol (C) having at least one acidic group is an organic amine having a boiling point of 100° C. or lower.
〔3〕根據〔1〕或〔2〕記載的塗膜劑，其特徵在於，上述(D)具有1個以上的氨基的化合物為選自己二酸二醯肼、肼和氨中的1種或2種以上。 [3] The coating agent according to [1] or [2], characterized in that the compound (D) having at least one amino group is selected from adipic acid dihydrazide, hydrazine, and ammonia. More than 2 types.
〔4〕根據〔1〕~〔3〕中任一項記載的塗膜劑，其特徵在於，進一步含有己二酸二醯肼。 [4] The coating agent according to any one of [1] to [3], further characterized by further containing adipic acid dihydrazide.
本發明可提供硬度、耐熱黃變性和透明性優異的塗膜劑。 The present invention can provide a coating agent excellent in hardness, heat yellowing resistance, and transparency.
本發明的塗膜劑含有聚氨酯水分散體。上述聚氨酯水分散體是使聚氨酯樹脂分散於水中而成的，上述聚氨酯樹脂是使(A)聚異氰酸酯、(B)含有聚酯多元醇和/或聚醚多元醇的多元醇、(C)具有1個以上的酸性基團的多元醇和(D)具有1個以上的氨基的化合物反應而得到的。 The coating agent of the present invention contains an aqueous polyurethane dispersion. The polyurethane aqueous dispersion is obtained by dispersing a polyurethane resin in water. The polyurethane resin is obtained by (A) a polyisocyanate, (B) a polyol containing a polyester polyol and/or a polyether polyol, and (C) having 1 It is obtained by reacting a polyhydric alcohol with more than one acidic group and (D) a compound having one or more amino groups.
上述(A)聚異氰酸酯沒有特別限定，可使用在本技術領域通常使用的聚異氰酸酯。具體而言，可舉出脂肪族聚異氰酸酯、脂環族聚異氰酸酯、芳香族聚異氰酸酯、芳香脂肪族聚異氰酸酯。 The (A) polyisocyanate is not particularly limited, and polyisocyanates generally used in the technical field can be used. Specific examples include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and aromatic aliphatic polyisocyanate.
作為脂肪族聚異氰酸酯，可舉出四亞甲基二異氰酸酯、十二亞甲基二異氰酸酯、六亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4- 三甲基六亞甲基二異氰酸酯、賴氨酸二異氰酸酯、2-甲基戊烷-1,5-二異氰酸酯、3-甲基戊烷-1,5-二異氰酸酯等。 Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4. ,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, etc.
作為脂環族聚異氰酸酯，可舉出異氟爾酮二異氰酸酯、氫化苯二亞甲基二異氰酸酯、4,4’-二環己基甲烷二異氰酸酯、1,4-環己烷二異氰酸酯、甲基環己烯二異氰酸酯、1,3-雙(二異氰酸酯甲基)環己烷等。 Examples of the alicyclic polyisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, and methyl Cyclohexene diisocyanate, 1,3-bis (diisocyanate methyl) cyclohexane, etc.
作為芳香族聚異氰酸酯，可舉出甲苯二異氰酸酯、2,2’-二苯基甲烷二異氰酸酯、2,4’-二苯基甲烷二異氰酸酯、4,4’-二苯基甲烷二異氰酸酯(MDI)、4,4’-二苄基二異氰酸酯、1,5-亞萘基二異氰酸酯、苯二亞甲基二異氰酸酯、1,3-亞苯基二異氰酸酯、1,4-亞苯基二異氰酸酯等。 Examples of the aromatic polyisocyanate include toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate (MDI ), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate Wait.
作為芳香脂肪族聚異氰酸酯，可舉出二烷基二苯基甲烷二異氰酸酯、四烷基二苯基甲烷二異氰酸酯、α,α,α,α-四甲基苯二亞甲基二異氰酸酯等。 Examples of the aromatic aliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α,α,α,α-tetramethylxylylene diisocyanate, and the like.
另外，可舉出這些聚異氰酸酯的2聚體、3聚體或雙縮脲化異氰酸酯等改性物。這些化合物，也可單獨或將2種以上並用而使用。 In addition, modified products such as dimers, trimers, and biuret isocyanates of these polyisocyanates can be mentioned. These compounds may be used alone or in combination of two or more.
上述聚異氰酸酯中，從耐熱黃變性、耐光性的觀點出發，優選為選自脂肪族聚異氰酸酯、脂環族聚異氰酸酯和芳香脂肪族聚異氰酸酯中的1種或2種以上，特別優選為芳香脂肪族聚異氰酸酯。 Among the above-mentioned polyisocyanates, from the viewpoint of heat yellowing resistance and light resistance, one or more kinds selected from aliphatic polyisocyanates, alicyclic polyisocyanates and aromatic aliphatic polyisocyanates are preferred, and aromatic fats are particularly preferred Group polyisocyanate.
上述(B)多元醇含有選自聚酯多元醇和聚醚多元醇中的1種或2種以上。 The above-mentioned (B) polyol contains one kind or two or more kinds selected from polyester polyols and polyether polyols.
上述聚酯多元醇通常可通過將多元羧酸和多元醇進行縮合反應而得到。 The above-mentioned polyester polyol can usually be obtained by subjecting a polycarboxylic acid and a polyhydric alcohol to a condensation reaction.
作為上述多元羧酸沒有特別限定，具體而言，可舉出草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、1,12-十二烷二羧酸、鄰苯二甲酸酐、間苯二甲酸、對苯二甲酸、二聚酸、鹵化鄰苯二甲酸酐、四氫鄰苯二甲酸、四氫鄰苯二甲酸酐、六氫鄰苯二甲酸、六氫鄰苯二甲酸酐、六氫對苯二甲酸、六氫間苯二甲酸、2,6-萘二酸、2,7-萘二酸、2,3-萘二酸、2,3-萘二酸酐、4,4’-聯苯二酸、以及這些羧酸的二烷基酯等二元酸、或者與這些羧酸對應的酸酐等、均苯四酸等多元酸。可單獨使用這些多元羧酸或將2 種以上組合使用。作為α,β-不飽和二元酸，可舉出馬來酸、馬來酸酐、富馬酸、衣康酸、衣康酸酐等。 The above polycarboxylic acid is not particularly limited, and specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1 ,12-dodecanedicarboxylic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimer acid, halogenated phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic acid Anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3 -Dibasic acids such as naphthalenedicarboxylic acid, 2,3-naphthalenediic anhydride, 4,4'-biphenyldioic acid, and dialkyl esters of these carboxylic acids, or anhydrides corresponding to these carboxylic acids, etc. Acid and other polyacids. These polycarboxylic acids can be used alone or in combination of two or more. Examples of the α,β-unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride.
作為上述多元醇沒有特別限定，具體而言，可舉出乙二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、2-甲基-1,3-丙二醇、1,4-丁二醇、新戊二醇、1,5-戊二醇、3-甲基-1,5-戊二醇、1,6-己二醇、2-甲基-2-丁基-1,3-丙二醇、2,2,4-三甲基-1,3-戊二醇、2-乙基-1,3-己二醇、2-甲基-1,8-辛二醇、1,9-壬二醇、2,4-二乙基-1,5-戊二醇、2-乙基-2-丁基-1,3-丙二醇、二乙二醇、二丙二醇、三乙二醇等二元醇，甘油、三羥甲基丙烷、季戊四醇、山梨糖醇等。 The polyhydric alcohol is not particularly limited, and specific examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 2-methyl 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-2-butyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl 1,1,8-octanediol, 1,9-nonanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, Diethylene glycol, dipropylene glycol, triethylene glycol and other glycols, glycerin, trimethylolpropane, pentaerythritol, sorbitol, etc.
作為多元羧酸和多元醇進行的縮合反應中使用的酯化催化劑，可使用路易士酸類、鹼金屬類、磺酸類等，具體而言，作為路易士酸，可例示鋁衍生物、錫衍生物、鈦衍生物，作為鹼金屬類，可例示烷醇鈉、烷醇鉀等，另外作為磺酸類可例示對甲苯磺酸、甲磺酸、硫酸等，其中特別是從可抑制著色和副反應的觀點出發優選為路易士酸類。作為這樣的路易士酸類，具體而言，可舉出四甲基鈦酸酯、四乙基鈦酸酯、四正丙基鈦酸酯、四異丙基鈦酸酯、四正丁基鈦酸酯等鈦化合物、二丁基二月桂酸錫、二丁基氧化錫、二丁基二乙酸錫、辛酸錫、氧化錫等錫化合物。 As the esterification catalyst used in the condensation reaction between the polycarboxylic acid and the polyhydric alcohol, Lewis acids, alkali metals, sulfonic acids, etc. can be used. Specifically, as the Lewis acid, aluminum derivatives and tin derivatives can be exemplified. , Titanium derivatives, as alkali metals, can be exemplified sodium alkoxide, potassium alkoxide, etc., and as sulfonic acids, can be exemplified p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, etc., especially from the coloring and side reactions From a viewpoint, Lewis acids are preferable. Specific examples of such Lewis acids include tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, and tetra-n-butyl titanate. Titanium compounds such as esters, tin compounds such as dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, tin octoate and tin oxide.
使用金屬化合物作為這些酯化催化劑的情況下的催化劑使用量，以相對於生成的聚酯多元醇的金屬換算的重量濃度計，通常優選為1ppm以上，更優選為3ppm以上，通常優選為30000ppm以下，更優選為1000ppm以下，進一步優選為250ppm以下，特別優選為130ppm以下。通過將使用的催化劑量設為30000ppm以下，不僅在經濟上是有利的，而且可提高得到的聚酯多元醇的熱穩定性。另外，通過設為1ppm以上，可提高聚酯多元醇製造反應時的聚合活性。 When the metal compound is used as these esterification catalysts, the amount of catalyst used is generally preferably 1 ppm or more, more preferably 3 ppm or more, and usually preferably 30,000 ppm or less in terms of the metal-based weight concentration of the polyester polyol produced. It is more preferably 1000 ppm or less, still more preferably 250 ppm or less, and particularly preferably 130 ppm or less. By setting the amount of the catalyst used to be 30,000 ppm or less, not only is it economically advantageous, but also the thermal stability of the obtained polyester polyol can be improved. In addition, by setting it to 1 ppm or more, the polymerization activity during the polyester polyol production reaction can be improved.
作為上述聚醚多元醇沒有特別限定，可使用本技術領域通常使用的聚醚多元醇。具體而言，可舉出乙二醇、丙二醇、丙烷二醇、丁二醇、戊二醇、3-甲基-1,5-戊二醇、己二醇、新戊二醇、二乙二醇、三乙二醇、四乙二醇、聚乙二醇、二丙二醇、三丙二醇、1,4-環己烷二甲醇、雙酚A、雙酚F、雙酚S、氫化雙酚A、二溴雙酚A、1,4-環己烷二甲醇、二羥基乙基對苯二甲酸、氫醌 二羥基乙基醚、三羥甲基丙烷、甘油、季戊四醇等多元醇、這些醇的環氧乙烷、環氧丙烷、環氧丁烷等的氧亞烷基衍生物等。 The polyether polyol is not particularly limited, and polyether polyols generally used in the technical field can be used. Specifically, ethylene glycol, propylene glycol, propane glycol, butylene glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, neopentyl glycol, diethylene glycol Alcohol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, hydrogenated bisphenol A, Polyhydric alcohols such as dibromobisphenol A, 1,4-cyclohexanedimethanol, dihydroxyethyl terephthalic acid, hydroquinone dihydroxyethyl ether, trimethylolpropane, glycerin, pentaerythritol, etc. Oxyalkylene derivatives such as ethylene oxide, propylene oxide, butylene oxide, etc.
本發明中，出於對含有UV固化樹脂的硬塗層的密合性提高、耐UV性的目的，作為(B)多元醇可以使用具有乙烯基的多元醇。作為上述具有乙烯基的多元醇，具體而言，可舉出丙烯酸-2-羥基乙酯、丙烯酸-2-羥基丙酯、丙烯酸-4-羥基丁酯、甲基丙烯酸-2-羥基乙酯、甲基丙烯酸-2-羥基丙酯、甘油單烯丙基醚、三羥甲基丙烷二烯丙基醚、季戊四醇三烯丙基醚等。這些多元醇中，從耐UV性的觀點出發優選為甘油單烯丙基醚。上述具有乙烯基的多元醇從對含有UV固化樹脂的硬塗層的密合性提高、耐UV性的的觀點出發，相對於上述聚氨酯100品質份，優選為1品質份以上，更優選為10品質份以上。另一方面，優選為50品質份以下，更優選為30品質份以下。 In the present invention, for the purpose of improving the adhesion to the UV-curable resin-containing hard coat layer and UV resistance, a polyol having a vinyl group can be used as the (B) polyol. Specific examples of the vinyl group-containing polyol include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 2-hydroxyethyl methacrylate. 2-Hydroxypropyl methacrylate, glycerol monoallyl ether, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, etc. Among these polyols, glycerol monoallyl ether is preferred from the viewpoint of UV resistance. The above-mentioned vinyl group-containing polyol is preferably 1 part by mass or more and more preferably 10 parts by mass with respect to 100 parts by mass of the polyurethane from the viewpoints of improved adhesion to a UV-curable hard coat layer and UV resistance. Above quality. On the other hand, it is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less.
在不損害本發明的效果的範圍內，可以使用上述聚酯多元醇和聚醚多元醇以外的多元醇。作為上述聚酯多元醇和聚醚多元醇以外的多元醇，具體而言，可使用公知的聚碳酸酯、聚醚酯、聚縮醛、聚烯烴、氟系、植物油系等。更具體而言，可舉出1,6-己二醇的碳酸酯多元醇、1,4-丁二醇和1,6-己二醇的碳酸酯多元醇、1,5-戊二醇和1,6-己二醇的碳酸酯、3-甲基-1,5-戊二醇和1,6-己二醇的碳酸酯多元醇、1,9-壬二醇和2-甲基-1,8-辛二醇的碳酸酯、1,4-環己烷二甲醇和1,6-己二醇的碳酸酯、1,4-環己烷二甲醇的碳酸酯、聚己內酯多元醇、聚酯多元醇、聚硫醚多元醇、聚縮醛多元醇、聚四亞甲基二醇、聚丁二烯多元醇、蓖麻油多元醇、大豆油多元醇、氟多元醇、矽多元醇等多元醇化合物或其改性物。 Polyols other than the above-mentioned polyester polyols and polyether polyols can be used as long as the effects of the present invention are not impaired. As the polyol other than the polyester polyol and the polyether polyol, specifically known polycarbonates, polyetheresters, polyacetals, polyolefins, fluorine-based, vegetable oil-based, and the like can be used. More specifically, carbonate polyols of 1,6-hexanediol, carbonate polyols of 1,4-butanediol and 1,6-hexanediol, 1,5-pentanediol and 1, Carbonate of 6-hexanediol, carbonate polyol of 3-methyl-1,5-pentanediol and 1,6-hexanediol, 1,9-nonanediol and 2-methyl-1,8- Carbonate of octanediol, carbonate of 1,4-cyclohexanedimethanol and 1,6-hexanediol, carbonate of 1,4-cyclohexanedimethanol, polycaprolactone polyol, polyester Polyols, polythioether polyols, polyacetal polyols, polytetramethylene glycol, polybutadiene polyols, castor oil polyols, soybean oil polyols, fluorine polyols, silicon polyols and other polyols Compounds or their modifications.
本發明中，上述聚酯多元醇和/或聚醚多元醇的含量，相對於上述多元醇100品質份，下限優選為20品質份以上，更優選為30品質份以上，上限優選為100品質份以下。如果上述聚酯多元醇和/或聚醚多元醇的含量為上述範圍內，則從折射率、硬度的觀點出發優選。 In the present invention, the content of the polyester polyol and/or polyether polyol is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and the upper limit is preferably 100 parts by mass or less relative to 100 parts by mass of the polyol. . If the content of the polyester polyol and/or polyether polyol is within the above range, it is preferable from the viewpoint of refractive index and hardness.
另外，聚酯多元醇和聚醚多元醇的含有比率是相對於聚酯多元醇100品質份，聚醚多元醇的含量優選為50品質份以上，更優選為80品質份以上。另一方面，優選為200品質份以下，更優選為120品質份以下。在含有比 率為上述範圍內的情況下，從折射率、硬度和耐熱性的觀點出發優選。 In addition, the content ratio of the polyester polyol and the polyether polyol is 100 parts by mass with respect to the polyester polyol, and the content of the polyether polyol is preferably 50 parts by mass or more, and more preferably 80 parts by mass or more. On the other hand, it is preferably 200 parts by mass or less, and more preferably 120 parts by mass or less. When the content ratio is within the above range, it is preferable from the viewpoint of refractive index, hardness and heat resistance.
本發明中，上述多元醇可以含有數均分子量為400以下的多元醇。 In the present invention, the polyol may contain a polyol having a number average molecular weight of 400 or less.
作為上述數均分子量為400以下的多元醇，前述的多元醇中，為以下記載的多元醇。即，可舉出乙二醇、二乙二醇、三乙二醇、1,2-丙二醇、1,3-丙二醇、新戊二醇、1,3-丁二醇、1,4-丁二醇、3-甲基戊二醇、1,6-己二醇、1,8-辛二醇、2-甲基-1,3-丙二醇、雙酚A、氫化雙酚A、環己烷二甲醇、甘油或三羥甲基丙烷等。這些多元醇中，從耐溶劑性的觀點出發優選為選自甘油和三羥甲基丙烷中的1種或2種。 As the polyol having the number average molecular weight of 400 or less, among the aforementioned polyols, the polyols described below. That is, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol Alcohol, 3-methylpentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,3-propanediol, bisphenol A, hydrogenated bisphenol A, cyclohexane di Methanol, glycerin or trimethylolpropane, etc. Among these polyols, one or two selected from glycerin and trimethylolpropane are preferred from the viewpoint of solvent resistance.
上述數均分子量為400以下的多元醇的含量，相對於上述聚氨酯樹脂100品質份，優選為0.1品質份以上，更優選為0.3品質份以上。另外，優選為3品質份以下，更優選為1品質份以下。在含量為上述範圍內的情況下，從聚氨酯樹脂製造時的操作的觀點出發優選。 The content of the polyol having a number average molecular weight of 400 or less is preferably 0.1 part by mass or more, and more preferably 0.3 part by mass or more with respect to 100 parts by mass of the polyurethane resin. In addition, it is preferably 3 parts by mass or less, and more preferably 1 part by mass or less. When the content is within the above range, it is preferable from the viewpoint of handling at the time of polyurethane resin production.
作為上述(C)具有酸性基團的多元醇的酸性基團，可舉出羧基及其鹽、磺酸基及其鹽等。 Examples of the acidic group of the polyol having an acidic group (C) include a carboxyl group and its salt, a sulfonic acid group and its salt, and the like.
作為上述具有羧基的多元醇，例如，可舉出2,2-二羥甲基丙酸、2,2-二羥甲基丁酸、2,2-二羥甲基戊酸、二羥基馬來酸、2,6-二羥基苯甲酸、3,4-二氨基苯甲酸等含羧酸化合物和它們的衍生物以及它們的鹽，以及使用這些它們而得到的聚酯多元醇。此外，也可舉出丙氨酸、氨基丁酸、氨基己酸、甘氨酸、谷氨酸、天冬氨酸、組氨酸等氨基酸類，琥珀酸、己二酸、馬來酸酐、鄰苯二甲酸、偏苯三酸酐等羧酸類。 Examples of the polyol having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, and dihydroxymaleic acid. Carboxylic acid-containing compounds such as acids, 2,6-dihydroxybenzoic acid, 3,4-diaminobenzoic acid, and their derivatives and their salts, and polyester polyols obtained by using these. In addition, amino acids such as alanine, aminobutyric acid, aminocaproic acid, glycine, glutamic acid, aspartic acid, histidine, and the like, succinic acid, adipic acid, maleic anhydride, phthalic acid Carboxylic acids such as formic acid and trimellitic anhydride.
作為上述具有磺酸基及其鹽的多元醇，例如，可舉出2-羥基乙磺酸、苯酚磺酸、磺基苯甲酸、磺基琥珀酸、5-磺基間苯二甲酸、對氨基苯磺酸、1,3-亞苯基二胺-4,6-二磺酸、2,4-二氨基甲苯-5-磺酸等含磺酸化合物及它們的衍生物、以及將它們共聚而得到的聚酯多元醇、聚醯胺多元醇、聚醯胺聚酯多元醇等。 Examples of the polyol having the sulfonic acid group and its salt include 2-hydroxyethanesulfonic acid, phenolsulfonic acid, sulfobenzoic acid, sulfosuccinic acid, 5-sulfoisophthalic acid, and p-amino group. Sulfonic acid-containing compounds such as benzenesulfonic acid, 1,3-phenylenediamine-4,6-disulfonic acid, 2,4-diaminotoluene-5-sulfonic acid, and their derivatives, and copolymerizing them The obtained polyester polyol, polyamide polyol, polyamide polyester polyol and the like.
這些羧基或磺酸基，通過中和製成鹽，可使最終得到的聚氨酯變 為水分散性。作為此時的中和劑，例如，可舉出氫氧化鈉、氫氧化鉀等非揮發性堿，三甲胺、三乙胺、二甲基乙醇胺、甲基二乙醇胺、三乙醇胺等叔胺類，氨等揮發性堿等。中和可在聚氨酯化反應前、反應中或反應後的任意一個中進行。 By neutralizing these carboxyl groups or sulfonic acid groups to form a salt, the resulting polyurethane can be made water-dispersible. Examples of the neutralizing agent at this time include nonvolatile sodium hydroxide and potassium hydroxide, and tertiary amines such as trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, and triethanolamine. Volatile compounds such as ammonia. Neutralization can be carried out before, during or after the polyurethane reaction.
作為上述中和劑，優選為沸點為100℃以下的胺化合物。具體而言，可舉出三甲胺、三乙胺、二甲基乙醇胺、甲基二乙醇胺、三乙醇胺等叔胺類，氨等揮發性堿。 As the neutralizing agent, an amine compound having a boiling point of 100° C. or lower is preferred. Specific examples include tertiary amines such as trimethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, and triethanolamine, and volatile compounds such as ammonia.
本發明中，上述具有酸性基團的多元醇，從原料供給穩定性、通用性的觀點出發，優選為上述具有羧基的多元醇，特別優選為2,2-二羥甲基丙酸。 In the present invention, the polyhydric alcohol having an acidic group is preferably the polyhydric alcohol having a carboxyl group from the viewpoints of raw material supply stability and versatility, and particularly preferably 2,2-dimethylolpropionic acid.
作為上述(D)具有1個以上的氨基的化合物，可使用選自氨、肼、碳醯二肼、己二酸二醯肼、癸二酸二醯肼和鄰苯二甲酸二醯肼等肼類中的1種或2種以上。作為上述具有1個以上的氨基的化合物，從耐熱黃變性的觀點出發優選為選自氨、肼、和己二酸二醯肼中的1種或2種以上，更優選為己二酸二醯肼。 As the compound (D) having one or more amino groups, hydrazines selected from ammonia, hydrazine, carbodihydrazine, adipic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide can be used. One or more than two in the category. The compound having one or more amino groups is preferably one or more selected from ammonia, hydrazine, and adipic dihydrazide from the viewpoint of heat yellowing resistance, and more preferably is adipic dihydrazide. .
本發明的聚氨酯水分散體的製造方法沒有特別限定，通常，相對於(B)含有聚酯多元醇和/或聚醚多元醇的多元醇、(C)具有1個以上的酸性基團的多元醇和(D)具有1個以上的氨基的化合物所含有的羥基和氨基的合計，以化學計量上過量的(A)聚異氰酸酯的異氰酸酯基與羥基和氨基的合計量的當量比1：0.85~1.1，在不含有溶劑或不具有活性氫基團的有機溶劑中使其反應而合成聚氨酯預聚物，然後進行(C)具有1個以上的酸性基團的多元醇的酸性基團的中和，然後通過在水中進行分散乳化，從而得到聚氨酯水分散體。然後，根據需要除去使用的溶劑，從而可得到聚氨酯水分散體。 The method for producing the polyurethane aqueous dispersion of the present invention is not particularly limited, and generally, it is (B) a polyol containing a polyester polyol and/or a polyether polyol, and (C) a polyol having one or more acid groups and (D) The stoichiometric excess of the total amount of hydroxyl groups and amino groups contained in the compound having one or more amino groups (A) The equivalent ratio of the total amount of isocyanate groups of the polyisocyanate group and the hydroxyl groups and amino groups is 1: 0.85 to 1.1, It is reacted in an organic solvent that does not contain a solvent or has no active hydrogen group to synthesize a polyurethane prepolymer, and then (C) neutralizes the acid group of the polyol having at least one acid group, and then By dispersing and emulsifying in water, an aqueous polyurethane dispersion is obtained. Then, if necessary, the solvent used is removed to obtain an aqueous polyurethane dispersion.
作為上述不具有活性氫基團的有機溶劑沒有特別限制，具體而言，可舉出二
本發明的聚氨酯水分散體的聚氨酯的數均分子量，從耐溶劑性、 基材密合性、與UV固化樹脂(硬塗層)的密合性的觀點出發，優選為2000以上，更優選為4000以上。另一方面優選為500000以下，更優選為100000以下。 The number average molecular weight of the polyurethane in the polyurethane aqueous dispersion of the present invention is preferably 2,000 or more from the viewpoint of solvent resistance, substrate adhesion, and adhesion to a UV-curable resin (hard coat layer), and more preferably Above 4000. On the other hand, it is preferably 500,000 or less, and more preferably 100,000 or less.
上述聚氨酯的酸值，從基材密合性的觀點出發，優選為20mgKOH/g以上，更優選為30mgKOH/g以上。另一方面，優選為50mgKOH/g以下，更優選為40mgKOH/g以下。 The acid value of the above-mentioned polyurethane is preferably 20 mgKOH/g or more, and more preferably 30 mgKOH/g or more from the viewpoint of base material adhesion. On the other hand, it is preferably 50 mgKOH/g or less, and more preferably 40 mgKOH/g or less.
上述聚氨酯的交聯度，從基材密合性、耐溶劑性的觀點出發，優選為0.01mol/Kg以上，更優選為0.03mol/Kg以上。另一方面，優選為1mol/Kg以下，更優選為0.5mol/Kg以下。 The degree of cross-linking of the polyurethane is preferably 0.01 mol/Kg or more, and more preferably 0.03 mol/Kg or more from the viewpoint of substrate adhesion and solvent resistance. On the other hand, it is preferably 1 mol/Kg or less, and more preferably 0.5 mol/Kg or less.
上述聚氨酯的氨基甲酸酯鍵量，從硬度、耐熱性、基材密合性的觀點出發，優選為2.0mol/Kg以上，更優選為2.5mol/Kg以上。另一方面，優選為10.0mol/Kg以下，更優選為7.5mol/Kg以下。 The urethane bond amount of the polyurethane is preferably 2.0 mol/Kg or more, and more preferably 2.5 mol/Kg or more from the viewpoint of hardness, heat resistance, and substrate adhesion. On the other hand, it is preferably 10.0 mol/Kg or less, and more preferably 7.5 mol/Kg or less.
本發明的塗膜劑，從透明性、耐熱黃變性、基材密合性、與UV固化樹脂(硬塗層)的密合性的觀點出發，上述聚氨酯相對於塗膜劑100品質份，優選含有20品質份以上、更優選含有50品質份以上。另外，優選含有90品質份以下、更優選含有80品質份以下。 The coating agent of the present invention is preferably the polyurethane described above with respect to 100 parts by mass of the coating agent from the viewpoints of transparency, heat yellowing resistance, substrate adhesion, and adhesion with a UV-curable resin (hard coat layer). The content is 20 parts by mass or more, and more preferably 50 parts by mass or more. Moreover, it is preferable to contain 90 mass parts or less, and it is more preferable to contain 80 mass parts or less.
本發明的塗膜劑，從透明性、耐熱黃變性、基材密合性、與UV固化樹脂(硬塗層)的密合性的觀點出發，可以添加己二酸二醯肼。己二酸二醯肼的添加量，相對於聚氨酯100品質份，優選為1品質份以上，更優選為10品質份以上，優選為20品質份以下。 The coating agent of the present invention may be added with adipic acid dihydrazide from the viewpoints of transparency, heat yellowing resistance, substrate adhesion, and adhesion with a UV-curable resin (hard coat layer). The addition amount of adipic acid dihydrazide is preferably 1 part by mass or more relative to 100 parts by mass of polyurethane, more preferably 10 parts by mass or more, and preferably 20 parts by mass or less.
本發明的塗膜劑只要不損害本發明的效果，根據需要，可含有顏料、增稠劑、紫外線吸收劑、抗氧化劑、光穩定劑、消泡劑、增塑劑、表面調整劑、抗沉降劑等其它添加劑。添加劑可以單獨使用1種，也可以並用2種以上。 The coating agent of the present invention may contain pigments, thickeners, ultraviolet absorbers, antioxidants, light stabilizers, defoamers, plasticizers, surface conditioners, anti-settling as long as it does not impair the effects of the present invention. Agent and other additives. One type of additive may be used alone, or two or more types may be used in combination.
作為上述顏料沒有特別限定，具體而言，例如、可舉出二氧化鈦、氧化鋅、氧化鐵、碳酸鈣、硫酸鋇、鉻黃、黏土、滑石、炭黑等無機顏料，偶氮系、重氮系、縮合偶氮系、硫靛系、陰丹酮系、蒽醌系、苯並咪唑系、酞菁 系、異吲哚啉酮系、苝系、喹吖啶酮系、二
作為上述增稠劑沒有特別限定，具體而言，可舉出選自合成高分子、纖維素和多糖類、松節油乳液中的至少一種(各自單獨或它們的2種以上的混合物)。 The thickener is not particularly limited, and specifically, at least one kind selected from synthetic polymers, cellulose, polysaccharides, and turpentine emulsion (individually or a mixture of two or more kinds thereof) may be mentioned.
作為合成高分子，例如可舉出聚丙烯酸類、聚乙烯醇、聚環氧乙烷、聚乙烯基吡咯烷酮、聚乙烯基甲醚、聚丙烯醯胺等。作為纖維素，可舉出乙基纖維素、甲基纖維素、羥甲基纖維素、羧甲基纖維素等。作為多糖類，例如可舉出黃原膠、瓜兒豆膠、酪蛋白、***膠、明膠、卡拉膠、精氨酸、黃蓍膠、刺槐豆膠、果膠等。 Examples of the synthetic polymer include polyacrylic acid, polyvinyl alcohol, polyethylene oxide, polyvinylpyrrolidone, polyvinyl methyl ether, and polypropylene amide. Examples of cellulose include ethyl cellulose, methyl cellulose, hydroxymethyl cellulose, and carboxymethyl cellulose. Examples of the polysaccharides include xanthan gum, guar gum, casein, gum arabic, gelatin, carrageenan, arginine, tragacanth gum, locust bean gum, and pectin.
作為松節油乳液，可舉出利用非離子系表面活性劑使礦質松節油和水乳化而得到的慕斯風格(
作為上述紫外線吸收劑沒有特別限定，具體而言，可舉出二苯甲酮系、苯並***系、氰基丙烯酸酯系、水楊酸酯系、草酸醯基苯胺系。作為紫外線穩定劑，可舉出受阻胺系化合物。更具體而言，可舉出“TINUVIN622LD”、“TINUVIN765”(以上，Ciba Specialty Chemicals公司生產)、“SANOL LS-2626”和“SANOL LS-765”(以上，三共公司生產)等光穩定劑、“TINUVIN328”和“TINUVIN234”(以上，Ciba Specialty Chemicals公司生產)等。 The ultraviolet absorber is not particularly limited, and specific examples include benzophenone-based, benzotriazole-based, cyanoacrylate-based, salicylate-based, and oxalic acid-based aniline-based. Examples of the ultraviolet stabilizer include hindered amine compounds. More specifically, light stabilizers such as "TINUVIN622LD", "TINUVIN765" (above, produced by Ciba Specialty Chemicals), "SANOL LS-2626" and "SANOL LS-765" (above, produced by Sankyo), etc., may be mentioned. "TINUVIN328" and "TINUVIN234" (above, produced by Ciba Specialty Chemicals), etc.
作為上述抗氧化劑沒有特別限定，具體而言，可舉出“IRGANOX245”、“IRGANOX1010”(以上，Ciba Specialty Chemicals公司生產)、“Sumilizer GA-80”(住友化學公司生產)和2,6-二丁基-4-甲基苯酚(BHT)等。 The antioxidant is not particularly limited, and specific examples include "IRGANOX245", "IRGANOX1010" (above, produced by Ciba Specialty Chemicals), "Sumilizer GA-80" (manufactured by Sumitomo Chemical), and 2,6-di Butyl-4-methylphenol (BHT), etc.
實施例 Examples
以下關於實施例和比較例，將本發明具體進行說明，但本發明不限定於此。 The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
〔聚酯多元醇(a-1)的合成〕 [Synthesis of polyester polyol (a-1)]
邊在具有溫度計、氮氣導入管和攪拌機的反應容器中吹入氮氣，邊投入馬 來酸酐16.76品質份、雙酚A-2EO加成物83.14品質份、二辛基錫0.1品質份，以塔頂溫度為50~60℃的方式將反應溫度設定為160~170℃，進行反應至酸值變為2.6mgKOH/g以下，得到羥值98.9mgKOH/g、重均分子量1100的聚酯多元醇(a-1)。 While blowing nitrogen into a reaction vessel equipped with a thermometer, a nitrogen introduction tube, and a stirrer, 16.76 parts by mass of maleic anhydride, 83.14 parts by mass of bisphenol A-2EO adduct, and 0.1 parts by mass of dioctyl tin were added to the top of the tower The reaction temperature is set to 160 to 170°C with the temperature of 50 to 60°C, and the reaction is carried out until the acid value becomes 2.6 mgKOH/g or less to obtain a polyester polyol with a hydroxyl value of 98.9 mgKOH/g and a weight average molecular weight of 1100 (a -1).
多元醇的平均羥值按照JIS K 1557進行測定。 The average hydroxyl value of the polyol is measured in accordance with JIS K 1557.
〔聚酯多元醇(a-2)的合成〕 [Synthesis of polyester polyol (a-2)]
邊在具有溫度計、氮氣導入管和攪拌機的反應容器中吹入氮氣，邊投入琥珀酸17.05品質份、雙酚A-2EO加成物82.85品質份、二辛基錫0.1品質份，以塔頂溫度為50~60℃的方式將反應溫度設定為160~170℃，進行反應至酸值變為2.6mgKOH/g以下，得到羥值98.5mgKOH/g、重均分子量1100的聚酯多元醇(a-2)。 While blowing nitrogen into a reaction vessel equipped with a thermometer, a nitrogen introduction tube and a stirrer, 17.05 parts by mass of succinic acid, 82.85 parts by mass of bisphenol A-2EO adduct, and 0.1 parts by mass of dioctyltin were added at the top temperature The reaction temperature is set to 160 to 170°C in the manner of 50 to 60°C, and the reaction is carried out until the acid value becomes 2.6 mgKOH/g or less to obtain a polyester polyol with a hydroxyl value of 98.5 mgKOH/g and a weight average molecular weight of 1100 (a- 2).
〔聚酯多元醇(b)的合成〕 [Synthesis of polyester polyol (b)]
邊在具有溫度計、氮氣導入管和攪拌機的反應容器中吹入氮氣，邊投入間苯二甲酸28.27品質份、對苯二甲酸14.14品質份、己二酸18.65品質份、新戊二醇31.02品質份、乙二醇7.92品質份、二辛基錫0.1品質份，以塔頂溫度為50~60℃的方式將反應溫度設為160~170℃，進行反應至酸值變為2.2mgKOH/g以下，得到羥值56.1mgKOH/g、重均分子量2000的聚酯多元醇(b)。 While blowing nitrogen into a reaction vessel with a thermometer, a nitrogen introduction tube, and a stirrer, 28.27 parts by mass of isophthalic acid, 14.14 parts by mass of terephthalic acid, 18.65 parts by mass of adipic acid, and 31.02 parts by mass of neopentyl glycol were added. , 7.92 parts by mass of ethylene glycol and 0.1 parts by mass of dioctyl tin, the reaction temperature is set to 160-170°C with the top temperature of 50-60°C, and the reaction is carried out until the acid value becomes 2.2 mgKOH/g or less, Polyester polyol (b) having a hydroxyl value of 56.1 mgKOH/g and a weight average molecular weight of 2000 was obtained.
<聚氨酯水分散體的合成> <Synthesis of polyurethane aqueous dispersion>
〔實施例1〕 [Example 1]
在具有攪拌機、回流冷凝管、溫度計和氮吹入管的4口燒瓶中，添加聚酯多元醇(a-1)(重量平均分子量：1100、羥值：98.9mgKOH/g)61.82品質份、三羥甲基丙烷0.54品質份、二羥甲基丙酸9.14品質份、甲乙酮100品質份並充分攪拌溶解，接著添加二甲苯二異氰酸酯28.5品質份在75℃使其反應至NCO含量變為1.0%。然後，將該預聚物溶液冷卻至45℃，添加作為中和劑的氨1.16品質份(1當量)、水300品質份，使用均質混合機乳化，然後添加氨0.41品質份，在30℃進行封端反應30分鐘。使該樹脂溶液在加熱減壓下餾去甲乙酮，得到固體成分25%的聚氨酯水分散體。 In a 4-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, add polyester polyol (a-1) (weight average molecular weight: 1100, hydroxyl value: 98.9 mgKOH/g) 61.82 parts by mass, trihydroxyl 0.54 parts by mass of methylpropane, 9.14 parts by mass of dimethylolpropionic acid, and 100 parts by mass of methyl ethyl ketone were thoroughly stirred and dissolved, and then 28.5 parts by mass of xylene diisocyanate was added to react at 75°C until the NCO content became 1.0%. Then, the prepolymer solution was cooled to 45°C, 1.16 parts by mass (1 equivalent) of ammonia and 300 parts by mass of water were added as a neutralizing agent, emulsified using a homomixer, and then 0.41 parts by mass of ammonia was added at 30°C. End-capping reaction for 30 minutes. The resin solution was distilled off under heating and reduced pressure to obtain an aqueous polyurethane dispersion having a solid content of 25%.
〔實施例2〕、〔實施例5〕、〔實施例8〕、〔實施例10〕和〔實施例13〕，如下述表1所示變更各原料的種類和投入量，除此以外，與〔實施例1〕同樣地進行製造，得到各聚氨酯水分散體。 [Example 2], [Example 5], [Example 8], [Example 10] and [Example 13], as shown in Table 1 below, change the type and input amount of each raw material, except [Example 1] The production was carried out in the same manner to obtain each polyurethane dispersion.
〔實施例3〕 [Example 3]
在具有攪拌機、回流冷凝管、溫度計和氮吹入管的4口燒瓶中，添加雙酚A的環氧乙烷4摩爾加成物(製品名：NEWPOL BPE-20NK、三洋化成工業株式會公司生產，重均分子量：400，羥值：345mgKOH/g)33.72品質份、甘油單烯丙基醚(製品名：NEOALLYLE-10、株式會社大阪SODA生產)10.00品質份、二羥甲基丙酸8.40品質份、甲乙酮100品質份並充分攪拌溶解，接著添加二甲苯二異氰酸酯44.88品質份在75℃使其反應至NCO含量變為1.0%。然後，添加己二酸二醯肼4.15品質份並在30℃進行封端反應30分鐘。然後，添加作為中和劑的氨1.07品質份、水300品質份，使用均質混合機進行乳化。然後，添加作為添加劑的己二酸二醯肼10品質份。使該樹脂溶液在加熱減壓下，餾去甲乙酮，得到固體成分25%的聚氨酯水分散體。 In a 4-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, add 4 moles of ethylene oxide bisphenol A adduct (product name: NEWPOL BPE-20NK, produced by Sanyo Chemical Industry Co., Ltd., Weight average molecular weight: 400, hydroxyl value: 345 mgKOH/g) 33.72 parts by mass, glycerol monoallyl ether (product name: NEOALLYLE-10, manufactured by Osaka SODA Co., Ltd.) 10.00 parts by mass, dimethylol propionic acid 8.40 parts by mass 1. 100 parts by mass of methyl ethyl ketone was thoroughly stirred and dissolved, and then 44.88 parts by mass of xylene diisocyanate was added to react at 75°C until the NCO content became 1.0%. Then, 4.15 parts by mass of adipic acid dihydrazide was added and the end-capping reaction was carried out at 30°C for 30 minutes. Then, 1.07 parts by mass of ammonia and 300 parts by mass of water were added as neutralizing agents, and emulsification was performed using a homomixer. Then, 10 parts by mass of adipic acid dihydrazide as an additive was added. This resin solution was heated under reduced pressure, and methyl ethyl ketone was distilled off to obtain a polyurethane aqueous dispersion having a solid content of 25%.
〔實施例4〕、〔實施例6〕、〔實施例7〕、〔實施例9〕、〔實施例11〕、和〔實施例12〕，如下述表1所示變更各原料的種類和投入量，除此以外，與〔實施例3〕同樣地進行製造，得到各聚氨酯水分散體。 [EXAMPLE 4], [EXAMPLE 6], [EXAMPLE 7], [EXAMPLE 9], [EXAMPLE 11], and [EXAMPLE 12], change the type and input of each raw material as shown in Table 1 below Except for the amount, it was manufactured in the same manner as [Example 3] to obtain each polyurethane aqueous dispersion.
〔比較例1〕 [Comparative Example 1]
在具有攪拌機、回流冷凝管、溫度計和氮吹入管的4口燒瓶中，添加雙酚A的環氧乙烷2摩爾加成物(製品名：NEWPOL BPE-20NK、三洋化成工業株式會公司生產、重均分子量：400、羥值：345mgKOH/g)33.72品質份、甘油單烯丙基醚(製品名：NEOALLYL E-10、株式會社大阪SODA生產)10.00品質份、二羥甲基丙酸8.40品質份、甲乙酮100品質份並充分攪拌溶解，接著添加二甲苯二異氰酸酯44.88品質份在75℃使其反應至NCO含量變為1.0%。然後，添加作為中和劑的氨1.07品質份、水300品質份使用均質混合機進行乳化，繼而繼續進行利用均質混合機的攪拌，進行利用水的鏈延伸反應。使該樹脂溶液在加熱減壓下，餾去甲乙酮，得到固體成分25%的聚氨酯水分散體。 In a 4-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, add 2 moles of ethylene oxide bisphenol A adduct (product name: NEWPOL BPE-20NK, manufactured by Sanyo Chemical Industry Co., Ltd., Weight average molecular weight: 400, hydroxyl value: 345 mgKOH/g) 33.72 parts by mass, glycerol monoallyl ether (product name: NEOALLYL E-10, manufactured by Osaka SODA Co., Ltd.) 10.00 parts by mass, dimethylol propionic acid 8.40 quality Parts, 100 parts by mass of methyl ethyl ketone and fully stirred to dissolve, and then 44.88 parts by mass of xylene diisocyanate was added to react at 75°C until the NCO content became 1.0%. Then, 1.07 parts by mass of ammonia and 300 parts by mass of water were added as a neutralizing agent for emulsification using a homomixer, and then the stirring by the homomixer was continued to perform a chain extension reaction using water. This resin solution was heated under reduced pressure, and methyl ethyl ketone was distilled off to obtain a polyurethane aqueous dispersion having a solid content of 25%.
〔比較例2〕如下述表1所示變更各原料的種類和投入量，除此以外，與〔比較例1〕同樣地進行製造，得到各聚氨酯水分散體。 [Comparative Example 2] Except for changing the type and input amount of each raw material as shown in Table 1 below, it was produced in the same manner as [Comparative Example 1] to obtain each polyurethane aqueous dispersion.
表1
〔聚氨酯水分散體的評價〕 [Evaluation of Aqueous Polyurethane Dispersion]
通過下述評價方法和評價基準進行評價。將評價結果示於表1。 The evaluation was performed by the following evaluation methods and evaluation criteria. Table 1 shows the evaluation results.
<外觀> <Appearance>
通過目測進行判定。 Determine by visual inspection.
<不揮發成分> <non-volatile components>
依照JIS K 6828進行測定。 Measured according to JIS K 6828.
<pH> <pH>
按照JIS Z8802進行評價。 Evaluation was performed in accordance with JIS Z8802.
<黏度> <viscosity>
按照JIS Z8803使用BM型黏度計(單圓筒型旋轉黏度計)測定25℃的黏度。此時，(a)將轉子速度設為60rpm進行測定，(b)在上述(a)中的測定值為8000mPa‧s以上的情況下，將轉子速度變更為30rpm進行測定，(c)在上述(b)中的測定值為16000mPa‧s以上的情況下，將轉子速度變更為12rpm進行測定。 The viscosity at 25° C. was measured in accordance with JIS Z8803 using a BM-type viscometer (single-cylinder rotary viscometer). At this time, (a) the rotor speed was measured at 60 rpm, (b) when the measured value in (a) above was 8000 mPa‧s or more, the rotor speed was changed to 30 rpm for measurement, (c) at the above When the measured value in (b) is 16000 mPa‧s or more, the rotor speed is changed to 12 rpm for measurement.
<平均粒徑> <average particle size>
通過MicrotracUPA-UZ152(日機裝公司生產)進行測定，計算50%平均值作為粒徑。 The measurement was performed by MicrotracUPA-UZ152 (manufactured by Nikkiso Co., Ltd.), and the 50% average value was calculated as the particle size.
〔耐熱黃變性的評價〕 [Evaluation of heat yellowing resistance]
如以下所示進行評價。將評價結果示於表1。 The evaluation is performed as shown below. Table 1 shows the evaluation results.
(聚氨酯水分散體的評價) (Evaluation of polyurethane aqueous dispersion)
通過目測將在70℃保存各聚氨酯水分散體3天後的顏色與保存前的顏色進行比較。評價基準如以下所示。 The color of each polyurethane aqueous dispersion stored at 70°C for 3 days was compared with the color before storage by visual inspection. The evaluation criteria are shown below.
◎：沒有變化 ◎: No change
○：略微黃變 ○: Slight yellowing
×：黃變。 ×: Yellowing.
(被膜的評價) (Evaluation of coating)
將各聚氨酯水分散體以乾燥厚度為約200~300μm的方式進行塗布，進行室溫乾燥(25℃)24小時，然後在50℃乾燥3小時，然後在120℃乾燥20分鐘，製作被膜。通過目測評價在200℃加熱製作的被膜2小時後的被膜的顏色。 Each polyurethane aqueous dispersion was applied so as to have a dry thickness of about 200 to 300 μm, dried at room temperature (25° C.) for 24 hours, then dried at 50° C. for 3 hours, and then dried at 120° C. for 20 minutes to produce a coating. The color of the film after heating the film produced at 200°C for 2 hours was evaluated by visual observation.
◎：沒有變化 ◎: No change
○：略微黃變 ○: Slight yellowing
×：變色為黑褐色 ×: The color changes to dark brown
如表1所示，不使(D)具有1個以上的氨基的化合物反應、使進行了鏈延長的聚氨酯預聚物分散於水中而得的聚氨酯水分散體，結果為被膜的耐熱黃變性劣化(比較例1、2)。 As shown in Table 1, a polyurethane aqueous dispersion obtained by dispersing (D) a compound having one or more amino groups and dispersing a chain-extended polyurethane prepolymer in water results in deterioration of the heat-resistant yellowing property of the coating (Comparative examples 1, 2).
產業上的可利用性 Industrial availability
本發明的塗膜劑可作為PET膜等的塗布劑使用，特別是作為光學用途的塗膜劑是有用的。 The coating agent of the present invention can be used as a coating agent for PET films and the like, and is particularly useful as a coating agent for optical applications.
Claims (4)
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| JP2018-105769 | 2018-06-01 | ||
| JP2018105769 | 2018-06-01 |
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| TW108114963A TW202003731A (en) | 2018-06-01 | 2019-04-29 | Film coating agent |
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| WO (1) | WO2019230393A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3641494A1 (en) * | 1986-12-04 | 1988-06-09 | Bayer Ag | POYLURETHANE SOLUBLE OR DISPERSABLE IN WATER, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COATING ANY SUBSTRATE |
| GB9211794D0 (en) * | 1992-06-04 | 1992-07-15 | Ici Resins Bv | Aqueous coating compositions |
| JP3282301B2 (en) * | 1993-07-16 | 2002-05-13 | 東洋インキ製造株式会社 | Aqueous coating composition and coating |
| JP2657203B2 (en) * | 1993-10-01 | 1997-09-24 | 中小企業事業団 | Aqueous printing ink composition |
| JPH07331169A (en) * | 1994-06-10 | 1995-12-19 | Toyo Ink Mfg Co Ltd | Water-based coating material |
| JP4117948B2 (en) * | 1998-11-05 | 2008-07-16 | 株式会社Ａｄｅｋａ | Water-based polyurethane resin composition |
| US7902291B2 (en) * | 2007-03-30 | 2011-03-08 | Nicca Chemical Co., Ltd. | Aqueous polyurethane resin composition and one-component adhesive agent and laminated body that use the same, and method for manufacturing aqueous polyurethane resin composition |
| WO2014050656A1 (en) * | 2012-09-27 | 2014-04-03 | Dic株式会社 | Coating agent and article produced using same |
| KR102412821B1 (en) * | 2014-11-04 | 2022-06-24 | 다이이치 고교 세이야쿠 가부시키가이샤 | Aqueous polyurethane resin composition |
-
2019
- 2019-04-29 TW TW108114963A patent/TW202003731A/en unknown
- 2019-05-15 WO PCT/JP2019/019258 patent/WO2019230393A1/en active Application Filing
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| WO2019230393A1 (en) | 2019-12-05 |
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