TWI470350B - A photohardenable resin composition and an article having a hardened film - Google Patents
A photohardenable resin composition and an article having a hardened film Download PDFInfo
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本發明係關於一種用於塗料、被覆等之光硬化性樹脂組成物、及具有其硬化皮膜之物品，更詳言之，係關於一種保存安定性良好、透明性高、且賦予高硬度、耐擦傷性、抗靜電性優異之硬化皮膜的光硬化性樹脂組成物、及具有其硬化皮膜之物品。The present invention relates to a photocurable resin composition for coating, coating, etc., and an article having the same, and more particularly to a storage stability, high transparency, high hardness, and resistance A photocurable resin composition of a hardened film excellent in abrasion resistance and antistatic property, and an article having a cured film.
聚甲基甲基丙烯酸酯樹脂、聚碳酸酯樹脂、聚苯乙烯樹脂、環狀聚烯烴樹脂、聚對苯二甲酸乙二酯樹脂、三乙醯纖維素樹脂等之合成樹脂，係具有輕量‧透明性‧易加工性等之優點。因此，如此之合成樹脂，近年來係被利用於CD、DVD等之光碟、液晶、EL面板等之顯示螢幕、各種機能性薄膜等各種領域上。a synthetic resin such as polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cyclic polyolefin resin, polyethylene terephthalate resin or triethylene glycol resin, which is lightweight ‧The advantages of transparency, easy processing and so on. Therefore, in recent years, such a synthetic resin has been used in various fields such as a display screen such as a CD, a DVD, or the like, a display screen such as a liquid crystal or an EL panel, and various functional films.
為使該等之表面的耐擦傷性向上提升，一般係實施有於媒體的記錄及/或再生光束入射側表面形成透明且具有耐擦傷性之硬被覆層。硬被覆層之形成，係藉由將含有分子中具有2個以上(甲基)丙烯基等之光反應性基的化合物、或使具有(甲基)丙烯基等之光反應性基的烷氧基矽烷於鹼性觸媒存在下進行了水解縮合之籠型構造的矽氧烷化合物(特開2002-363414號公報、特開2004-143449號公報：專利文獻1，2)、或具有光反應性基之烷氧基矽烷與膠質氧化矽之反應物等的組成物塗佈於媒體表面，且將此以紫外線等之活性能量線的照射而使其硬化而實施。In order to improve the scratch resistance of the surfaces, a hard coating layer which is transparent and scratch-resistant is formed on the recording side surface of the recording and/or reproducing light beam of the medium. The hard coating layer is formed by a compound containing a photoreactive group having two or more (meth)acryl groups in the molecule or an alkoxy group having a photoreactive group such as a (meth)acryl group. A oxane compound having a cage structure in which a hydrazine is hydrolyzed and condensed in the presence of a basic catalyst (Japanese Laid-Open Patent Publication No. 2002-363414, JP-A-2004-143449: Patent Document 1, 2), or has a photoreaction A composition such as a reaction product of alkoxy decane and colloidal cerium oxide is applied to the surface of the medium, and is cured by irradiation with an active energy ray such as ultraviolet rays.
又，以抗靜電性的提升為目的，係檢討有各種抗靜電劑的添加。雖有聚醚改性矽酮與過氯酸鋰的反應物(特開平5-320626號公報：專利文獻3)、或多官能丙烯酸酯與過氯酸鋰的反應物(特許第3673590號公報：專利文獻4)、多官能丙烯酸酯與(CF3 SO2 )2 NLi的混合物(特開平9-278831號公報、特開2001-288325號公報：專利文獻5，6)被提案，但其耐擦傷性並不充分。In addition, for the purpose of improving the antistatic property, it is reviewed that various antistatic agents are added. A reaction product of a polyether-modified fluorenone and lithium perchlorate (Japanese Patent Laid-Open No. Hei 5-320626: Patent Document 3) or a reaction product of a polyfunctional acrylate and lithium perchlorate (Japanese Patent No. 3673590: Patent Document 4), a mixture of a polyfunctional acrylate and (CF 3 SO 2 ) 2 NLi (Japanese Patent Laid-Open No. Hei 9-278831, JP-A-2001-288325: Patent Document 5, 6) is proposed, but it is resistant to abrasion. Sex is not sufficient.
因此，以改善耐擦傷性之目的的雖有氧化矽及矽烷水解物與(CF3 SO2 )2 NLi的混合物(特開2005-146110號公報、特開2006-70120號公報、特開2008-222951號公報：專利文獻7～9)被提案，但其為含有溶劑者。Therefore, a mixture of cerium oxide and decane hydrolyzate and (CF 3 SO 2 ) 2 NLi is used for the purpose of improving the scratch resistance (Japanese Unexamined Patent Publication No. Hei No. Hei No. 2005-146110, No. 2006-70120, JP-A-2008- Japanese Patent Publication No. 222951: Patent Documents 7 to 9) is proposed, but it is a solvent.
[專利文獻1]特開2002-363414號公報[Patent Document 1] JP-A-2002-363414
[專利文獻2]特開2004-143449號公報[Patent Document 2] JP-A-2004-143449
[專利文獻3]特開平5-320626號公報[Patent Document 3] JP-A-H05-320626
[專利文獻4]特許第3673590號公報[Patent Document 4] Patent No. 3673590
[專利文獻5]特開平9-278831號公報[Patent Document 5] JP-A-9-278831
[專利文獻6]特開2001-288325號公報[Patent Document 6] JP-A-2001-288325
[專利文獻7]特開2005-146110號公報[Patent Document 7] JP-A-2005-146110
[專利文獻8]特開2006-70120號公報[Patent Document 8] JP-A-2006-70120
[專利文獻9]特開2008-222951號公報[Patent Document 9] JP-A-2008-222951
本發明係有鑑於上述情事而成者，其係以提供一種保存安定性良好、透明性高、且賦予耐擦傷性、抗靜電性優異之硬化皮膜的光硬化性樹脂組成物、及具有其硬化皮膜之物品為目的。In view of the above, the present invention provides a photocurable resin composition which has good storage stability, high transparency, and imparts a scratch-resistant film having excellent scratch resistance and antistatic property, and has a hardening property. The purpose of the film is for the purpose.
本發明者為達成上述目的而一再專硏反覆檢討的結果，發現一種使含有(1)平均粒子徑為80nm以下之無機氧化物微粒子、(2)含有3個以上(甲基)丙烯基之化合物、(3)含有1個或2個(甲基)丙烯基之化合物、(4)下述所示之脂肪族胺系離子性化合物及(5)自由基系光聚合起始劑，且儘管實質上不含溶劑，其保存安定性良好、在25℃之黏度為500mPa‧s以下及塗佈作業性優異之光硬化性樹脂組成物硬化而成之皮膜，其對支持基體而言密著性良好、透明性高、在耐擦傷性、抗靜電性上表現優異，遂達成本發明。As a result of repeating the review, the present inventors have found that (1) inorganic oxide fine particles having an average particle diameter of 80 nm or less and (2) compounds containing three or more (meth)acryl groups are contained. (3) a compound containing one or two (meth)acryl groups, (4) an aliphatic amine-based ionic compound shown below, and (5) a radical photopolymerization initiator, and in spite of the substance The film which does not contain a solvent, and which has good stability, and has a viscosity of 500 mPa·s or less at 25 ° C and a photocurable resin composition excellent in coating workability, is excellent in adhesion to the support substrate. The invention is excellent in transparency, excellent in scratch resistance and antistatic property, and the present invention has been achieved.
因此，本發明係提供下述所示之光硬化性樹脂組成物及具有其硬化皮膜之物品。Therefore, the present invention provides a photocurable resin composition shown below and an article having the cured film thereof.
[請求項1][Request 1]
一種光硬化性樹脂組成物，其特徵係含有A photocurable resin composition characterized by
(1)平均粒子徑為80nm以下之無機氧化物微粒子、(1) inorganic oxide fine particles having an average particle diameter of 80 nm or less,
(2)含有3個以上(甲基)丙烯基之化合物、(2) a compound containing three or more (meth) propylene groups,
(3)含有1個或2個(甲基)丙烯基之化合物、(3) a compound containing one or two (meth) propylene groups,
(4)以R1 R2 R3 R4 N+ X- (R1 、R2 、R3 、R4 係由CH3 、C2 H5 、C2 H4 OCH3 、C6 H13 、C8 H17 所選出之基，各自的基可相同或相異；X係由N(SO2 CF2 )2 、BF4 、PF6 所選出之基)所表示之離子性化合物、(4) R 1 R 2 R 3 R 4 N + X - (R 1 , R 2 , R 3 , R 4 are from CH 3 , C 2 H 5 , C 2 H 4 OCH 3 , C 6 H 13 , a selected group of C 8 H 17 , each of which may be the same or different; X is an ionic compound represented by N(SO 2 CF 2 ) 2 , BF 4 , or a group selected by PF 6 ,
(5)自由基系光聚合起始劑所成，且(1)、(2)、(3)成分之合計100質量份中，(1)成分為25～70質量份、(2)成分為20～70質量份、(3)成分為5～30質量份，且相對於(1)、(2)、(3)成分之合計100質量份，(4)成分為0.05～3質量份、(5)成分為1～8質量份，又實質上不含溶劑，在25℃之黏度為500mPa‧s以下。(5) The radical photopolymerization initiator is formed, and in the total of 100 parts by mass of the components (1), (2), and (3), the component (1) is 25 to 70 parts by mass, and the component (2) is 20 to 70 parts by mass, and the component (3) is 5 to 30 parts by mass, and the component (4) is 0.05 to 3 parts by mass based on 100 parts by mass of the components (1), (2), and (3), ( 5) The component is 1 to 8 parts by mass, and substantially contains no solvent, and has a viscosity at 25 ° C of 500 mPa ‧ or less.
[請求項2][Request 2]
如請求項1所記載之光硬化性樹脂組成物，其中，(1)成分之平均粒子徑為80nm以下之無機氧化物微粒子係氧化矽微粒子。The photocurable resin composition according to claim 1, wherein the inorganic oxide fine particles of the component (1) having an average particle diameter of 80 nm or less are cerium oxide fine particles.
[請求項3][Request 3]
如請求項2所記載之光硬化性樹脂組成物，其中，氧化矽微粒子係經含有(甲基)丙烯基之矽烷耦合劑所處理者。The photocurable resin composition according to claim 2, wherein the cerium oxide fine particles are treated by a (meth)acryl-based decane coupling agent.
[請求項4][Request Item 4]
如請求項1～3中任1項所記載之光硬化性樹脂組成物，其係於(1)成分已預先分散於(2)成分及/或(3)成分所成之混合物中，混合(4)、(5)成分而成。The photocurable resin composition according to any one of claims 1 to 3, wherein the component (1) is previously dispersed in a mixture of the component (2) and/or the component (3), and is mixed ( 4), (5) ingredients.
[請求項5][Request 5]
一種物品，其特徵係形成有如請求項1～4中任1項所記載之光硬化性樹脂組成物的硬化皮膜所成之物品。An article formed by the hardened film of the photocurable resin composition according to any one of claims 1 to 4, wherein the article is formed.
本發明之光硬化性樹脂組成物，係在分散於含有(甲基)丙烯基之化合物中的無機氧化物微粒子中，藉由混合離子性化合物，以使無機氧化物微粒子與離子性化合物的相乘效果寄予抗靜電性與分散安定性雙方之效果，且實質上即使未搭配溶劑，亦能獲得保存安定性良好、透明性高、在耐磨耗性、抗靜電性上優異之皮膜。The photocurable resin composition of the present invention is obtained by mixing an ionic compound in the inorganic oxide fine particles dispersed in the (meth)acryl group-containing compound so that the inorganic oxide fine particles and the ionic compound are in phase. The effect of both the antistatic property and the dispersion stability is imparted to the effect, and even if the solvent is not used, a film excellent in storage stability, high transparency, and excellent in abrasion resistance and antistatic property can be obtained.
本發明之光硬化性樹脂組成物，係含有The photocurable resin composition of the present invention contains
(1)平均粒子徑為80nm以下之無機氧化物微粒子、(1) inorganic oxide fine particles having an average particle diameter of 80 nm or less,
(2)含有3個以上(甲基)丙烯基之化合物、(2) a compound containing three or more (meth) propylene groups,
(3)含有1個或2個(甲基)丙烯基之化合物、(3) a compound containing one or two (meth) propylene groups,
(4)脂肪族胺系離子性化合物、(4) an aliphatic amine-based ionic compound,
(5)自由基系光聚合起始劑，且實質上不含有溶劑，在25℃之黏度為500mPa‧s以下者。(5) A radical photopolymerization initiator which does not substantially contain a solvent and has a viscosity at 25 ° C of 500 mPa ‧ s or less.
(1)無機氧化物微粒子(1) Inorganic oxide microparticles
本發明之(1)無機氧化物微粒子，可舉例如Si、Ti、Al、Zn、Zr、In、Sn、Sb、Ce、Fe等之氧化物微粒子，或者是此等之複合氧化物微粒子等。金屬氧化物微粒子方面，具體而言，可舉例如氧化矽、氧化鋁、氧化鋯、氧化鈦、氧化鈰等之微粒子。(1) The inorganic oxide fine particles of the present invention include, for example, oxide fine particles of Si, Ti, Al, Zn, Zr, In, Sn, Sb, Ce, Fe, or the like, or composite oxide fine particles or the like. Specific examples of the metal oxide fine particles include fine particles such as cerium oxide, aluminum oxide, zirconium oxide, titanium oxide, and cerium oxide.
此等之無機氧化物微粒子的平均粒子徑為80nm以下，較佳為50nm以下。若使用大於80nm者，則安定性變差、皮膜上可見粒子狀異物，且有損其透明性。此外，其下限通常為10nm以上。又，本發明中，平均粒子徑係可藉由以動態光散射光子相關方法之粒度分佈測定裝置進行測定。The inorganic oxide fine particles have an average particle diameter of 80 nm or less, preferably 50 nm or less. When the use is larger than 80 nm, the stability is deteriorated, and particulate foreign matter is visible on the film, and the transparency is impaired. Further, the lower limit thereof is usually 10 nm or more. Further, in the present invention, the average particle diameter system can be measured by a particle size distribution measuring apparatus using a dynamic light scattering photon correlation method.
特別好的無機氧化物微粒子方面，係氧化矽微粒子，又以平均粒子徑為50nm以下者更佳。又，氧化矽微粒子亦可使用低折射率等之效果可期之中空、多孔質者。如此之無機氧化物微粒子方面，係可使用市售品，例如ELECOM ST-1003SIV(日揮觸媒化成(股)製)等。Particularly preferable inorganic oxide fine particles are cerium oxide fine particles, and those having an average particle diameter of 50 nm or less are more preferable. Further, the cerium oxide microparticles may have a hollow or porous effect such as a low refractive index. As such inorganic oxide fine particles, a commercially available product such as ELECOM ST-1003SIV (made by Nikko Catalyst) can be used.
氧化矽微粒子之中，更以使用藉由具有活性能量線反應性基之水解性矽烷化合物予以表面修飾者為佳。如此之反應性氧化矽微粒子，係藉由使組成物硬化時的活性能量線照射，而發生交聯反應，以固定於聚合物基質中。Among the cerium oxide microparticles, it is preferred to use a hydrolyzable decane compound having an active energy ray-reactive group for surface modification. Such a reactive cerium oxide microparticle is subjected to a crosslinking reaction by irradiation with an active energy ray when the composition is cured to be fixed in a polymer matrix.
在此，具有活性能量線反應性基之水解性矽烷化合物方面，可舉出含有(甲基)丙烯基之矽烷耦合劑，具體而言，可例示γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷、γ-甲基丙烯醯氧基丙基三氯矽烷、γ-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、γ-甲基丙烯醯氧基丙基甲基二氯矽烷、γ-甲基丙烯醯氧基丙基二甲基甲氧基矽烷、γ-甲基丙烯醯氧基丙基二甲基乙氧基矽烷、γ-甲基丙烯醯氧基丙基二甲基氯矽烷、γ-丙烯醯氧基丙基三甲氧基矽烷、γ-丙烯醯氧基丙基三乙氧基矽烷、γ-丙烯醯氧基丙基三氯矽烷、γ-丙烯醯氧基丙基甲基二甲氧基矽烷、γ-丙烯醯氧基丙基甲基二乙氧基矽烷、γ-丙烯醯氧基丙基甲基二氯矽烷、γ-丙烯醯氧基丙基二甲基甲氧基矽烷、γ-丙烯醯氧基丙基二甲基乙氧基矽烷、γ-丙烯醯氧基丙基二甲基氯矽烷、γ-丙烯醯氧基甲基三甲氧基矽烷、γ-丙烯醯氧基甲基三乙氧基矽烷、γ-丙烯醯氧基甲基三氯矽烷、γ-丙烯醯氧基甲基甲基二甲氧基矽烷、γ-丙烯醯氧基甲基甲基二乙氧基矽烷、γ-丙烯醯氧基甲基甲基二氯矽烷、γ-丙烯醯氧基甲基二甲基甲氧基矽烷、γ-丙烯醯氧基甲基二甲基乙氧基矽烷、γ-丙烯醯氧基甲基二甲基氯矽烷。Here, examples of the hydrolyzable decane compound having an active energy ray-reactive group include a (meth) propylene group-containing decane coupling agent, and specifically, γ-methyl propylene methoxy propyl trimethoxide is exemplified. Baseline, γ-methacryloxypropyltriethoxydecane, γ-methylpropenyloxypropyltrichlorodecane, γ-methylpropenyloxypropylmethyldimethoxydecane γ-Methyl propylene methoxy propyl methyl diethoxy decane, γ-methyl propylene methoxy propyl methyl dichloro decane, γ-methyl propylene methoxy propyl dimethyl methoxy Base decane, γ-methacryloxypropyl dimethyl ethoxy decane, γ-methyl propylene methoxy propyl dimethyl chloro decane, γ-propylene methoxy propyl trimethoxy decane, Γ-propylene methoxypropyl triethoxy decane, γ-propylene methoxy propyl trichloro decane, γ-propylene methoxy propyl methyl dimethoxy decane, γ-acryloxypropyl propyl Methyl diethoxy decane, γ-propylene methoxy propyl methyl dichloro decane, γ-propylene methoxy propyl dimethyl methoxy decane, γ-propylene methoxy propyl dimethyl oxygen Decane, γ-propylene methoxypropyl dimethyl chlorodecane, γ-propylene methoxymethyl trimethoxy decane, γ-propylene methoxymethyl triethoxy decane, γ-acryloxy group Trichloromethane, γ-propylene methoxymethyl methyl dimethoxy decane, γ-propylene methoxymethyl methyl diethoxy decane, γ-propylene methoxymethyl methyl dichloro decane And γ-propylene methoxymethyl dimethyl methoxy decane, γ-propylene methoxymethyl dimethyl ethoxy decane, γ-propylene methoxymethyl dimethyl chloro decane.
又，具有活性能量線反應性基之水解性矽烷化合物的表面修飾量，較佳為0.1～10質量%、更佳為0.5～8質量%、特別佳為1～5質量%。Further, the amount of surface modification of the hydrolyzable decane compound having an active energy ray-reactive group is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 8% by mass, particularly preferably from 1 to 5% by mass.
具有活性能量線反應性基之水解性矽烷化合物的表面修飾之方法方面，係可舉出在氧化矽微粒子存在下將具有活性能量線反應性基之水解性矽烷化合物進行水解之方法，此時所副生之具有活性能量線反應性基之水解性矽烷化合物的水解物，因會成為使保存安定性惡化、或使硬度降低之原因等之故，不得不消除。In the method of surface modification of the hydrolyzable decane compound having an active energy ray-reactive group, a method of hydrolyzing a hydrolyzable decane compound having an active energy ray-reactive group in the presence of cerium oxide microparticles is exemplified. The hydrolyzate of the hydrolyzable decane compound having an active energy ray-reactive group in the by-products has to be eliminated because the storage stability is deteriorated or the hardness is lowered.
較佳係使用將此等(1)無機氧化物微粒子，直接以1次粒子分散於後述之(2)含有3個以上(甲基)丙烯基之化合物、或(3)含有1個或2個(甲基)丙烯基之化合物中者，而因使其以1次粒子存在，而可獲得透明性等之外觀良好的皮膜。It is preferable to use such (1) inorganic oxide fine particles as a primary particle dispersed in the following (2) a compound containing three or more (meth)acryl groups, or (3) one or two. Among the (meth)acryl-based compounds, a film having a good appearance such as transparency can be obtained by being present as primary particles.
具體而言，可舉出將無機氧化物微粒子以分散劑或使用分散機器物理性地分散於含有(甲基)丙烯基之化合物中的方法、或於無機氧化物微粒子所分散之溶液中添加含有(甲基)丙烯基之化合物後，餾去分散劑之方法。Specifically, a method of physically dispersing the inorganic oxide fine particles in a compound containing a (meth)acryl group as a dispersing agent or a dispersing device, or adding a solution in a solution in which the inorganic oxide fine particles are dispersed may be mentioned. After the (meth)acryl-based compound, the dispersant is distilled off.
(2)含有3個以上(甲基)丙烯基之化合物(2) Compounds containing more than 3 (meth) propylene groups
本發明之(2)含有3個以上(甲基)丙烯基之化合物，係與(1)無機氧化物微粒子及(3)含有1個或2個(甲基)丙烯基之化合物共同成為硬化性成分之主成分者，且為形成於硬化後所得之皮膜的基質者。(2) The compound containing three or more (meth) propylene groups of the present invention is cured together with (1) inorganic oxide fine particles and (3) a compound containing one or two (meth) propylene groups. The main component of the component is a matrix formed on the film obtained after curing.
含有3個以上(甲基)丙烯基之化合物，係於分散(1)成分之無機氧化物微粒子的同時之黏合劑成分，藉由該化合物，係可獲得耐磨耗性優異、高硬度之硬化物者。The compound containing three or more (meth) propylene groups is a binder component which disperses the inorganic oxide fine particles of the component (1), and the compound is excellent in abrasion resistance and hardness. Object.
(2)成分之含有(甲基)丙烯基之化合物，係分子內具有3個以上之(甲基)丙烯基的化合物，可舉例如三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、甲氧基化季戊四醇四(甲基)丙烯酸酯、乙氧基化季戊四醇四(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三丙烯酸化異氰酸酯等。又，亦可舉出3官能以上之胺基甲酸酯丙烯酸酯、聚酯丙烯酸酯、具有活性能量線反應性基之水解性矽烷化合物的水解縮合物等之聚合物成分，但並非僅受限於此等者。(2) A compound containing a (meth)acryl group as a component, and a compound having three or more (meth)acryl groups in the molecule, and examples thereof include trimethylolpropane tri(meth)acrylate and pentaerythritol IV. (Meth) acrylate, methoxylated pentaerythritol tetra(meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, dipentaerythritol Hexa(meth)acrylate, pentaerythritol tri(meth)acrylate, triacrylated isocyanate, and the like. Further, a polymer component such as a trifunctional or higher urethane acrylate, a polyester acrylate, or a hydrolysis condensate of a hydrolyzable decane compound having an active energy ray-reactive group may be used, but it is not limited only. These are the same.
此等之化合物係可僅使用1種，亦可2種以上併用。These compounds may be used alone or in combination of two or more.
(3)含有1個或2個(甲基)丙烯基之化合物(3) Compounds containing one or two (meth) propylene groups
本發明之(3)含有1個或2個(甲基)丙烯基之化合物，係與(1)無機氧化物微粒子及(2)含有3個以上(甲基)丙烯基之化合物共同成為硬化性成分之主成分者，且為形成於硬化後所得之皮膜的基質者。(3) The compound containing one or two (meth)acrylyl groups of the present invention is cured together with (1) inorganic oxide fine particles and (2) a compound containing three or more (meth)acryl groups. The main component of the component is a matrix formed on the film obtained after curing.
特別是用以使黏度降低的成分，同時也是用以使與聚甲基甲基丙烯酸酯樹脂、聚碳酸酯樹脂、聚苯乙烯樹脂、環狀聚烯烴樹脂、聚對苯二甲酸乙二酯樹脂、三乙醯纖維素樹脂等之密著性向上提升用的成分。In particular, the component for lowering the viscosity is also used to make polymethyl methacrylate resin, polycarbonate resin, polystyrene resin, cyclic polyolefin resin, polyethylene terephthalate resin. A component for improving the adhesion of triacetyl phthalocyanine resin or the like.
(3)成分在用以使黏度降低方面，在25℃之黏度為100mPa‧s以下、特別是以50mPa‧s以下者為佳。下限雖無特別限制，但通常為1mPa‧s以上。此外，黏度係可藉由旋轉式黏度劑進行測定(以下相同)。(3) The component has a viscosity at 25 ° C of 100 mPa ‧ s or less, particularly 50 mPa ‧ s or less, in order to lower the viscosity. Although the lower limit is not particularly limited, it is usually 1 mPa ‧ or more. Further, the viscosity can be measured by a rotary viscosity agent (the same applies hereinafter).
此含有(甲基)丙烯基之化合物，特別是為了使密著性向上提升，係以於分子內具有羥基、環氧基等之官能基者為佳。又，以皮膚刺激性PII值為4.0以上者為佳。此外，各化合物的皮膚刺激性PII值，係可藉由文獻等查得。The compound containing a (meth)acryl group is particularly preferably a functional group having a hydroxyl group, an epoxy group or the like in the molecule in order to enhance the adhesion. Further, it is preferred that the skin irritation PII value is 4.0 or more. Further, the skin irritation PII value of each compound can be found by literature or the like.
可舉例如羥基乙基(甲基)丙烯酸酯、環氧丙基(甲基)丙烯酸酯、四氫糠基(甲基)丙烯酸酯、1，6-己烷二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、二丙烯酸化異氰酸酯、氧化乙烯改性雙酚A二(甲基)丙烯酸酯等，但並非僅受限於此等者。For example, hydroxyethyl (meth) acrylate, epoxy propyl (meth) acrylate, tetrahydroindenyl (meth) acrylate, 1,6-hexane diol di (meth) acrylate And triethylene glycol di(meth)acrylate, diacrylated isocyanate, ethylene oxide modified bisphenol A di(meth)acrylate, etc., but are not limited thereto.
此等之化合物係可僅使用1種，亦可2種以上併用。These compounds may be used alone or in combination of two or more.
(1)成分之搭配量，係於(1)成分與(2)成分與(3)成分之合計100質量份中，為25～70質量份、較佳為35～60質量份，且(2)成分之搭配量，係於(1)成分與(2)成分與(3)成分之合計100質量份中，為20～70質量份、較佳為30～55質量份，且(3)成分之搭配量，係於(1)成分與(2)成分與(3)成分之合計100質量份中，為5～30質量份、較佳為10～20質量份。(1) The amount of the component is 25 to 70 parts by mass, preferably 35 to 60 parts by mass, based on 100 parts by mass of the total of the components (1) and (2) and (3), and (2) The amount of the component is 20 to 70 parts by mass, preferably 30 to 55 parts by mass, and (3) of the total amount of the component (1) and the component (2) and the component (3). The amount of the component is 5 to 30 parts by mass, preferably 10 to 20 parts by mass, per 100 parts by mass of the total of the component (1) and the component (3).
(1)成分與(2)成分與(3)成分之合計100質量份中，若(1)成分之搭配量低於25質量份，則硬度會降低，無法獲得充分的耐磨耗性，若超過70質量份，則皮膜的外觀變差。又，若(2)成分之搭配量低於20質量份，則分散安定性會變差，且會使皮膜外觀惡化，若超過70質量份，則硬度會降低。若(3)成分之搭配量低於5質量份，則密著性變差，若超過30質量份，則硬度會降低。When the amount of the component (1) and the component (3) is less than 25 parts by mass, the hardness is lowered, and sufficient abrasion resistance cannot be obtained. When it exceeds 70 mass parts, the appearance of a film deteriorates. In addition, when the amount of the component (2) is less than 20 parts by mass, the dispersion stability is deteriorated and the appearance of the film is deteriorated, and if it exceeds 70 parts by mass, the hardness is lowered. When the amount of the component (3) is less than 5 parts by mass, the adhesion is deteriorated, and if it exceeds 30 parts by mass, the hardness is lowered.
(4)脂肪族胺系離子性化合物(4) Aliphatic amine ionic compounds
本發明中，(4)以R1 R2 R3 R4 N+ X- (R1 、R2 、R3 、R4 係由CH3 、C2 H5 、C2 H4 OCH3 、C6 H13 、C8 H17 所選出之基，各自的基可相同或相異。X係由N(SO2 CF3 )2 、BF4 、PF6 所選出之基)所表示之脂肪族胺系離子性化合物，係可用為相溶性及溶解性良好之抗靜電劑。又，因具有分散性改善之效果，可藉由添加而抑制保存時的凝集或沈降，更可防止皮膜白濁。In the present invention, (4) is R 1 R 2 R 3 R 4 N + X - (R 1 , R 2 , R 3 , and R 4 are derived from CH 3 , C 2 H 5 , C 2 H 4 OCH 3 , C 6 H 13 , C 8 H 17 selected groups, the respective groups may be the same or different. X is an aliphatic amine represented by N(SO 2 CF 3 ) 2 , BF 4 , PF 6 selected) An ionic compound is an antistatic agent which is excellent in compatibility and solubility. Further, since the effect of improving the dispersibility is obtained, aggregation or sedimentation during storage can be suppressed by addition, and the film can be prevented from being cloudy.
此等之中，更以常溫(通常5～40℃、特別是25℃)為液體之脂肪族胺系離子性化合物特別好。Among these, an aliphatic amine-based ionic compound which is liquid at normal temperature (usually 5 to 40 ° C, particularly 25 ° C) is particularly preferable.
在此，R1 ～R4 係由CH3 、C2 H5 、C2 H4 OCH3 、C6 H13 、C8 H17 所選出之基，各自的基可相同或相異。又，X係由N(SO2 CF3 )2 、BF4 、PF6 所選出之基。Here, R 1 to R 4 are groups selected from CH 3 , C 2 H 5 , C 2 H 4 OCH 3 , C 6 H 13 , and C 8 H 17 , and the respective groups may be the same or different. Further, X is a group selected from N(SO 2 CF 3 ) 2 , BF 4 and PF 6 .
以R1 R2 R3 R4 N+ X- 所表示之脂肪族胺系離子性化合物方面，具體而言，可舉出下述者等。Specific examples of the aliphatic amine-based ionic compound represented by R 1 R 2 R 3 R 4 N + X - include the following.
(C2 H5 )4 N+ BF4 - 、(CH3 )(C2 H5 )3 N+ BF4 - 、(CH3 )(C2 H5 )2 (C2 H4 OCH3 )N+ BF4 - 、(CH3 )3 (C6 H13 )N+ BF4 - 、(CH3 )(C8 H17 )3 N+ BF4 - 、(C2 H5 )4 N+ PF6 - 、(CH3 )(C2 H5 )3 N+ PF6 - 、(CH3 )(C2 H5 )2 (C2 H4 OCH3 )N+ PF6 - 、(CH3 )3 (C6 H13 )N+ PF6 - 、(CH3 )(C8 H17 )3 N+ PF6 - 、(C2 H5 )4 N+ (CF3 SO2 )2 N- 、(CH3 )(C2 H5 )3 N+ (CF3 SO2 )2 N- 、(CH3 )(C2 H5 )2 (C2 H4 OCH3 )N+ (CF3 SO2 )2 N- 、(CH3 )3 (C6 H13 )N+ (CF3 SO2 )2 N- 、(CH3 )(C8 H17 )3 N+ (CF3 SO2 )2 N- 。(C 2 H 5 ) 4 N + BF 4 - , (CH 3 )(C 2 H 5 ) 3 N + BF 4 - , (CH 3 )(C 2 H 5 ) 2 (C 2 H 4 OCH 3 )N + BF 4 - , (CH 3 ) 3 (C 6 H 13 )N + BF 4 - , (CH 3 )(C 8 H 17 ) 3 N + BF 4 - , (C 2 H 5 ) 4 N + PF 6 - , (CH 3 )(C 2 H 5 ) 3 N + PF 6 - , (CH 3 )(C 2 H 5 ) 2 (C 2 H 4 OCH 3 )N + PF 6 - , (CH 3 ) 3 ( C 6 H 13 )N + PF 6 - , (CH 3 )(C 8 H 17 ) 3 N + PF 6 - , (C 2 H 5 ) 4 N + (CF 3 SO 2 ) 2 N - , (CH 3 (C 2 H 5 ) 3 N + (CF 3 SO 2 ) 2 N - , (CH 3 )(C 2 H 5 ) 2 (C 2 H 4 OCH 3 )N + (CF 3 SO 2 ) 2 N - (CH 3 ) 3 (C 6 H 13 )N + (CF 3 SO 2 ) 2 N - , (CH 3 )(C 8 H 17 ) 3 N + (CF 3 SO 2 ) 2 N - .
使用上述離子性化合物時，硬化物的表面阻抗值在初期及高溫高濕時皆為1012 Ω以下，可獲得充分的抗塵埃附著效果。此外，本發明中，表面阻抗值係可藉由高阻抗阻抗率計進行測定。When the ionic compound is used, the surface resistance value of the cured product is 10 12 Ω or less at the initial stage and at the time of high temperature and high humidity, and a sufficient anti-dust adhesion effect can be obtained. Further, in the present invention, the surface impedance value can be measured by a high impedance impedance meter.
(4)成分之搭配量，相對於(1)成分與(2)成分與(3)成分之合計100質量份，為0.05～3質量份、較佳為0.1～2.5質量份、特別佳為0.1～2質量份。搭配量若過少，則無法獲得抗靜電效果，再者，安定性也變差。搭配量若過多，硬度會降低。(4) The amount of the component is 0.05 to 3 parts by mass, preferably 0.1 to 2.5 parts by mass, particularly preferably 0.1, based on 100 parts by mass of the total of the components (1) and (2) and (3). ~ 2 parts by mass. If the amount of the collocation is too small, the antistatic effect cannot be obtained, and further, the stability is also deteriorated. If the amount is too much, the hardness will decrease.
(5)自由基系光聚合起始劑(5) Free radical photopolymerization initiator
本發明之組成物中，含有(5)自由基系光聚合起始劑。自由基系光聚合起始劑方面，可選擇苯乙酮系、安息香系、醯膦基氧化物系、二苯基酮系、噻噸酮系等之一般者。具體而言，可舉出二苯基酮、苯甲酮、米希勒酮(Michler’s ketone)、噻噸酮衍生物、安息香乙基醚、二乙氧基苯乙酮、苯甲基二甲基縮酮、2-羥基-2-甲基乙基苯基酮、1-羥基環己基苯基酮、醯膦基氧化物衍生物、2-甲基-1-{4-(甲硫基)苯基}-2-嗎福啉基丙烷-1-酮、4-苯甲醯基-4’-甲基二苯基硫化物、2,4,6-三甲基苯甲醯基二苯基膦等。此等可單獨使用或組合2種以上使用之。The composition of the present invention contains (5) a radical photopolymerization initiator. The radical photopolymerization initiator may be selected from the group consisting of acetophenone-based, benzoin-based, phosphonium-based oxide-based, diphenylketone-based, and thioxanthone-based. Specific examples thereof include diphenyl ketone, benzophenone, Michler's ketone, thioxanthone derivative, benzoin ethyl ether, diethoxyacetophenone, benzyldimethyl group. Ketal, 2-hydroxy-2-methylethyl phenyl ketone, 1-hydroxycyclohexyl phenyl ketone, fluorenylphosphine oxide derivative, 2-methyl-1-{4-(methylthio)benzene -2-}-2-fosfolinylpropan-1-one, 4-benzylidene-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzhydryldiphenylphosphine Wait. These may be used alone or in combination of two or more.
此等之中，更以苯甲基二甲基縮酮、1-羥基環己基苯基酮、羥基二甲基苯乙酮、2-甲基-1-{4-(甲硫基)苯基}-2-嗎福啉基丙烷-1-酮、4-苯甲醯基-4’-甲基二苯基硫化物、2,4,6-三甲基苯甲醯基二苯基膦因表面硬化性良好之點而較佳。Among these, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, hydroxy dimethyl acetophenone, 2-methyl-1-{4-(methylthio)phenyl }-2-oxalinylpropan-1-one, 4-benzylidene-4'-methyldiphenyl sulfide, 2,4,6-trimethylbenzimidyldiphenylphosphine It is preferred that the surface hardenability is good.
自由基系光聚合起始劑的搭配量，相對於(1)成分與(2)成分與(3)成分之合計100質量份，為1～8質量份、較佳為2～6質量份。搭配量若過少，則硬化性惡化，若過多則密著性會降低。The amount of the radical photopolymerization initiator is from 1 to 8 parts by mass, preferably from 2 to 6 parts by mass, per 100 parts by mass of the total of the components (1) and (2) and (3). If the amount of the collocation is too small, the hardenability deteriorates, and if it is too much, the adhesion is lowered.
本發明之光硬化性樹脂組成物中，雖可進一步因應需要，而在不損及本發明之目的的範圍下含有矽烷耦合劑、聚合禁止劑、抗氧化劑、紫外線吸收劑、光安定劑、消泡劑、調平劑、表面張力降低劑等，但溶劑則實質上不含。在此，所謂實質上不含意指，容許以組成物中3質量%以下、特別是1質量%以下之比例含有。The photocurable resin composition of the present invention may further contain a decane coupling agent, a polymerization inhibiting agent, an antioxidant, an ultraviolet absorber, a light stabilizer, or a consumer, without departing from the object of the present invention. A foaming agent, a leveling agent, a surface tension reducing agent, etc., but the solvent is substantially absent. Here, the term "substantially does not mean" is allowed to be contained in a ratio of 3% by mass or less, particularly preferably 1% by mass or less, based on the composition.
本發明之組成物，雖使上述各成分依常法而藉由均一混合所得，但本發明中，係以使上述(1)成分預先與(2)成分或者是(3)成分混合，再將此與剩餘的成分混合為佳。In the composition of the present invention, the above components are obtained by uniform mixing according to a usual method. However, in the present invention, the component (1) is previously mixed with the component (2) or the component (3), and then This is preferably mixed with the remaining ingredients.
再者，此等之組成物係經調整使其在25℃之黏度為500mPa‧s以下，較佳為300mPa‧s以下。黏度若過高，則塗佈作業性會惡化，容易產生筋紋不均等。此外，本組成物在25℃之黏度係以10mPa‧s以上者為佳。Further, these compositions are adjusted so as to have a viscosity at 25 ° C of 500 mPa ‧ or less, preferably 300 mPa ‧ or less. If the viscosity is too high, the coating workability is deteriorated, and rib unevenness is likely to occur. Further, it is preferred that the composition has a viscosity at 25 ° C of 10 mPa ‧ s or more.
本發明之光硬化性樹脂組成物係塗佈於其表面必須賦予有耐磨耗性、抗靜電性之物品，特別是重播再生專用光碟、光記錄碟片、光磁記錄碟片等之光資訊媒體的表面，更詳言之，記錄或者是再生光束入射側表面、或光學透鏡、光學濾光鏡、抗反射膜、抗反射膜下層膜、及液晶顯示器、CRT顯示器、電漿顯示器、EL顯示器等之各種顯示元件等之表面上，且藉由成為硬化皮膜，而可賦予此等之表面的耐擦傷性、防污性，具有此硬化皮膜之物品，係在耐擦傷性、耐磨耗性及抗靜電性上表現優異者。The photocurable resin composition of the present invention is applied to an article having an abrasion resistance and an antistatic property, and particularly a light information such as a replaying dedicated optical disc, an optical recording disc, or a magneto-optical recording disc. The surface of the media, in more detail, the recording or reproduction of the incident side surface of the beam, or optical lens, optical filter, anti-reflection film, anti-reflection film underlayer film, and liquid crystal display, CRT display, plasma display, EL display On the surface of various display elements and the like, and by forming a hardened film, scratch resistance and antifouling properties can be imparted to such surfaces, and articles having such a cured film are resistant to abrasion and abrasion. And excellent in antistatic properties.
形成上述光硬化性樹脂組成物之皮膜的方法方面，係可藉由輥塗佈法、旋轉塗佈法等製作皮膜。In the method of forming the film of the photocurable resin composition, a film can be produced by a roll coating method, a spin coating method, or the like.
所形成之皮膜的膜厚為0.1～50μm、特別是以在0.5～30μm之範圍為佳。膜厚若過薄，則耐磨耗性有降低的情況，又若過厚，則耐裂性有降低的情況。The film thickness of the film formed is preferably from 0.1 to 50 μm, particularly preferably from 0.5 to 30 μm. If the film thickness is too thin, the abrasion resistance may be lowered, and if it is too thick, the crack resistance may be lowered.
使光硬化性樹脂組成物硬化用的光源方面，通常可使用包含在200～450nm之範圍波長的光之光源，例如高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、氙氣燈、碳弧燈等。照射量雖無特別限制，但以10～5,000mJ/cm2 、特別是20～1,000mJ/cm2 者為佳。硬化時間通常為0.5秒～2分、較佳為1秒～1分。In the light source for curing the photocurable resin composition, a light source including light having a wavelength in the range of 200 to 450 nm, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp or the like can be used. Although the irradiation amount is not particularly limited, it is preferably from 10 to 5,000 mJ/cm 2 , particularly preferably from 20 to 1,000 mJ/cm 2 . The hardening time is usually from 0.5 second to 2 minutes, preferably from 1 second to 1 minute.
以下，係顯示實施例及比較例以具體說明本發明，但本發明非僅限於下述之實施例。此外，下述例中，黏度係藉由旋轉式黏度劑所測定之值。Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited to the examples described below. Further, in the following examples, the viscosity is a value measured by a rotary viscosity agent.
[實施例1][Example 1]
將分散有經γ-甲基丙烯醯氧基丙基三甲氧基矽烷處理之氧化矽的乙氧基化季戊四醇四丙烯酸酯(以下稱S-PETTA；氧化矽濃度50質量%、氧化矽粒子徑30nm)80質量份、己烷二醇二丙烯酸酯(以下、HDODA、PII值5.5)20質量份、(CH3 )(C8 H17 )3 N+ (CF3 SO2 )2 N- (以下、MTOTFSI)0.2質量份、Darocure 1173(以下稱D1173；2-羥基-2-甲基-1-苯基丙烷-1-酮、自由基系光聚合起始劑、Ciba Specialty Chemicals公司製、商品名)3質量份予以混合，得到在25℃之黏度為180mPa‧s之光硬化性樹脂組成物。將此組成物塗佈於聚碳酸酯上使其厚度為5μm，以80W高壓水銀燈照射光2秒鐘(累積照射量200mJ/cm2 )，使其硬化，得到透明的膜。Ethoxylated pentaerythritol tetraacrylate (hereinafter referred to as S-PETTA; cerium oxide concentration: 50% by mass, cerium oxide particle diameter: 30 nm) in which cerium oxide treated with γ-methacryloxypropyltrimethoxydecane is dispersed 80 parts by mass of hexanediol diacrylate (hereinafter, HDODA, PII value: 5.5) 20 parts by mass, (CH 3 )(C 8 H 17 ) 3 N + (CF 3 SO 2 ) 2 N - (below, MTOTFSI) 0.2 parts by mass, Darocure 1173 (hereinafter referred to as D1173; 2-hydroxy-2-methyl-1-phenylpropan-1-one, a radical photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name) 3 parts by mass were mixed to obtain a photocurable resin composition having a viscosity at 25 ° C of 180 mPa ‧ s. This composition was coated on a polycarbonate to have a thickness of 5 μm, and irradiated with an 80 W high-pressure mercury lamp for 2 seconds (accumulated irradiation amount: 200 mJ/cm 2 ) to be cured to obtain a transparent film.
使用所得之膜，進行下述所示之評價。將此等之結果顯示於表1。Using the obtained film, the evaluation shown below was performed. The results of these are shown in Table 1.
保存安定性：Save stability:
40℃、14日後，目視判定有無沈降物，以下述基準進行評價。After 40 days and 14 days, the presence or absence of sediment was visually judged and evaluated based on the following criteria.
○：無沈降物○: no sediment
×：有沈降物×: There is sediment
皮膜透明性：Film transparency:
置入100cc的燒杯中目視判定，以下述基準進行評價。The measurement was visually judged by placing in a 100 cc beaker, and evaluation was performed based on the following criteria.
○：透明○: transparent
△：稍微白化△: slightly whitened
×：白化×: whitening
耐擦傷性、耐磨耗性：Scratch resistance, wear resistance:
以ASTM D 1044為基準，使用TABER磨耗試驗機(使用磨耗輪CS-10F)進行硬化皮膜的磨耗試驗(500g荷重、100回轉)，而磨耗試驗前後之硬化皮膜的濁度則使用濁度計(NDH2000、日本電色工業製)進行測定，使(磨耗試驗後之濁度減去磨耗試驗前之濁度)為ΔHaze(ΔHaze為15以下時，表示耐擦傷性、耐磨耗性良好)。The abrasion test of the hardened film (500 g load, 100 turns) was carried out using a TABER abrasion tester (using the wear wheel CS-10F) based on ASTM D 1044, and the turbidity of the hardened film before and after the abrasion test was measured using a turbidimeter ( NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd., and measured (the turbidity after the abrasion test minus the turbidity before the abrasion test) was ΔHaze (when ΔHaze was 15 or less, the scratch resistance and the abrasion resistance were good).
表面阻抗值：Surface resistance value:
使用高阻抗阻抗率計(Hiresta UP MCP-HT450型、DIA Instruments公司製)，於25℃、50%RH之氛圍下進行測定。The measurement was carried out in an atmosphere of 25 ° C and 50% RH using a high-impedance impedance meter (Hiresta UP MCP-HT450 type, manufactured by DIA Instruments).
半衰期：half life:
使用帶電電荷衰減度測定器(STATIC HONEST METER、SHISHIDO靜電公司製)，於25℃、50%RH之氛圍下進行測定。The measurement was carried out in an atmosphere of 25 ° C and 50% RH using a charged charge decay degree measuring instrument (STATIC HONEST METER, manufactured by SHISHADO ELECTRONICS CO., LTD.).
密著性：Adhesion:
藉由棋盤格膠帶剝離試驗，以下述基準進行評價。The board was peeled and tested by the checkerboard tape and evaluated on the basis of the following criteria.
○：無異常○: No abnormality
×：有剝離之處×: There is a stripping place
在TABER磨耗性試驗中，ΔHaze若為8，則耐磨耗性也高。又，表面阻抗值係低為5×1012 Ω，且半衰期也短為小於60秒。In the TABER abrasion test, if ΔHaze is 8, the abrasion resistance is also high. Further, the surface resistance value is as low as 5 × 10 12 Ω, and the half life is also as short as less than 60 seconds.
[實施例2，3及比較例1～7][Examples 2, 3 and Comparative Examples 1 to 7]
同樣地，改變搭配如下述表1、2中所示而得到膜，並進行評價。將此等之結果顯示於表1、2中。Similarly, the film was changed and the film was obtained as shown in the following Tables 1 and 2, and evaluated. The results of these are shown in Tables 1 and 2.
S-PETTA：分散有經γ-甲基丙烯醯氧基丙基三甲氧基矽烷處理之氧化矽的乙氧基化季戊四醇四丙烯酸酯、氧化矽濃度50質量%、氧化矽粒子徑30nmS-PETTA: ethoxylated pentaerythritol tetraacrylate in which cerium oxide treated with γ-methyl propylene methoxy propyl trimethoxy decane is dispersed, cerium oxide concentration: 50% by mass, cerium oxide particle diameter: 30 nm
S-PETTA-2：分散有經γ-甲基丙烯醯氧基丙基三甲氧基矽烷處理之氧化矽的乙氧基化季戊四醇四丙烯酸酯、氧化矽濃度50質量%、氧化矽粒子徑120nmS-PETTA-2: ethoxylated pentaerythritol tetraacrylate having cerium oxide treated by γ-methyl propylene methoxy propyl trimethoxy decane, cerium oxide concentration of 50% by mass, and cerium oxide particle diameter of 120 nm
HDODA：己烷二醇二丙烯酸酯HDODA: Hexanediol diacrylate
THFFA：四氫糠基丙烯酸酯THFFA: tetrahydrofurfuryl acrylate
MTOTFSI：(CH3 )(C8 H17 )3 N+ (CF3 SO2 )2 N- MTOTFSI: (CH 3 )(C 8 H 17 ) 3 N + (CF 3 SO 2 ) 2 N -
D1173：Darocure 1173、2-羥基-2-甲基-1-苯基丙烷-1-酮、Ciba Specialty Chemicals公司製、商品名D1173: Darocure 1173, 2-hydroxy-2-methyl-1-phenylpropan-1-one, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name
PGM：丙二醇單甲基醚PGM: propylene glycol monomethyl ether
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| JP6467122B2 (en) * | 2012-12-28 | 2019-02-06 | 第一工業製薬株式会社 | Method for producing coating agent for film formation and method for producing cured product thereof |
| JP6450531B2 (en) * | 2014-06-11 | 2019-01-09 | 日揮触媒化成株式会社 | Manufacturing method of substrate with antireflection film |
| JP6470498B2 (en) * | 2014-03-31 | 2019-02-13 | 日揮触媒化成株式会社 | Coating liquid for forming transparent film and method for producing substrate with transparent film |
| KR102379944B1 (en) * | 2014-03-31 | 2022-03-29 | 니끼 쇼꾸바이 카세이 가부시키가이샤 | Coating liquid for forming transparent coating and method for producing said coating liquid, organic resin-dispersed sol, and substrate with transparent coating and method for producing said substrate |
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| TW200734391A (en) * | 2005-10-28 | 2007-09-16 | Sumitomo Osaka Cement Co Ltd | Transparent dispersion liquid of inorganic oxide, resin composition containing inorganic oxide particles, encapsulating composition for light-emitting element, light-emitting element, hardocoat film, optical function film, optical parts and production me |
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