TWI430022B - Radiation-sensitive resin composition, spacer and protective film of liquid crystal display element, and liquid crystal display element - Google Patents

Description

感放射線性樹脂組成物、液晶顯示元件之間隔物與保護膜、及液晶顯示元件Radiation-sensitive linear resin composition, spacer and protective film of liquid crystal display element, and liquid crystal display element

本發明是關於感放射線性樹脂組成物、液晶顯示元件的間隔物與保護膜及液晶顯示元件。The present invention relates to a radiation sensitive resin composition, a spacer of a liquid crystal display element, a protective film, and a liquid crystal display element.

於液晶顯示元件所使用的構件之中，間隔物、保護膜等大多係藉由微影術來形成(例如參照專利文獻1、專利文獻2)。此方法係將感放射線性樹脂組成物塗布在基板上，隔著指定的光罩以紫外線曝光後，進行顯像，形成點狀或條紋狀的圖案。又，依照此方法，亦具有藉由控制感放射線性樹脂組成物的塗布膜厚，而容易控制間隔物的晶胞間隙寬度之優點等。Among the members used for the liquid crystal display device, a spacer, a protective film, and the like are often formed by lithography (see, for example, Patent Document 1 and Patent Document 2). In this method, a radiation-sensitive resin composition is applied onto a substrate, and after exposure to ultraviolet light through a predetermined mask, development is performed to form a dot-like or striped pattern. Further, according to this method, it is also advantageous to control the thickness of the cell gap of the spacer by controlling the coating film thickness of the radiation sensitive resin composition.

然而，於液晶表示面板的製造中，從生產性的提高、對於應大型畫面的觀點來看，基板尺寸的大型化係正進行著。基板尺寸係經過300mm×400m的第一世代、370mm×470mm的第二世代、620mm×750mm的第三世代、960mm×1,100mm的第四世代，現在成為主流的是1,100mm×1,300mm的第五世代。再者，1,500mm×1,850mm的第六世代、1,850mm×2,100mm的第七世代、2,200mm×2,600mm的第八世代的基板尺寸係在今後更大型化。However, in the manufacture of the liquid crystal display panel, the increase in productivity and the increase in the size of the substrate are progressing from the viewpoint of a large-sized screen. The substrate size is the first generation of 300mm × 400m, the second generation of 370mm × 470mm, the third generation of 620mm × 750mm, the fourth generation of 960mm × 1,100mm, and now the mainstream is the fifth of 1,100mm × 1,300mm Generations. Furthermore, the seventh generation of 1,500 mm × 1,850 mm, the seventh generation of 1,850 mm × 2,100 mm, and the eighth generation of 2,200 mm × 2,600 mm have a larger substrate size in the future.

於基板尺寸為小型，例如為370mm×470mm以下時，感放射線性樹脂組成物在基板上於中央滴下，藉由旋轉塗布法而塗布。於此方法中，塗布係需要大量的感放射線樹脂組成物溶液，而且有無法應付大型基板的缺點。When the substrate size is small, for example, 370 mm × 470 mm or less, the radiation-sensitive resin composition is dropped on the substrate at the center, and is applied by a spin coating method. In this method, the coating system requires a large amount of a radiation-sensitive resin composition solution, and there is a disadvantage that it cannot cope with a large-sized substrate.

於基板尺寸為960mm×1,100mm以下時，以感放射線性樹脂組成物溶液的省液為目的，藉由狹縫及旋轉法來進行塗布。此方法係將來自縫型噴嘴的感放射線性樹脂組成物溶液塗布到基板面，然後藉由將基板旋轉，而形成均勻的塗膜。此方法雖然有效於省液，但是難以應付第五世代以後的基板尺寸。When the substrate size is 960 mm × 1,100 mm or less, the coating is performed by a slit and a spin method for the purpose of liquid-saving of the radiation-sensitive resin composition solution. In this method, a solution of a radiation-sensitive resin composition from a slit nozzle is applied to a substrate surface, and then a uniform coating film is formed by rotating the substrate. Although this method is effective for liquid saving, it is difficult to cope with the substrate size after the fifth generation.

根據如此的背景，隨著基板尺寸的大型化，變成藉由縫模(slit die)機來進行塗布。然而，於縫模機的情況，容易發生筋狀的瑕疵、莫阿瑕疵、基板輸送臂或針、吸附墊的痕跡(針跡)、基板端部的膜厚之不均勻化。According to such a background, as the size of the substrate is increased, coating is performed by a slit die machine. However, in the case of a slitting machine, unevenness of the rib-shaped ruthenium, mo A 瑕疵, the substrate transfer arm or the needle, the trace of the adsorption pad (stitch), and the film thickness at the end portion of the substrate tend to occur.

根據如此的理由，於縫模法中，強烈希望開發出所用的膜厚為均勻且沒有瑕疵的感放射線性樹脂組成物溶液。For this reason, in the slit die method, it has been strongly desired to develop a radiation-sensitive resin composition solution having a uniform film thickness and no flaw.

[專利文獻1]特開平5-165214號公報[Patent Document 1] Japanese Patent Publication No. Hei 5-165214

[專利文獻2]特開2001-261761號公報[Patent Document 2] JP-A-2001-261761

因此，本發明之目的為提供適合於藉由縫模塗布法來形成膜厚均勻且沒有瑕疵的塗膜之感放射線性樹脂組成物，由其所形成的間隔物或保護膜，以及具備彼等的的液晶顯示元件。Accordingly, it is an object of the present invention to provide a radiation-sensitive resin composition suitable for forming a coating film having a uniform film thickness and no flaw by a slit die coating method, a spacer or a protective film formed therefrom, and having such a spacer Liquid crystal display elements.

本發明的其它目的及優點係可由以下的說明所明知。Other objects and advantages of the invention will be apparent from the description which follows.

依照本發明，本發明的上述目的及優點之第一係藉由一種感放射線性樹脂組成物來達成，其特徵為含有： (A)(a1)與(a2)的共聚物，該(a1)係由不飽和羧酸及不飽和羧酸酐所組成族群所選出的至少1種，該(a2)係與前述(a1)不同的其它不飽和化合物，(B)聚合性不飽和化合物，(C)感放射線性聚合引發劑，及(D)下述式(1)所示的溶劑。In accordance with the present invention, a first aspect of the above objects and advantages of the present invention is achieved by a radiation sensitive resin composition characterized by: (A) a copolymer of (a1) and (a2) which is at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and the (a2) is different from the above (a1) The other unsaturated compound, (B) a polymerizable unsaturated compound, (C) a radiation-sensitive polymerization initiator, and (D) a solvent represented by the following formula (1).

[式(1)中，R₁ 係碳數1~9的烷基]。 [In the formula (1), R ₁ is an alkyl group having 1 to 9 carbon atoms].

本發明的上述目的及優點之第二係藉由一種液晶顯示元件的間隔物或保護膜來達成，其係由前述感放射線性樹脂組成物所形成。The second object of the above objects and advantages of the present invention is achieved by a spacer or a protective film of a liquid crystal display element which is formed of the above-mentioned radiation sensitive resin composition.

本發明的上述目的及優點之第三係藉由一種液晶顯示元件來達成，其具備由前述感放射線性樹脂組成物所形成的間隔物或保護膜。A third aspect of the above objects and advantages of the present invention is achieved by a liquid crystal display device comprising a spacer or a protective film formed of the radiation sensitive resin composition.

本發明的感放射線性樹脂組成物係可給予膜厚均勻且沒有瑕疵的塗膜，適用於縫模塗布法。The radiation sensitive resin composition of the present invention can be applied to a slit die coating method by giving a coating film having a uniform film thickness and no flaw.

實施發明的最佳形態Best form for implementing the invention ＜感放射液性樹脂組成物＞<The radiation-sensitive resin composition>

以下詳述本發明的感放射線性樹脂組成物之各成分。Each component of the radiation sensitive resin composition of the present invention will be described in detail below.

[A]共聚物[A] copolymer

作為本發明的感放射線性樹脂組成物所含有的[A]共聚物，例如是(a1)由不飽和羧酸及不飽和羧酸酐所組成族群所選出的至少1種(以下稱為「化合物(a1)」)與(a2)與(a1)不同的其它不飽和化合物(以下稱為「化合物(a2)」)之共聚物。於本發明中，作為[A]共聚物，較佳為從[A1]使化合物(a1)與1分子中具有至少1個羥基的不飽和化合物(以下稱為「化合物(a2-1)」)的共聚物(以下稱為「共聚物[α]」)與不飽和異氰酸酯化合物反應而得之聚合物(以下稱為「[A]聚合物」)、及[A2]化合物(a1)與具有環氧乙烷基或氧雜環丁烷基的不飽和化合物(以下稱為「化合物(a2-2)」)的共聚物(以下稱為「共聚物[β]」)所組成族群所選出的至少1種。The [A] copolymer contained in the radiation sensitive resin composition of the present invention is, for example, at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter referred to as "compound ( A1)") A copolymer of another unsaturated compound (hereinafter referred to as "compound (a2)") which is different from (a2) and (a1). In the present invention, the [A] copolymer is preferably an unsaturated compound having at least one hydroxyl group in one molecule from [A1] (hereinafter referred to as "compound (a2-1)"). a copolymer obtained by reacting a copolymer (hereinafter referred to as "copolymer [α]") with an unsaturated isocyanate compound (hereinafter referred to as "[A] polymer"), and [A2] compound (a1) and having a ring At least one selected from the group consisting of a copolymer of an oxyethane group or an oxetanyl group unsaturated compound (hereinafter referred to as "compound (a2-2)") (hereinafter referred to as "copolymer [β]") 1 species.

作為化合物(a1)，例如可舉出丙烯酸、甲基丙烯酸、巴豆酸、2-丙烯醯氧基乙基琥珀酸、2-甲基丙烯醯氧基乙基琥珀酸、2-丙烯醯氧基乙基六氫酞酸、2-甲基丙烯醯氧基乙基六氫酞酸等的單羧酸；馬來酸、富馬酸、檸康酸、中康酸、伊康酸等的二羧酸；前述二羧酸的酸酐等。Examples of the compound (a1) include acrylic acid, methacrylic acid, crotonic acid, 2-propenylmethoxyethyl succinic acid, 2-methylpropenyloxyethyl succinic acid, and 2-acryloxy ethoxy a monocarboxylic acid such as hexahydrofurfuric acid or 2-methylpropenyloxyethyl hexahydrophthalic acid; a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid An acid anhydride or the like of the above dicarboxylic acid.

於此等化合物(a1)之中，從共聚合反應性、所得到的聚合物及共聚物在鹼顯像液中的溶解性及取得容易之點來看，較佳為丙烯酸、甲基丙烯酸、馬來酸酐等。Among these compounds (a1), acrylic acid, methacrylic acid, and acrylic acid are preferred from the viewpoints of copolymerization reactivity, solubility of the obtained polymer and copolymer in an alkali developing solution, and ease of availability. Maleic anhydride, etc.

於共聚物[α]及共聚物[β]中，化合物(a1)可為單獨或混合2種以上來使用。In the copolymer [α] and the copolymer [β], the compound (a1) may be used alone or in combination of two or more.

於共聚物[α]及共聚物[β]中，從化合物(a1)而來的重 複單位之含有率較佳為5~50重量%，更佳為10~40重量%，特佳為15~30重量%。從化合物(a1)而來的重複單位之含有率若低於5重量%，則所得到的聚合物在鹼顯像液中的溶解性有降低的傾向，另一方面若超過50重量%，則該聚合物在鹼顯像液中的溶解性有變過大之虞。In the copolymer [α] and the copolymer [β], the weight derived from the compound (a1) The content of the complex unit is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, particularly preferably from 15 to 30% by weight. When the content of the repeating unit derived from the compound (a1) is less than 5% by weight, the solubility of the obtained polymer in the alkali developing solution tends to decrease, and if it exceeds 50% by weight, The solubility of the polymer in the alkali developing solution is excessively large.

再者，於化合物(a1)具有羧基的情況中，將羧基保護後供應給聚合，接著亦可藉由脫保護而將羧基再生。此處，作為保護羧基的保護基，並沒有特別的限定，可使用作為羧基的保護基之眾所周知者。例如，可舉出三烷基矽烷基、1-烷氧基烷基、環狀1-烷氧基烷基等。更具體地，例如可舉出三甲基矽烷基、二甲基丁基矽烷基、1-乙氧基乙基、1-丙氧基乙基、四氫呋喃基、四氫吡喃基、三苯基甲基等。Further, in the case where the compound (a1) has a carboxyl group, the carboxyl group is protected and supplied to the polymerization, and then the carboxyl group can be regenerated by deprotection. Here, the protecting group for protecting the carboxyl group is not particularly limited, and a known one as a protecting group for a carboxyl group can be used. For example, a trialkylalkylalkyl group, a 1-alkoxyalkyl group, a cyclic 1-alkoxyalkyl group, etc. are mentioned. More specifically, for example, trimethyldecylalkyl group, dimethylbutylsulfanyl group, 1-ethoxyethyl group, 1-propoxyethyl group, tetrahydrofuranyl group, tetrahydropyranyl group, triphenyl group Methyl and the like.

又，作為化合物(a2-1)，例如可舉出：如(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸3-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸5-羥戊酯、(甲基)丙烯酸6-羥己酯、(甲基)丙烯酸7-羥庚酯、(甲基)丙烯酸8-羥辛酯、(甲基)丙烯酸9-羥壬酯、(甲基)丙烯酸10-羥癸酯、(甲基)丙烯酸11-羥基十一基酯、(甲基)丙烯酸12-羥基十二基酯的(甲基)丙烯酸羥烷基酯；Further, examples of the compound (a2-1) include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. 5-hydroxypentyl methacrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 9-(meth) acrylate Hydroxyl oxime ester, 10-hydroxydecyl (meth) acrylate, 11-hydroxyundecyl (meth) acrylate, 12-hydroxydodecyl (meth) acrylate (hydroxy) (meth) acrylate ;

以及，如(甲基)丙烯酸4-羥基-環己基酯、(甲基)丙烯酸4-羥基基-環己基甲基酯、(甲基)丙烯酸4-羥乙基-環己基乙基酯、(甲基)丙烯酸3-羥基-雙環[2.2.1]庚-5-烯-2-基酯、(甲基)丙烯酸3-羥甲基-雙環[2.2.1]庚-5-烯-2-基甲基 酯、(甲基)丙烯酸3-羥乙基-雙環[2.2.1]庚-5-烯-2-基乙基酯、(甲基)丙烯酸8-羥基-雙環[2.2.1]庚-5-烯-2-基酯、(甲基)丙烯酸2-羥基-八氫-4,7-亞甲基-茚-5-基酯、(甲基)丙烯酸2-羥甲基-八氫-4,7-亞甲基-茚-5-基甲基酯、(甲基)丙烯酸2-羥乙基-八氫-4,7-亞甲基-茚-5-基乙基酯、(甲基)丙烯酸3-羥基-金剛烷-1-基酯、(甲基)丙烯酸3-羥基甲基-金剛烷-1-基甲基酯、(甲基)丙烯酸3-羥乙基-金剛烷-1-基乙基酯的具有脂環式構造的(甲基)丙烯酸羥烷基酯；And, for example, 4-hydroxy-cyclohexyl (meth)acrylate, 4-hydroxy-cyclohexylmethyl (meth)acrylate, 4-hydroxyethyl-cyclohexylethyl (meth)acrylate, 3-Hydroxy-bicyclo[2.2.1]hept-5-en-2-yl (meth)acrylate, 3-hydroxymethyl-bicyclo[2.2.1]hept-5-ene-2-(meth)acrylate Methyl Ester, 3-hydroxyethyl-bicyclo[2.2.1]hept-5-en-2-ylethyl (meth)acrylate, 8-hydroxy-bicyclo[2.2.1]hept-5 -al-2-yl ester, 2-hydroxy-octahydro-4,7-methylene-indol-5-yl (meth)acrylate, 2-hydroxymethyl-octahydro-4(meth)acrylate , 7-methylene-indol-5-ylmethyl ester, 2-hydroxyethyl-octahydro-4,7-methylene-indol-5-ylethyl (meth)acrylate, (methyl) ) 3-hydroxy-adamantan-1-yl acrylate, 3-hydroxymethyl-adamantane-1-yl (meth)acrylate, 3-hydroxyethyl-adamantane-1 (meth)acrylate a hydroxyalkyl (meth) acrylate having an alicyclic structure;

如(甲基)丙烯酸1,2-二羥乙基酯、(甲基)丙烯酸2,3-二羥丙基酯、(甲基)丙烯酸1,3-二羥丙基酯、(甲基)丙烯酸3,4-二羥基丁基酯、(甲基)丙烯酸3-[3-(2,3-二羥基丙氧基)-2-羥基丙氧基]-2-羥丙基酯等的(甲基)丙烯酸二羥烷基酯；丙烯酸2-(6-羥基己醯氧基)乙基酯、丙烯酸3-(6-羥基己醯氧基)丙基酯、丙烯酸4-(6-羥基己醯氧基)丁基酯、丙烯酸5-(6-羥基己醯氧基)戊基酯、丙烯酸6-(6-羥基己醯氧基)己基酯的丙烯酸(6-羥基己醯氧基)烷基酯；Such as 1,2-dihydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 1,3-dihydroxypropyl (meth)acrylate, (methyl) 3,4-dihydroxybutyl acrylate, 3-[3-(2,3-dihydroxypropoxy)-2-hydroxypropoxy]-2-hydroxypropyl (meth)acrylate, etc. Dihydroxyalkyl (meth)acrylate; 2-(6-hydroxyhexyloxy)ethyl acrylate, 3-(6-hydroxyhexyloxy) propyl acrylate, 4-(6-hydroxyl acrylate) Alkyloxy)butyl acrylate, 5-(6-hydroxyhexyloxy)pentyl acrylate, 6-(6-hydroxyhexyloxy)hexyl acrylate, (6-hydroxyhexyloxy)alkyl acrylate Base ester

如甲基丙烯酸2-(6-羥基己醯氧基)乙基酯、甲基丙烯酸3-(6-羥基己醯氧基)丙基酯、甲基丙烯酸4-(6-羥基己醯氧基)丁基酯、甲基丙烯酸5-(6-羥基乙基己醯氧基)戊基酯、甲基丙烯酸6-(6-羥基己醯氧基)己基酯的甲基丙烯酸(6-羥基己醯氧基)烷基酯等(以下將上述(甲基)丙烯酸(6-羥基己醯氧基)烷基酯稱為「其它化合物(a2-1)」)。Such as 2-(6-hydroxyhexyloxy)ethyl methacrylate, 3-(6-hydroxyhexyloxy) propyl methacrylate, 4-(6-hydroxyhexyloxy) methacrylate Butyl ester, 5-(6-hydroxyethylhexyloxy)pentyl methacrylate, methacrylic acid 6-(6-hydroxyhexyloxy)hexyl methacrylate (6-hydroxyl A decyloxy)alkyl ester or the like (hereinafter, the above (meth)acrylic acid (6-hydroxyhexyloxy)alkyl ester is referred to as "other compound (a2-1)").

於此等化合物(a2-1)之中，從共聚合反應性及與異氰酸酯化合物的反應性之點來看，較佳為丙烯酸2-羥乙酯、 丙烯酸3-羥丙酯、丙烯酸4-羥丁酯、甲基丙烯酸2-羥乙酯、甲基丙烯酸3-羥丙酯、甲基丙烯酸4-羥丁酯、丙烯酸4-羥甲基-環己基甲基酯、甲基丙烯酸4-羥甲基-環己基甲基酯、丙烯酸2,3-二羥丙基酯、甲基丙烯酸2,3-二羥丙基酯、其它化合物(a2-1)等。Among these compounds (a2-1), 2-hydroxyethyl acrylate is preferred from the viewpoints of copolymerization reactivity and reactivity with an isocyanate compound. 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxymethyl-cyclohexyl acrylate Methyl ester, 4-hydroxymethyl-cyclohexylmethyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, other compounds (a2-1) Wait.

又，於化合物(a2-1)之中，從顯像性的提高之點或所得到的間隔物之壓縮性能提高之觀點來看，特佳為其它化合物(a2-1)。於其它化合物(a2-1)之中，特佳為丙烯酸2-(6-羥基己醯氧基)乙基酯、甲基丙烯酸2-(6-羥基己醯氧基)乙基酯，作為甲基丙烯酸2-(6-羥基己醯氧基)乙基酯及甲基丙烯酸2-羥乙酯的混合物之市售品，可舉出商品名的PLACCEL FM1D、FM2D(Daicel化學工業(股)製)等。Further, among the compound (a2-1), the other compound (a2-1) is particularly preferable from the viewpoint of improving the development property or improving the compression performance of the obtained spacer. Among other compounds (a2-1), particularly preferred is 2-(6-hydroxyhexyloxy)ethyl acrylate and 2-(6-hydroxyhexyloxy)ethyl methacrylate as a nail. Commercial products of a mixture of 2-(6-hydroxyhexyloxy)ethyl acrylate and 2-hydroxyethyl methacrylate may be exemplified by PLACEL FM1D and FM2D (Daicel Chemical Industry Co., Ltd.). )Wait.

於共聚物[α]中，化合物(a2-1)可為單獨或混合2種以上來使用。In the copolymer [α], the compound (a2-1) may be used alone or in combination of two or more.

於共聚物[α]中，從化合物(a2-1)而來的重複單位之含有率較佳為1~50重量%，更佳為3~40重量%，特佳為5~30重量%。從化合物(a2-1)而來的重複單位之含有率若低於1重量%，對不飽和異氰酸酯化合物的聚合物之導入率會降低，感度有降低的傾向，另一方面若超過50重量%，則與不飽和異氰酸酯化合物之反應所得到的聚合物之保存安定性有降低的傾向。In the copolymer [α], the content of the repeating unit derived from the compound (a2-1) is preferably from 1 to 50% by weight, more preferably from 3 to 40% by weight, particularly preferably from 5 to 30% by weight. When the content of the repeating unit derived from the compound (a2-1) is less than 1% by weight, the introduction rate of the polymer to the unsaturated isocyanate compound is lowered, and the sensitivity tends to be lowered. On the other hand, if it exceeds 50% by weight Further, the storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound tends to be lowered.

又，作為共聚物[β]的化合物(a2-2)，例如可舉出：(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸2-甲基縮水甘油酯、4-羥丁基(甲基)丙烯酸酯縮水甘油基醚、(甲基)丙烯 酸3,4-環氧基丁酯、(甲基)丙烯酸6,7-環氧基庚酯、(甲基)丙烯酸3,4-環氧基環己酯、(甲基)丙烯酸3,4-環氧基環己基甲酯等的(甲基)丙烯酸環氧基(環)烷基酯；α-乙基丙烯酸縮水甘油酯、α-正丙基丙烯酸縮水甘油酯、α-正丁基丙烯酸縮水甘油酯、α-乙基丙烯酸6,7-環氧基庚酯、α-乙基丙烯酸3,4-環氧基環己酯等的其它α-烷基丙烯酸環氧基(環)烷基酯；鄰乙烯基苄基縮水甘油基醚、間乙烯基苄基縮水甘油基醚、對乙烯基苄基縮水甘油基醚等的縮水甘油基醚；3-(甲基丙烯醯氧基甲基)氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-3-乙基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-甲基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-三氟甲基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-五氟乙基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2-苯基氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2,2-二氟氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2,2,4-三氟氧雜環丁烷、3-(甲基丙烯醯氧基甲基)-2,2,4,4-四氟氧雜環丁烷、3-(甲基丙烯醯氧基乙基)氧雜環丁烷、3-(甲基丙烯醯氧基乙基)-3-乙基氧雜環丁烷、2-乙基-3-(甲基丙烯醯氧基乙基)氧雜環丁烷、3-(甲基丙烯醯氧基乙基)-2-三氟甲基氧雜環丁烷、3-(甲基丙烯醯氧基乙基)-2-五氟乙基氧雜環丁烷、3-(甲基丙烯醯氧基乙基)-2-苯基氧雜環丁烷、2,2-二氟-3-(甲基丙烯醯氧基乙基)氧雜環丁烷、3-(甲基丙烯醯氧基乙基)-2,2,4-三氟氧雜環丁烷、3-(甲基丙烯醯氧基乙基)-2,2,4,4-四氟氧雜環丁烷 等的甲基丙烯酸酯；3-(丙烯醯氧基甲基)氧雜環丁烷、3-(丙烯醯氧基甲基)-3-乙基氧雜環丁烷、3-(丙烯醯氧基甲基)-2-甲基氧雜環丁烷、3-(丙烯醯氧基甲基)-2-三氟甲基氧雜環丁烷、3-(丙烯醯氧基甲基)-2-五氟乙基氧雜環丁烷、3-(丙烯醯氧基甲基)-2-苯基氧雜環丁烷、3-(丙烯醯氧基甲基)-2,2-二氟氧雜環丁烷、3-(丙烯醯氧基甲基)-2,2,4-三氟氧雜環丁烷、3-(丙烯醯氧基甲基)-2,2,4,4-四氟氧雜環丁烷、3-(丙烯醯氧基乙基)氧雜環丁烷、3-(丙烯醯氧基乙基)-3-乙基氧雜環丁烷、2-乙基-3-(丙烯醯氧基乙基)氧雜環丁烷、3-(丙烯醯氧基乙基)-2-三氟甲基氧雜環丁烷、3-(丙烯醯氧基乙基)-2-五氟乙基氧雜環丁烷、3-(丙烯醯氧基乙基)-2-苯基氧雜環丁烷、2,2-二氟-3-(丙烯醯氧基乙基)氧雜環丁烷、3-(丙烯醯氧基乙基)-2,2,4-三氟氧雜環丁烷、3-(丙烯醯氧基乙基)-2,2,4,4-四氟氧雜環丁烷等的丙烯酸酸酯。Further, examples of the compound (a2-2) as the copolymer [β] include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, and 4-hydroxybutyl (A). Acrylate glycidyl ether, (meth) propylene Acid 3,4-epoxybutyl ester, 6,7-epoxyheptyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4 (meth)acrylic acid - (meth)acrylic acid epoxy (cyclo)alkyl esters such as epoxycyclohexyl methyl ester; ?-glycidyl methacrylate, glycidyl α-n-propyl acrylate, α-n-butyl acrylate Other α-alkyl acrylate epoxy (cyclo)alkyl groups such as glycidyl ester, α-ethyl acrylate 6,7-epoxyheptyl ester, α-ethyl acrylate 3,4-epoxycyclohexyl ester Ester; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, glycidyl ether of p-vinylbenzyl glycidyl ether; 3-(methacryloxymethyl) Oxetane, 3-(methacryloxymethyl)-3-ethyloxetane, 3-(methacryloxymethyl)-2-methyloxetane Alkane, 3-(methacryloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloxymethyl)-2-pentafluoroethyl oxetane Alkane, 3-(methacryloxymethyl)-2-phenyloxetane, 3-(methacryloxymethyl)-2,2-difluorooxetane 3-(methacryloxymethyl)-2,2,4-trifluorooxetane, 3-(methacryloxymethyl)-2,2,4,4-tetrafluoro Oxetane, 3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-3-ethyloxetane, 2-B 3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-2-trifluoromethyloxetane, 3-(methyl Propylene methoxyethyl)-2-pentafluoroethyl oxetane, 3-(methacryloxyethyl)-2-phenyl oxetane, 2,2-difluoro- 3-(methacryloxyethyl)oxetane, 3-(methacryloxyethyl)-2,2,4-trifluorooxetane, 3-(methyl Propylene oxiranyl ethyl)-2,2,4,4-tetrafluorooxetane Ethylene methacrylate; 3-(acryloxymethyl)oxetane, 3-(acryloxymethyl)-3-ethyloxetane, 3-(propylene oxide) Methyl)-2-methyloxetane, 3-(acryloxymethyl)-2-trifluoromethyloxetane, 3-(acryloxymethyl)-2 - pentafluoroethyl oxetane, 3-(acryloxymethyl)-2-phenyl oxetane, 3-(acryloxymethyl)-2,2-difluoroox Heterocyclobutane, 3-(acryloxymethyl)-2,2,4-trifluorooxetane, 3-(acryloxymethyl)-2,2,4,4-tetra Fluoxetane, 3-(acryloxyethyl)oxetane, 3-(acryloxyethyl)-3-ethyloxetane, 2-ethyl-3 -(propenyloxyethyl)oxetane, 3-(acryloxyethyl)-2-trifluoromethyloxetane, 3-(acryloxyethyl)-2 - pentafluoroethyl oxetane, 3-(acryloxyethyl)-2-phenyl oxetane, 2,2-difluoro-3-(acryloxyethyl)oxy Heterocyclobutane, 3-(acryloxyethyl)-2,2,4-trifluorooxetane, 3-(acryloxyethyl)-2,2,4,4-tetra C, such as fluorooxetane Acid esters.

於此等之中，從聚合性之點來看，特佳為甲基丙烯酸縮水甘油酯、甲基丙烯酸2-甲基縮水甘油酯、甲基丙烯酸3,4-環氧基環己酯、甲基丙烯酸3,4-環氧基環己基甲酯、3-甲基-3-甲基丙烯醯氧基甲基氧雜環丁烷、3-乙基-3-甲基丙烯醯氧基甲基氧雜環丁烷等。Among these, from the viewpoint of polymerizability, it is particularly preferably glycidyl methacrylate, 2-methyl glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and A. 3,4-Epoxycyclohexylmethyl acrylate, 3-methyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-methylpropenyloxymethyl Oxetane and the like.

於共聚物[β]中，化合物(a2-2)可為單獨或混合2種以上來使用。In the copolymer [β], the compound (a2-2) may be used alone or in combination of two or more.

於共聚物[β]中，從化合物(a2-2)而來的重複單位之含有率，較佳為0.5~70重量%，更佳為1~60重量%，特 佳為3~50重量%。從化合物(a2-2)而來的重複單位之含有率若低於0.5重量%，則所得到的共聚物之耐熱性有降低的傾向，另一方面若超過70重量%，則共聚物的保存安定性有降低的傾向。In the copolymer [β], the content of the repeating unit derived from the compound (a2-2) is preferably 0.5 to 70% by weight, more preferably 1 to 60% by weight. Good is 3~50% by weight. When the content of the repeating unit derived from the compound (a2-2) is less than 0.5% by weight, the heat resistance of the obtained copolymer tends to be lowered. On the other hand, if it exceeds 70% by weight, the copolymer is preserved. Stability has a tendency to decrease.

又，於共聚物[α]及共聚物[β]中，可使用化合物(a2-1)及化合物(a2-2)以外的化合物(a2)「以下稱為「化合物(a2-3)」」當作共聚物的成分來使用。作為其具體例子，例如可舉出：丙烯酸甲酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸第二丁酯、丙烯酸第三丁酯等的丙烯酸烷基酯；甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯酸正丁酯、甲基丙烯酸第二丁酯、甲基丙烯酸第三丁酯等的甲基丙烯酸烷基酯；丙烯酸環己酯、丙烯酸2-甲基環己酯、丙烯酸三環[5.2.1.0^2,6 ]癸烷-8-基酯、丙烯酸2-(三環[5.2.1.0^2,6 ]癸烷-8-基氧基)乙酯、丙烯酸異冰片酯等的丙烯酸脂環式酯；甲基丙烯酸環己酯、甲基丙烯酸2-甲基環己酯、甲基丙烯酸三環[5.2.1.0^2,6 ]癸烷-8-基酯、甲基丙烯酸2-(三環[5.2.1.0^2,6 ]癸烷-8-基氧基)乙酯、甲基丙烯酸異冰片酯等的甲基丙烯酸脂環式酯；丙烯酸苯酯、丙烯酸苄酯等的丙烯酸之芳基酯或芳烷基酯；甲基丙烯酸苯酯、甲基丙烯酸苄基等的甲基丙烯酸之芳基酯或芳烷基酯； 馬來酸二乙酯、富馬酸二乙酯、伊康酸二乙酯等的不飽和二羧酸二烷基酯；丙烯酸四氫呋喃-2-基酯、丙烯酸四氫吡喃-2-基酯、丙烯酸2-甲基四氫吡喃-2-基酯等之具有含氧雜5員環或含氧雜6員環的丙烯酸酯；甲基丙烯酸四氫呋喃-2-基酯、甲基丙烯酸四氫吡喃-2-基酯、甲基丙烯酸2-甲基四氫吡喃-2-基酯等之具有含氧雜5員環或含氧雜6員環的甲基丙烯酸酯；苯乙烯、α-甲基苯乙烯、間甲基苯乙烯、對甲基苯乙烯、對甲氧基苯乙烯等的乙烯基芳香族化合物；1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等的共軛二烯系化合物，以及丙烯睛、甲基丙烯腈、丙烯醯胺、甲基丙烯醯胺、氯乙烯、偏二氯乙烯、醋酸乙烯基等。Further, in the copolymer [α] and the copolymer [β], the compound (a2-1) and the compound (a2) other than the compound (a2-2) can be used (hereinafter referred to as "compound (a2-3)"" Used as a component of the copolymer. Specific examples thereof include alkyl acrylates such as methyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, second butyl acrylate, and tributyl acrylate; methacrylic acid; Methyl acrylate, methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, second butyl methacrylate, butyl methacrylate Alkyl ester; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate, 2-(tricyclic [5.2.1.0 ^2,6] Acrylate cyclic esters such as decane-8-yloxy)ethyl ester, isobornyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclomethacrylate [5.2] .1.0 ^2,6 ]decane-8-yl ester, 2-(tricyclo[5.2.1.0 ^2,6 ]decane-8-yloxy)ethyl methacrylate, isobornyl methacrylate, etc. Ethyl methacrylate; aryl or aralkyl acrylate of phenyl acrylate or benzyl acrylate; phenyl methacrylate, benzyl methacrylate, etc. An aryl or aralkyl ester of acrylic acid; an unsaturated dicarboxylic acid dialkyl ester such as diethyl maleate, diethyl fumarate or diethyl itaconate; tetrahydrofuran-2-yl acrylate An acrylate having an oxygen-containing heterocyclic ring or an oxygen-containing heterocyclic 6-membered ring, such as tetrahydropyran-2-yl acrylate or 2-methyltetrahydropyran-2-yl acrylate; tetrahydrofuran methacrylate -2-yl ester, tetrahydropyran-2-yl methacrylate, 2-methyltetrahydropyran-2-yl methacrylate, etc. having an oxygen-containing heterocyclic ring or an oxygen-containing hetero 6 member Ring methacrylate; vinyl aromatic compound of styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene; 1,3-butadiene a conjugated diene compound such as isoprene or 2,3-dimethyl-1,3-butadiene, and acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, and chlorine. Ethylene, vinylidene chloride, vinyl acetate, and the like.

於此等之中，從共聚合反應性之點來看，較佳為甲基丙烯酸正丁酯、甲基丙烯酸2-甲基縮水甘油酯、甲基丙烯酸苄酯、甲基丙烯酸三環[5.2.1.0^2,6 ]癸烷-8-基酯、苯乙烯、對甲氧基苯乙烯、甲基丙烯酸四氫呋喃-2-基酯、1,3-丁二烯等。Among these, from the viewpoint of copolymerization reactivity, n-butyl methacrylate, 2-methyl glycidyl methacrylate, benzyl methacrylate, methacrylic acid tricyclo[5.2 .1.0 ^2,6 ]decane-8-yl ester, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene, and the like.

於共聚物[α]及共聚物[β]中，化合物(a2-3)可為單獨或混合2種以上來使用。In the copolymer [α] and the copolymer [β], the compound (a2-3) may be used alone or in combination of two or more.

於共聚物[α]及共聚物[β]中，從化合物(a2-3)而來的重複單位之含有率較佳為10~70重量%，更佳為20~50重量%，特佳為30~50重量%。化合物(a2-3)的重複單位之含有率若低於10重量%，則共聚物的分子量有降低的 傾向，另一方面若超過70重量%，則化合物(a1)、化合物(a2-1)及化合物(a2-2)成分的奏成效果會降低。In the copolymer [α] and the copolymer [β], the content of the repeating unit derived from the compound (a2-3) is preferably from 10 to 70% by weight, more preferably from 20 to 50% by weight, particularly preferably 30~50% by weight. When the content of the repeating unit of the compound (a2-3) is less than 10% by weight, the molecular weight of the copolymer is lowered. On the other hand, if it exceeds 70% by weight, the effect of the compound (a1), the compound (a2-1) and the compound (a2-2) may be lowered.

共聚物[α]及共聚物[β]係可藉由在適當的溶劑中，於自由基聚合引發劑的存在下聚合而製造。The copolymer [α] and the copolymer [β] can be produced by polymerization in the presence of a radical polymerization initiator in a suitable solvent.

作為前述聚合所用的溶劑，例如可舉出：甲醇、乙醇、正丙醇、異丙醇等的醇；四氫呋喃、二烷等的醚；乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單正丙基醚、乙二醇單正丁基醚等的乙二醇單烷基醚；乙二醇單甲基醚醋酸酯、乙二醇單乙基醚、乙二醇單正丙基醚醋酸酯、乙二醇單正丁基醚醋酸酯等的乙二醇單烷基醚醋酸酯；乙二醇單甲基醚丙酸酯、乙二醇單乙基醚丙酸酯、乙二醇單正丙基醚丙酸酯、乙二醇單正丁基醚丙酸酯等的乙二醇單烷基醚丙酸酯；二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚等的二乙二醇烷基醚；丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單正丙基醚、丙二醇單正丁基醚等的丙二醇單烷基醚；二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇二甲基醚、二丙二醇二乙基醚、二丙二醇甲基乙基醚等的二丙二醇烷基醚；丙二醇單甲基醚醋酸酯、丙二醇單乙基醚醋酸酯、丙 二醇單正丙基醚醋酸酯、丙二醇單正丁基醚醋酸酯等的丙二醇單烷基醚醋酸酯；丙二醇單甲基醚丙酸酯、丙二醇單乙基醚丙酸酯、丙二醇單正丙基醚丙酸酯、丙二醇單正丁基醚丙酸酯等的丙二醇單烷基醚丙酸酯；甲苯、二甲苯等的芳香族烴；甲基乙基酮、2-戊酮、3-戊酮、環己酮、4-羥基-4-甲基-2-戊酮等的酮；2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸正丙酯、2-甲氧基丙酸正丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸正丙酯、2-乙氧基丙酸正丁酯、2-正丙氧基丙酸甲酯、2-正丙氧基丙酸乙酯、2-正丙氧基丙酸正丙酯、2-正丙氧基丙酸正丁酯、2-正丁氧基丙酸甲酯、2-正丁氧基丙酸乙酯、2-正丁氧基丙酸正丙酯、2-正丁氧基丙酸正丁酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸正丙酯、3-甲氧基丙酸正丁酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸正丙酯、3-乙氧基丙酸正丁酯、3-正丙氧基丙酸甲酯、3-正丙氧基丙酸乙酯、3-正丙氧基丙酸正丙基、3-正丙氧基丙酸正丁酯、3-正丁氧基丙酸甲酯、3-正丁氧基丙酸乙酯、3-正丁氧基丙酸正丙酯、3-正丁氧基丙酸正丁酯等的烷氧基丙酸烷酯，或醋酸甲酯、醋酸乙酯、醋酸正丙酯、醋酸正丁酯、羥基醋酸甲酯、羥基醋酸乙酯、羥基醋酸正丙酯、羥基醋酸 正丁酯、醋酸4-甲氧基丁酯、醋酸3-甲氧基丁酯、醋酸2-甲氧基丁酯、醋酸3-乙氧基丁酯、醋酸3-丙氧基丁酯、乳酸甲酯、乳酸乙酯、乳酸正丙酯、乳酸正丁酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基丙酸乙酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸正丙酯、3-羥基丙酸正丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基醋酸甲酯、甲氧基醋酸乙酯、甲氧基醋酸正丙酯、甲氧基醋酸正丁酯、乙氧基醋酸甲酯、乙氧基醋酸乙酯、乙氧基醋酸正丙酯、乙氧基醋酸正丁酯、正丙氧基醋酸甲酯、正丙氧基醋酸乙酯、正丙氧基醋酸正丙酯、正丙氧基醋酸正丁酯、正丁氧基醋酸甲酯、正丁氧基醋酸乙酯、正丁氧基醋酸正丙酯、正丁氧基醋酸正丁酯等的其它酯等。Examples of the solvent used for the polymerization include alcohols such as methanol, ethanol, n-propanol, and isopropanol; tetrahydrofuran and An ether such as an alkane; an ethylene glycol monoalkyl ether such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether or ethylene glycol mono-n-butyl ether; Ethylene glycol monoalkyl ether acetate such as alcohol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate; Glycol monomer such as diol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, ethylene glycol mono-n-butyl ether propionate Alkyl ether propionate; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl Diethylene glycol alkyl ether such as propyl ether; propylene glycol monomethyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; dipropylene glycol monomethyl Dipropylene glycol alkyl ether such as ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether vinegar Propylene glycol monoalkyl ether acetate such as ester, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate; propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol single positive Propylene glycol monoalkyl ether propionate such as propyl ether propionate or propylene glycol mono-n-butyl ether propionate; aromatic hydrocarbon such as toluene or xylene; methyl ethyl ketone, 2-pentanone, 3- Ketones such as pentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone; methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropene N-propyl acrylate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, 2-B N-butyl oxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, 2-n-propoxypropionic acid N-butyl ester, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, 3-B Methyl propyl propionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, methyl 3-n-propoxypropionate, 3 -ethyl n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, 3-n-butoxy An alkoxypropionic acid alkyl ester such as ethyl propyl propionate, n-propyl 3-n-butoxypropionate or n-butyl 3-n-butoxypropionate, or methyl acetate, ethyl acetate or acetic acid Propyl ester, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, 4-methoxybutyl acetate, 3-methoxybutyl acetate, acetic acid 2 -Methoxybutyl ester, 3-ethoxybutyl acetate, 3-propoxybutyl acetate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, 2-hydroxy-2-methyl Methyl propyl propionate, ethyl 2-hydroxy-2-methylpropanoate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, 3-hydroxypropionic acid Butyl ester, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, n-propyl methoxyacetate, N-butyl oxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate, methyl n-propoxyacetate, n-propoxyacetic acid Ethyl ester, n-propyl n-propoxyacetate, n-butyl n-propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-propyl n-butoxyacetate, n-butoxy Other esters such as n-butyl acetate.

於此等溶劑之中，較佳為二乙二醇烷基醚、丙二醇單烷基醚醋酸酯、烷氧基丙酸烷基、醋酸酯等。Among these solvents, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkoxypropionic acid alkyl group, acetate, and the like are preferable.

前述溶劑可為單獨或混合2種以上來使用。The solvent may be used singly or in combination of two or more.

又，作為前述自由基聚合引發劑，並沒有特別的限定，例如可舉出2,2'-偶氮雙異丁腈、2,2'-偶氮雙-(2,4-二甲基戊腈)、2,2'-偶氮雙-(4-甲氧基-2,4-二甲基戊腈)、4,4'-偶氮雙(4-氰基戊酸)、二甲基-2,2'-偶氮雙(2-甲基丙酸酯)、2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊睛)等的偶氮化合物；苯甲醯基過氧化物、月桂醯基過氧化物、第三丁基過氧三甲基乙酸、1,1-雙(第三丁基過氧)環己烷等的有機過氧化物；過氧化氫等。In addition, the radical polymerization initiator is not particularly limited, and examples thereof include 2,2'-azobisisobutyronitrile and 2,2'-azobis-(2,4-dimethylpentyl). Nitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis(4-cyanovaleric acid), dimethyl An azo compound such as -2,2'-azobis(2-methylpropionate) or 2,2'-azobis(4-methoxy-2,4-dimethylpentanone); Organic peroxides such as benzammonium peroxide, lauryl peroxide, t-butyl peroxytrimethylacetic acid, 1,1-bis(t-butylperoxy)cyclohexane; Hydrogen peroxide, etc.

又，於使用過氧化物當作自由基聚合引發劑時，亦可 併用其與還原劑，當作氧化還原型引發劑。Moreover, when a peroxide is used as a radical polymerization initiator, It is used as a redox type initiator together with a reducing agent.

此等自由基聚合引發劑可為單獨或混合2種以上來使用。These radical polymerization initiators can be used alone or in combination of two or more.

如此所得之共聚物[α]及共聚物[β]係可照溶液原樣地供應給[A]聚合物的製造，也可一旦與溶液分離後，供應給[A]聚合物的製造。The copolymer [α] and the copolymer [β] thus obtained may be supplied to the [A] polymer as it is, or may be supplied to the [A] polymer once separated from the solution.

共聚物[α]及共聚物[β]之由凝膠滲透層析術(GPC)所測定的聚苯乙烯換算重量平均分子量(以下稱為「Mw」)較佳為2,000~100,000，更佳為5,000~50,000。Mw若低於2,000，則所得到的被膜之鹼顯像性、殘膜率等會降低，或有損害圖案形狀、耐熱性等之虞，另一方面若超過100,000，則解像度降低，或有損害圖案形狀之虞。The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC) of the copolymer [α] and the copolymer [β] is preferably 2,000 to 100,000, more preferably 5,000~50,000. When the Mw is less than 2,000, the alkali developability, the residual film ratio, and the like of the obtained film may be lowered, or the pattern shape, heat resistance, and the like may be impaired. On the other hand, if it exceeds 100,000, the resolution is lowered or damaged. The shape of the pattern.

本發明中的[A]聚合物係藉由使共聚物[α]與不飽和異氰酸酯化合物反應而得。The [A] polymer in the present invention is obtained by reacting a copolymer [α] with an unsaturated isocyanate compound.

作為不飽和異氰酸酯化合物，例如可舉出：2-丙烯醯氧基乙基異氰酸酯、3-丙烯醯氧基丙基異氰酸酯、4-丙烯醯氧基丁基異氰酸酯、6-丙烯醯氧基己基異氰酸酯、8-丙烯醯氧基辛基異氰酸酯、10-丙烯醯氧基癸基異氰酸酯、丙烯酸2-(2-異氰酸酯乙氧基)乙酯、丙烯酸2-[2-(2-異氰酸酯乙氧基)乙氧基]乙酯、丙烯酸2-[2-[2-(2-異氰酸酯乙氧基)乙氧基]乙氧基]乙酯、丙烯酸2-(2-異氰酸酯丙氧基)乙酯、丙烯酸2-[2-(2-異氰酸酯丙氧基)丙氧基]乙酯等的丙烯酸等的丙烯酸衍生物；2-甲基丙烯醯氧基乙基異氰酸酯、3-甲基丙烯醯氧基 丙基異氰酸酯、4-甲基丙烯醯氧基丁基異氰酸酯、6-甲基丙烯醯氧基己基異氰酸酯、8-甲基丙烯醯氧基辛基異氰酸酯、10-甲基丙烯醯氧基癸基異氰酸酯甲基丙烯酸、2-(2-異氰酸酯乙氧基)乙酯、甲基丙烯酸2-[2-(2-異氰酸酯乙氧基)乙氧基]乙酯、甲基丙烯酸2-[2-[2-(2-異氰酸酯乙氧基)乙氧基]乙氧基)乙酯、甲基丙烯酸2-(2-異氰酸酯丙氧基)乙酯、甲基丙烯酸2-[2-(2-異氰酸酯丙氧基)丙氧基]乙酯等的甲基丙烯酸衍生物。Examples of the unsaturated isocyanate compound include 2-propenyloxyethyl isocyanate, 3-propenylmethoxypropyl isocyanate, 4-propenyloxybutyl isocyanate, and 6-propyleneoxyloxy isocyanate. 8-Propylene octyl octyl isocyanate, 10-propylene decyl decyl isocyanate, 2-(2-isocyanate ethoxy)ethyl acrylate, 2-[2-(2-isocyanate ethoxy) acrylate Ethyl ester, 2-[2-[2-(2-isocyanate ethoxy)ethoxy]ethoxy]ethyl acrylate, 2-(2-isocyanate propoxy)ethyl acrylate, 2-propene Acrylic acid derivative such as acrylic acid such as [2-(2-isocyanatepropoxy)propoxy]ethyl ester; 2-methylpropenyloxyethyl isocyanate, 3-methylpropenyloxy group Propyl isocyanate, 4-methylpropenyloxybutyl isocyanate, 6-methylpropenyloxyhexyl isocyanate, 8-methylpropenyloxyoctyl isocyanate, 10-methylpropenyloxydecyl isocyanate Methacrylic acid, 2-(2-isocyanate ethoxy)ethyl ester, 2-[2-(2-isocyanate ethoxy)ethoxy]ethyl methacrylate, 2-[2-[2 -(2-Isocyanate ethoxy)ethoxy]ethoxy)ethyl ester, 2-(2-isocyanate propoxy)ethyl methacrylate, 2-[2-(2-isocyanatepropoxy) methacrylate A methacrylic acid derivative such as a propyloxy]ethyl ester.

又，作為2-丙烯醯氧基乙基異氰酸酯的市售品，可舉出商品名Karenz AOI(昭和電工(股)製)，作為2-甲基丙烯醯氧基乙基異氰酸酯的市售品，可舉出商品名Karenz MOI(昭和電工(股)製)、甲基丙烯酸2-(2-異氰酸酯乙氧基)乙基的市售品，可舉出商品名Karenz MOI-EG(昭和電工(股)製)。In addition, a commercially available product of 2-propenyloxyethyl isocyanate, which is a commercial product of 2-methyl propylene methoxyethyl isocyanate, is available as a product of the product name Karenz AOI (manufactured by Showa Denko KK). Commercial products of the product name Karenz MOI (made by Showa Denko Co., Ltd.) and 2-(2-isocyanate ethoxy)ethyl methacrylate are mentioned, and the brand name Karenz MOI-EG (Showa Denko) )system).

於此等不飽和異氰酸酯化合物之中，從與共聚物[α]的反應性之點來看，較佳為2-丙烯醯氧基乙基異氰酸酯、2-甲基丙烯醯氧基乙基異氰酸酯、4-甲基丙烯醯氧基丁基異氰酸酯、甲基丙烯酸2-(2-異氰酸酯乙氧基)乙酯等。Among these unsaturated isocyanate compounds, 2-propenyloxyethyl isocyanate and 2-methylpropenyloxyethyl isocyanate are preferred from the viewpoint of reactivity with the copolymer [α]. 4-methylpropenyloxybutyl isocyanate, 2-(2-isocyanate ethoxy)ethyl methacrylate, and the like.

於[A]聚合物中，不飽和異氰酸酯化合物可為單獨或混合2種以上來使用。In the [A] polymer, the unsaturated isocyanate compound may be used singly or in combination of two or more.

於本發明中，共聚物[α]與不飽和異氰酸酯化合物的反應，例如可藉由在含有二月桂酸二正丁錫(IV)等的觸媒或對甲氧基苯酚等的聚合抑制劑之共聚物[α]溶液中，於室溫或加溫下，邊攪拌邊投入不飽和異氰酸酯化合物而實 施。In the present invention, the reaction of the copolymer [α] with an unsaturated isocyanate compound can be carried out, for example, by a polymerization inhibitor containing a catalyst such as di-n-butyltin dilaurate (IV) or p-methoxyphenol. In the copolymer [α] solution, the unsaturated isocyanate compound is added while stirring at room temperature or under heating. Shi.

製造[A]聚合物時的不飽和異氰酸酯化合物之使用量，相對於共聚物[α]中的化合物(a2-1)之1當量羥基而言，較佳為0.1~95莫耳%，更佳為1.0~80莫耳%，特佳為5.0~75莫耳%。不飽和異氰酸酯化合物的使用量若低於0.1莫耳%，則對感度、耐熱性提高及彈性特性提高的效果小，另一方面若超過95莫耳%，則未反應的不飽和異氰酸酯化合物殘留，所得到的聚合物溶液或感放射線性樹脂組成物的保存安定性有降低的傾向。The amount of the unsaturated isocyanate compound used in the production of the [A] polymer is preferably from 0.1 to 95 mol%, more preferably from 1 to 95 mol%, based on 1 equivalent of the hydroxyl group of the compound (a2-1) in the copolymer [α]. It is 1.0~80% by mole, and especially preferably 5.0~75% by mole. When the amount of the unsaturated isocyanate compound used is less than 0.1 mol%, the effect of improving sensitivity, heat resistance, and elastic properties is small. On the other hand, when it exceeds 95 mol%, the unreacted unsaturated isocyanate compound remains. The storage stability of the obtained polymer solution or radiation sensitive resin composition tends to be lowered.

[A]聚合物及共聚物[β]亦可各自單獨使用，從可更提高所得到的感放射線性樹脂組成物的保存安定性、及間隔物的強度和耐熱性之點來看，更佳為併用[A]聚合物與共聚物[β]。[A] The polymer and the copolymer [β] may be used singly, and it is more preferable from the viewpoint of further improving the storage stability of the obtained radiation sensitive resin composition, the strength of the spacer, and heat resistance. For the combined use of [A] polymer and copolymer [β].

於本發明中併用[A]聚合物與共聚物[β]時，共聚物[β]的使用量，相對於100重量份的[A]聚合物而言，較佳為0.5~50重量份，更佳為1~40重量份，特佳為3~30重量份。共聚物[β]的使用量若低於0.5重量份，則間隔物的強度或耐熱性提高的效果小，另一方面若超過50重量份，則有降低感放射線性樹脂組成物的保存安定性的傾向。When the [A] polymer and the copolymer [β] are used in combination in the present invention, the copolymer [β] is used in an amount of preferably 0.5 to 50 parts by weight based on 100 parts by weight of the [A] polymer. More preferably, it is 1 to 40 parts by weight, and particularly preferably 3 to 30 parts by weight. When the amount of the copolymer [β] used is less than 0.5 part by weight, the effect of improving the strength and heat resistance of the separator is small, and if it exceeds 50 parts by weight, the storage stability of the radiation-sensitive resin composition is lowered. Propensity.

[B]聚合性不飽和化合物[B] Polymeric unsaturated compounds

[B]聚合性不飽和化合物係由在感放射線性聚合引發劑的存在下藉由放射線的曝光而聚合的不飽和化合物。[B] The polymerizable unsaturated compound is an unsaturated compound which is polymerized by exposure to radiation in the presence of a radiation-sensitive linear polymerization initiator.

作為如此的[B]聚合性不飽和化合物，並沒有特別的限定，例如從共聚合性良好，所得到的間隔物之強度向上 之點來看，較佳為單官能、2官能或3官能以上的(甲基)丙烯酸酯。The [B] polymerizable unsaturated compound is not particularly limited, and for example, the copolymerization property is good, and the strength of the obtained spacer is upward. From the viewpoint of the above, a monofunctional, bifunctional or trifunctional or higher (meth) acrylate is preferred.

作為前述單官能(甲基)丙烯酸酯，例如可舉出丙烯酸2-羥乙酯、甲基丙烯酸2-羥乙酯、二乙二醇單乙基醚丙烯酸酯、二乙二醇單乙基醚甲基丙烯酸酯、丙烯酸異冰片酯、甲基丙烯酸異冰片酯、丙烯酸3-甲氧基丁酯、甲基丙烯酸3-甲氧基丁酯、(2-丙烯醯氧基乙基)(2-羥丙基)酞酸酯、(2-甲基丙烯醯氧基乙基)(2-羥丙基)酞酸酯、ω-羧基聚己內酯單丙烯酸酯等。作為市售品，例如可舉出商品名Aronix M-101、同M-111、同M-114、同M-5300(以上為東亞合成(股)製)；KAYARAD TC-110S、同TC-120S(以上為日本化藥(股)製)；Biscoat 158、同2311(以上為大阪有機化學工業(股)製)等。Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, and diethylene glycol monoethyl ether. Methacrylate, isobornyl acrylate, isobornyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, (2-propenyloxyethyl) (2- Hydroxypropyl) phthalate, (2-methacryloxyethyl) (2-hydroxypropyl) phthalate, ω-carboxypolycaprolactone monoacrylate, and the like. Examples of commercially available products include Aronix M-101, M-111, M-114, and M-5300 (the above is East Asia Synthetic Co., Ltd.); KAYARAD TC-110S, and TC-120S. (The above is made by Nippon Kayaku Co., Ltd.); Biscoat 158, the same 2311 (above is Osaka Organic Chemical Industry Co., Ltd.).

又，作為前述2官能(甲基)丙烯酸酯，例如可舉出乙二醇二丙烯酸酯、乙二醇二甲基丙烯酸酯、二乙二醇二丙烯酸酯、二乙二醇二甲基丙烯酸酯、四乙二醇二丙烯酸酯、四乙二醇二甲基丙烯酸酯、1,6-己二醇二丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、1,9-壬二醇二丙烯酸酯、1,9-壬二醇二甲基丙烯酸酯、雙苯氧基乙醇茀二丙烯酸酯、雙苯氧基乙醇茀二甲基丙烯酸酯等。Further, examples of the bifunctional (meth) acrylate include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, and diethylene glycol dimethacrylate. , tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol Diacrylate, 1,9-nonanediol dimethacrylate, bisphenoxyethanol oxime diacrylate, bisphenoxyethanol oxime dimethacrylate, and the like.

另外，作為2官能的(甲基)丙烯酸酯之市售品，例如可舉出Aronix M-210、同M-215、同M-220、同M-240、M-260、同M-270、同M-1200、同M-1600、同M-6200(以上為東亞合成(股)製)、KAYARAD HDDA、KAYARAD HX- 220、同HX-620、同R-526、同R-167、同R-604、同R-684、同R-551、同R-712、UX-2201、UX-2301、UX-3204、UX-3301、UX-4101、UX-6101、UX-7101、UX-8101、UX-0937、MU-2100、MU-4001(以上為日本化藥(股)製)、Art-resin UN-9000PEP、同UN-9200A、同UN-7600、同UN-333、同UN-1003、同UN-1255、同UN-6060PTM、同UN-6060P(以上為根上工業(股)製)、同SH-500B、Biscoat 260、同215、同312、同335HP(以上為大阪有機化學工業(股)製)、Light-acrylate BEPG-A、同HPP-A、Light-ester G-201P、環氧基酯40EM、同70PA、同80MFA、同3002M、同3002A(以上共榮公司化學(股)製)、Denacol-acrylate DA-721、同DA-722、DM-201(以上為Nagasecbemtex(股)製)、BMI-70、BMI-80(以上為KI化成(股)製)等。Further, examples of the commercially available bifunctional (meth) acrylate include Aronix M-210, M-215, M-220, M-240, M-260, and M-270. Same as M-1200, same M-1600, same M-6200 (above is East Asian Synthetic (Share)), KAYARAD HDDA, KAYARAD HX- 220, with HX-620, with R-526, with R-167, with R-604, with R-684, with R-551, with R-712, UX-2201, UX-2301, UX-3204, UX -3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above is Nippon Chemical Co., Ltd.), Art-resin UN-9000PEP, same UN-9200A, with UN-7600, with UN-333, with UN-1003, with UN-1255, with UN-6060PTM, with UN-6060P (above is the root industrial (share) system), with SH-500B, Biscoat 260, the same 215, the same 312, the same 335HP (above is Osaka Organic Chemical Industry Co., Ltd.), Light-acrylate BEPG-A, with HPP-A, Light-ester G-201P, epoxy ester 40EM, the same 70PA , with 80MFA, the same 3002M, the same 3002A (the above Co., Ltd. chemical system), Denacol-acrylate DA-721, the same DA-722, DM-201 (above is Nagasecbemtex (share) system), BMI-70, BMI-80 (the above is KI Chemical Co., Ltd.) and so on.

再者，作為前述3官能以上的(甲基)丙烯酸酯，例如可舉出三羥甲基丙烷三丙烯酸酯、三羥甲基丙烷三甲基丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇五甲基丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇六甲基丙烯酸酯、三(2-丙烯醯氧基乙基)磷酸酯、三(2-丙烯醯氧基乙基)磷酸酯，或作為9官能以上的(甲基)丙烯酸酯，可舉出由具有直鏈伸烷基及脂環式構造且具有2個以上的異氰酸酯基之化合物、與分子內具有1個以上的羥基且具有3個、4個或5個丙烯醯氧基及/或甲基丙烯醯氧基的化合物反應而得之多 官能胺甲酸酯丙烯酸酯系化合物等。In addition, examples of the trifunctional or higher (meth) acrylate include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. Ester, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tris(2-propenyloxyl) Ethyl)phosphate, tris(2-propenyloxyethyl)phosphate, or a hexa- or higher-functional (meth) acrylate, which has a linear alkyl group and an alicyclic structure and has a compound obtained by reacting two or more isocyanate groups with a compound having one or more hydroxyl groups in the molecule and having three, four or five acryloxy groups and/or methacryloxy groups. A functional urethane acrylate compound or the like.

作為3官能以上的(甲基)丙烯酸酯之市售品，例如可舉出Aronix M-309、同M-315、同M-350、同M-400、同M-402、同M-405、同M-408、同M-450、同M-1310、同M-1600、同M-1960、同M-7100、同M-8030、同M-8060、同M-8100、同M-8530、同M-8560、同M-9050、Aronix TO-1450(以上為東亞合成(股)製)、KAYARAD TMPTA、同GPO-303、同DPHA、同DPCA-20、同DPCA-30、同DPCA-60、同DPCA-120、同MAX-3510(以上為日本化藥(股)製)、Biscoat 295、同300、同360、同GPT、同3PA、同400(以上為大阪有機化學工業(股)製)，或作為胺甲酸酯丙烯酸酯系化合物，可舉出New Frontier R-1150、同R-1303、同R-1304、同R-1305、同R-1306、同R-1308(第一工業製藥(股)製)、KAYARAD DPHA-40H、UX-5000(日本化藥(股)製)、Art-resin UN-9000H、同UN-3320HA、同UN-3320HB、同UN-3320HC、UN-3320HS、UN-904、UN-901T(根上工業(股)製)等。Examples of commercially available products of a trifunctional or higher (meth) acrylate include Aronix M-309, M-315, M-350, M-400, M-402, and M-405. Same as M-408, same M-450, same M-1310, same M-1600, same M-1960, same M-7100, same M-8030, same M-8060, same M-8100, same M-8530, Same as M-8560, same as M-9050, Aronix TO-1450 (above is East Asia Synthetic (stock) system), KAYARAD TMPTA, same GPO-303, same DPHA, same DPCA-20, same DPCA-30, same DPCA-60 , with DPCA-120, with MAX-3510 (the above is made by Nippon Kayaku Co., Ltd.), Biscoat 295, the same 300, the same 360, the same GPT, the same 3PA, the same 400 (above the Osaka Organic Chemical Industry Co., Ltd.) Or, as a urethane acrylate-based compound, New Frontier R-1150, the same R-1303, the same R-1304, the same R-1305, the same R-1306, the same R-1308 (the first industry) Pharmaceutical (share) system, KAYARAD DPHA-40H, UX-5000 (Nippon Chemical Co., Ltd.), Art-resin UN-9000H, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS , UN-904, UN-901T (Golden Industrial Co., Ltd.) and so on.

於此等單官能、2官能或3官能以上的(甲基)丙烯酸酯之中，更佳為3官能以上的(甲基)丙烯酸酯，特佳為三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯、或含有多官能胺甲酸酯丙烯酸酯系化合物的市售品等。Among these monofunctional, bifunctional or trifunctional or higher (meth)acrylates, a trifunctional or higher (meth)acrylate is more preferable, and trimethylolpropane triacrylate and pentaerythritol are particularly preferable. Acrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or a commercially available product containing a polyfunctional urethane acrylate compound.

前述單官能、2官能或3官能以上的(甲基)丙烯酸酯 可為單獨或混合2種以上來使用。The aforementioned monofunctional, bifunctional or trifunctional or higher (meth) acrylate These can be used individually or in mixture of 2 or more types.

於本發明的感放射線性樹脂組成物中，[B]聚合性不飽和化合物的使用量，相對於100重量份的[A]共聚物而言，較佳為1~300重量份，更佳為10~200重量份。[B]聚合性不飽和化合物的使用量若低於1重量份，則顯像時有生顯像殘渣之虞，另一方面若超過300重量份，則所得到的圖案之密合性有降低的傾向。In the radiation sensitive resin composition of the present invention, the amount of the [B] polymerizable unsaturated compound is preferably from 1 to 300 parts by weight, more preferably from 100 parts by weight to the [A] copolymer. 10 to 200 parts by weight. When the amount of the polymerizable unsaturated compound used is less than 1 part by weight, the residue of the developer residue may be formed during the development, and if it exceeds 300 parts by weight, the adhesion of the obtained pattern may be lowered. Propensity.

[C]感放射線性聚合引發劑[C] sensitizing radiation polymerization initiator

[C]感放射線性聚合引發劑係對放射線有感應，能產生開始[B]聚合性不飽和化合物的聚合之活性種的成分。The [C] radiation-sensitive polymerization initiator is a component which induces radiation and starts the active species of the polymerization of the [B] polymerizable unsaturated compound.

作為如此的[C]感放射線性聚合引發劑，例如可舉出O-醯基肟系化合物、苯乙酮系化合物、雙咪唑系化合物、苯偶姻系化合物、二苯基酮系化合物、α-二酮系化合物、多核醌系化合物、呫噸酮系化合物、膦系化合物、三系化合物等。Examples of such a [C] radiation-sensitive polymerization initiator include an O-mercaptoquinone-based compound, an acetophenone-based compound, a bisimidazole-based compound, a benzoin-based compound, a diphenylketone-based compound, and α. -diketone-based compound, polynuclear oxime-based compound, xanthone-based compound, phosphine-based compound, three A compound or the like.

作為O-醯基肟系化合物，較佳為9.H.-咔唑系的O-醯基肟型聚合引發劑。例如可舉出1-[9-乙基-6-苯甲醯基-9.H.-咔唑-3-基]-壬烷-1,2-壬烷-2-肟-O-醋酸酯、1-[9-乙基-6-苯甲醯基-9.H.-咔唑-3-基]-戊烷-1,2-戊烷-2-肟-O-醋酸酯、1-[9-乙基-6-苯甲醯基-9.H.-咔唑-3-基]-辛烷-1-酮肟-O-醋酸酯、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)、乙酮,1-[9-乙基-6-[2-甲基-4-(2,2-二甲基-1,3-二噁茂烷基)甲氧基苯甲醯基]-9.H.-咔唑-3-基]-,1-(O-乙醯基肟)、1-[9-乙基-6-(1,3,5-三甲基苯甲醯 基)-9.H.-咔唑-3-基]-乙烷-1-酮肟-O-苯甲酸酯、1-[9-丁基-6-(2-乙基苯甲醯基)-9.H.-咔唑-3-基]-乙烷-1-酮肟-O-苯甲酸酯、1-[9-乙基-6-(2-甲基-4-四氫吡喃基甲氧基苯甲醯基)-9.H.-咔唑-3-基]-乙烷-1-酮肟-O-醋酸酯、1-[9-乙基-6-(2-甲基-4-四氫呋喃基甲氧基苯甲醯基)-9.H.-咔唑-3-基]-乙烷-1-酮肟-O-醋酸酯等。As the O-fluorenyl fluorene-based compound, a 9.H.-carbazole-based O-fluorenyl hydrazine type polymerization initiator is preferred. For example, 1-[9-ethyl-6-benzhydryl-9.H.-oxazol-3-yl]-nonane-1,2-decane-2-indole-O-acetate can be mentioned. , 1-[9-ethyl-6-benzylidenyl-9.H.-oxazol-3-yl]-pentane-1,2-pentane-2-indole-O-acetate, 1- [9-ethyl-6-benzylidenyl-9.H.-oxazol-3-yl]-octane-1-one oxime-O-acetate, ethyl ketone, 1-[9-ethyl- 6-(2-methylbenzimidyl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), ethyl ketone, 1-[9-ethyl-6-[2 -methyl-4-(2,2-dimethyl-1,3-dioxoalkyl)methoxybenzylidene]-9.H.-carbazol-3-yl]-, 1- (O-acetamido), 1-[9-ethyl-6-(1,3,5-trimethylbenzhydrazide) -9.H.-oxazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-butyl-6-(2-ethylbenzylidene) )-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methyl-4-tetrahydro) Pyryl methoxy benzhydryl)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2 -Methyl-4-tetrahydrofuranylmethoxybenzylidene)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-acetate.

於此等O-醯基肟化合物之中，特佳為乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)、乙酮,1-[9-乙基-6-[2-甲基-4-(2,2-二甲基-1,3-二噁茂烷基)甲氧基苯甲醯基]-9.H.-咔唑-3-基1-,1-(O-乙醯基肟)。Among these O-mercaptopurine compounds, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetamidoxime), ethyl ketone, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl) Methoxybenzylidene]-9.H.-carbazol-3-yl 1-, 1-(O-ethylindenyl).

前述O-醯基肟化合物可為單獨或混合2種以上來使用。於本發明中，藉由使用O-醯基肟化合物，而可得到即使在1,500J/m² 以下的曝光量也具有充分的感度、密合性之感放射線性樹脂組成物。The above O-indenyl ruthenium compound may be used singly or in combination of two or more. In the present invention, by using an O-indenyl ruthenium compound, a radiation-sensitive resin composition having sufficient sensitivity and adhesion even at an exposure amount of 1,500 J/m ² or less can be obtained.

作為前述苯乙酮系化合物，例如可舉出α-羥基酮系化合物、α-胺基酮系化合物等。Examples of the acetophenone-based compound include an α-hydroxyketone compound and an α-aminoketone compound.

作為前述α-羥基酮系化合物，例如可舉出1-苯基-2-羥基-2-甲基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、4-(2-羥基乙氧基)苯基-(2-羥基-2-丙基)酮、1-羥基環己基苯基酮等，又作為前述α-胺基酮系化合物，例如可舉出2-甲基-1-(4-甲基硫代苯基)-2-嗎啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮、2-(4-甲基苄基)-2-(二甲基胺基)-1-(4-嗎啉基苯基)-丁烷-1-酮等。作為此等以外的化合物，例如可舉出2,2-二甲氧基 苯乙酮、2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮等。Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1-(4-isopropylphenyl)-2-hydroxy-2- Methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexyl phenyl ketone, etc., as the aforementioned α-amino group Examples of the ketone compound include 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one and 2-benzyl-2-dimethylamino group- 1-(4-morpholinylphenyl)-butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl) )-butane-1-one and the like. Examples of the compound other than these include 2,2-dimethoxy group. Acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like.

於此等苯乙酮系化合物之中，特佳為2-甲基-1-(4-甲基硫代苯基)-2-嗎啉基丙烷-1-酮、2-(4-甲基苄基)-2-(二甲基胺基)-1-(4-嗎啉基苯基)-丁烷-1-酮。Among these acetophenone-based compounds, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one and 2-(4-methyl group are particularly preferred. Benzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one.

於本發明中，藉由併用苯乙酮系化合物，而可能進一步改善感度、間隔物形狀或壓縮強度。In the present invention, it is possible to further improve sensitivity, spacer shape or compressive strength by using an acetophenone-based compound in combination.

又，作為前述雙咪唑系化合物，例如可舉出2,2'-雙(2-氯苯基)-4,4',5,5'-四(4-乙氧基羰基苯基)-1,2'-雙咪唑、2,2'-雙(2-溴苯基)-4,4',5,5'-四(4-乙氧基羰基苯基)-1,2'-雙咪唑、2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基-1,2'-雙咪唑、2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基-1,2'-雙咪唑、2,2'-雙(2,4,6-三氯苯基)-4,4',5,5'-四苯基-1,2'-雙咪唑、2,2'-雙(2-溴苯基)-4,4',5,5'-四苯基-1,2'-雙咪唑、2,2'-雙(2,4-二溴苯基)-4,4',5,5'-四苯基-1,2'-雙咪唑、2,2'-雙(2,4,6-三溴苯基)-4,4',5,5'-四苯基-1,2'-雙咪唑等。Further, examples of the bisimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1. , 2'-bisimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-bisimidazole , 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4-dichloro Phenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4', 5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'- Bisimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis (2 , 4,6-tribromophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, and the like.

於此等雙咪唑系化合物之中，較佳為2,2'-雙(2-氯苯基)-4,4',5,5'.-四苯基-1,2'-雙咪唑、2,2'-雙(2,4-二氯苯基)-4,4',5,5'-四苯基-1,2'-雙咪唑、2,2'-雙(2,4,6-三氯苯基)-4,4',5,5'-四苯基-1,2'-雙咪唑等，特佳為2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基-1,2'-雙咪唑。Among these diimidazole-based compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'.-tetraphenyl-1,2'-bisimidazole is preferred. 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, 2,2'-bis (2,4, 6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole, etc., particularly preferably 2,2'-bis(2-chlorophenyl)-4, 4',5,5'-Tetraphenyl-1,2'-bisimidazole.

於本發明中，藉由併用雙咪唑系化合物，而可能進一步改善感度、解像度或密合性。In the present invention, it is possible to further improve the sensitivity, the resolution or the adhesion by using a bisimidazole compound in combination.

又，於併用雙咪唑系化合物時，為了將其增感，可添加具有二烷基胺基的脂肪族系或芳香族系的化合物(以下稱為「胺系增感劑」)。Further, when a bisimidazole compound is used in combination, an aliphatic or aromatic compound having a dialkylamine group (hereinafter referred to as "amine sensitizer") may be added in order to sensitize the compound.

作為胺系增感劑，例如可舉出N-甲基二乙醇胺、4,4'-雙(二甲基胺基)二苯基酮、4,4'-雙(二乙基胺基)二苯基酮、對二甲基胺基苯甲酸乙酯、對二甲基胺基苯甲酸異戊酯等。Examples of the amine-based sensitizer include N-methyldiethanolamine, 4,4'-bis(dimethylamino)diphenyl ketone, and 4,4'-bis(diethylamino) bis. Phenyl ketone, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester, and the like.

於此等胺系增感劑之中，特佳為4,4'-雙(二乙基胺基)二苯基酮。Among these amine sensitizers, 4,4'-bis(diethylamino)diphenyl ketone is particularly preferred.

前述胺系增感劑可為單獨或混合2種以上來使用。The amine-based sensitizer may be used alone or in combination of two or more.

再者，於併用雙咪唑系化合物與胺系增感劑時，作為供氫化合物，可添加硫醇系化合物。雙咪唑系化合物雖然由於前述胺系增感劑而增感及裂解，產生咪唑自由基，但照原樣地係不能展現高的聚合開始能力，所得到的間隔物大多成為倒錐形狀般的不良形狀。但是，於雙咪唑系化合物與胺系增感劑共存的系統中，藉由添加硫醇系化合物，來自硫醇系化合物的氫自由基係供應給咪唑自由基，結果咪唑自由基轉換成為中性的咪唑，同時產生具聚合開始能力高的具有硫自由基的成分，因此可使間隔物的形狀成為更佳的順錐形狀。Further, when a bisimidazole compound and an amine sensitizer are used in combination, a thiol compound may be added as a hydrogen donor compound. The diimidazole-based compound is sensitized and cleaved by the amine-based sensitizer to produce an imidazole radical, but does not exhibit a high polymerization initiation ability as it is, and the obtained spacer is often in the shape of an inverted cone. . However, in a system in which a bisimidazole compound and an amine sensitizer coexist, a hydrogen radical derived from a thiol compound is supplied to an imidazole radical by adding a thiol compound, and the imidazole radical is converted into a neutral. The imidazole also produces a component having a sulfur radical having a high polymerization initiation ability, so that the shape of the spacer can be made into a better tapered shape.

作為前述硫醇系化合物，例如2-巰基苯并噻唑、2-巰基苯并唑、2-巰基苯并咪唑、2-巰基-5-甲氧基苯并噻唑、2-巰基-5-甲氧基苯并咪唑等的芳香族系化合物；3-巰基丙酸、3-巰基丙酸甲基、3-巰基丙酸乙基、3-巰基丙酸辛 基等的脂肪族系單硫醇；3,6-二氧雜-1,8-辛烷二硫醇、季戊四醇四(巰基醋酸酯)、季戊四醇四(3-巰基丙酸酯)等的2官能以上之脂肪族系硫醇。As the aforementioned thiol compound, for example, 2-mercaptobenzothiazole or 2-mercaptobenzoene An aromatic compound such as azole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole; 3-mercaptopropionic acid, 3-mercapto An aliphatic monothiol such as methyl propionate, ethyl 3-mercaptopropionate or octyl 3-mercaptopropionate; 3,6-dioxa-1,8-octanedithiol, pentaerythritol tetra(fluorenyl) A bifunctional or higher aliphatic thiol such as acetate or pentaerythritol tetrakis(3-mercaptopropionate).

於此等硫醇系化合物之中，特佳為2-巰基苯并噻唑。Among these thiol-based compounds, 2-mercaptobenzothiazole is particularly preferred.

又，於併用雙咪唑系化合物與胺系增感劑時，胺系增感劑的添加量，相對於100重量份的雙咪唑系化合物而言，較佳為0.1~50重量份，更佳為1~20重量份。胺系增感劑的添加量若低於0.1重量份，則感度、解像度或密合性的改善效果有降低的傾向，另一方面若超過50重量份，則有損害所得到的間隔物之形狀的傾向。When the bisimidazole compound and the amine sensitizer are used in combination, the amount of the amine sensitizer added is preferably from 0.1 to 50 parts by weight, more preferably from 100 to 50 parts by weight, based on 100 parts by weight of the bisimidazole compound. 1 to 20 parts by weight. When the amount of the amine-based sensitizer added is less than 0.1 part by weight, the effect of improving the sensitivity, the resolution, or the adhesion tends to be lowered. On the other hand, if it exceeds 50 parts by weight, the shape of the obtained spacer is impaired. Propensity.

又，於併用雙咪唑系化合物與胺系增感劑時，硫醇系化合物的添加量，相對於100重量份的雙咪唑系化合物而言，較佳為0.1~50重量份，更佳為1~20重量份。硫醇系化合物的添加量若低於0.1重量份，則間隔物的形狀之改善效果降低，容易發生膜減薄的傾向，另一方面若超過50重量份，則有損害所得到的間隔物之形狀的傾向。In addition, when the bisimidazole compound and the amine sensitizer are used in combination, the amount of the thiol compound added is preferably 0.1 to 50 parts by weight, more preferably 1 part by weight based on 100 parts by weight of the bisimidazole compound. ~20 parts by weight. When the amount of the thiol-based compound added is less than 0.1 part by weight, the effect of improving the shape of the spacer is lowered, and the film tends to be thinned. On the other hand, if it exceeds 50 parts by weight, the obtained spacer is impaired. The tendency of shape.

作為[C]感放射線性聚合引發劑，亦可使用感放射線陽離子聚合引發劑。作為其具體例，以鎓鹽為例，可舉出苯基重氮鎓四氟硼酸鹽、苯基重氮鎓六氟磷酸鹽、苯基重氮鎓六氟砷酸鹽、苯基重氮鎓三氟甲烷磺酸鹽、苯基重氮鎓三氟醋酸酯、苯基重氮鎓對甲苯磺酸鹽、4-甲氧基苯基重氮鎓四氟硼酸鹽、4-甲氧基苯基重氮鎓六氟磷酸鹽、4-甲氧基苯基重氮鎓六氟砷酸鹽、4-甲氧基苯基重氮鎓三氟甲烷磺酸鹽、4-甲氧基苯基重氮鎓三氟醋酸酯、4-甲氧基 苯基重氮鎓對甲苯磺酸鹽、4-第三丁基苯基重氮鎓四氟硼酸鹽、4-第三丁基苯基重氮鎓六氟磷酸鹽、4-第三丁基苯基重氮鎓六氟砷酸鹽、4-第三丁基苯基重氮鎓三氟甲烷磺酸鹽、4-第三丁基苯基重氮鎓三氟醋酸酯、4-第三丁基苯基重氮鎓對甲苯磺酸鹽等的重氮鎓鹽；三苯基鋶四氟硼酸鹽、三苯基鋶六氟磷酸鹽、三苯基鋶六氟砷酸鹽、三苯基鋶三氟甲烷磺酸鹽、三苯基鋶三氟醋酸酯、三苯基鋶對甲苯磺酸鹽、4-甲氧基苯基二苯基鋶四氟硼酸鹽、4-甲氧基苯基二苯基鋶六氟磷酸鹽、4-甲氧基苯基二苯基鋶六氟砷酸鹽、4-甲氧基苯基二苯基鋶三氟甲烷磺酸鹽、4-甲氧基苯基二苯基鋶三氟醋酸酯、4-甲氧基苯基二苯基鋶對甲苯磺酸鹽、4-苯基硫代苯基二苯基四氟硼酸鹽、4-苯基硫代苯基二苯基六氟磷酸鹽、4-苯基硫代苯基二苯基六氟砷酸鹽、4-苯基硫代苯基二苯基三氟甲烷磺酸鹽、4-苯基硫代苯基二苯基三氟醋酸酯、4-苯基硫代苯基二苯基對甲苯磺酸鹽等的鋶鹽；雙(對甲苯基)碘鎓四(五氟苯基)硼酸鹽、(對甲苯基)(對異丙基苯基)碘鎓四(五氟苯基)硼酸鹽等的碘鎓鹽。As the [C] radiation-sensitive polymerization initiator, a radiation-sensitive cationic polymerization initiator can also be used. As a specific example, the onium salt is exemplified by phenyldiazonium tetrafluoroborate, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroarsenate, and phenyldiazonium hydride. Trifluoromethanesulfonate, phenyldiazonium trifluoroacetate, phenyldiazonium p-toluenesulfonate, 4-methoxyphenyldiazonium tetrafluoroborate, 4-methoxyphenyl Diazo hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroarsenate, 4-methoxyphenyldiazonium trifluoromethanesulfonate, 4-methoxyphenyldiazo Trifluoroacetate, 4-methoxy Phenyldiazonium p-toluenesulfonate, 4-tert-butylphenyldiazonium tetrafluoroborate, 4-tert-butylphenyldiazonium hexafluorophosphate, 4-tert-butylbenzene Base heavy nitrogen hexafluoroarsenate, 4-t-butylphenyldiazonium trifluoromethanesulfonate, 4-tert-butylphenyldiazonium trifluoroacetate, 4-tert-butyl a diazonium salt such as phenyldiazonium p-toluenesulfonate; triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium Fluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxyphenyldiphenyl Based on hexafluorophosphate, 4-methoxyphenyldiphenylphosphonium hexafluoroarsenate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenyl di Phenylfluorene trifluoroacetate, 4-methoxyphenyldiphenylphosphonium p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyl Phenyl hexafluorophosphate, 4-phenylthiophenyl diphenyl hexafluoroarsenate, 4-phenylthiophenyl diphenyl three a sulfonium salt of methanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate or the like; bis(p-tolyl)iodonium An iodonium salt such as tetrakis(pentafluorophenyl)borate or (p-tolyl)(p-isopropylphenyl)iodonium tetrakis(pentafluorophenyl)borate.

又，作為金屬茂化合物，可舉出(1-6-η-異丙苯)(η-環戊二烯基)鐵(1+)六氟化磷酸(1-)等。Further, examples of the metallocene compound include (1-6-η-isopropylbenzene) (η-cyclopentadienyl) iron (1+) hexafluorophosphoric acid (1-).

作為此等感放射線陽離子聚合引發劑的市售品，例如重氮鎓鹽的Adekaultraset PP-33(旭電化工業(股)製)、鋶鹽的OPTOMER SP-150、同-170(旭電化工業(股)製)、及金屬茂化合物的Irgacure 261(汽巴特殊化學品公司製)等 。Commercial products such as these are radiation-based cationic polymerization initiators, such as Adekaultraset PP-33 (made by Asahi Kasei Co., Ltd.), OPTOMER SP-150 of bismuth salt, and the same -170 (Asahito Chemical Industry Co., Ltd.) (manufactured by the company) and the metallocene compound Irgacure 261 (made by Ciba Specialty Chemicals Co., Ltd.) .

上述感放射線性聚合引發劑可為單獨或混合2種類以上來使用。The above-mentioned radiation-sensitive polymerization initiator may be used alone or in combination of two or more.

於本發明的感放射線性樹脂組成物中，[C]感放射線性聚合引發劑的使用比例，相對於100重量份的[A]共聚物而言，較佳為1~50重量份，更佳為3~40重量份。In the radiation sensitive resin composition of the present invention, the ratio of use of the [C] radiation-sensitive polymerization initiator is preferably from 1 to 50 parts by weight, more preferably 100 parts by weight of the [A] copolymer. It is 3 to 40 parts by weight.

[D]溶劑[D] solvent

本發明的感放射線性樹脂組成物之特徵為含有前述式(I)所示的溶劑。式(1)中，R₁ 係碳數1~9的烷基。該烷基可為直鏈狀、支鏈狀及環狀中任一者。The radiation sensitive resin composition of the present invention is characterized by containing the solvent represented by the above formula (I). In the formula (1), R ₁ is an alkyl group having 1 to 9 carbon atoms. The alkyl group may be any of a linear chain, a branched chain, and a cyclic chain.

作為式(1)所示的化合物，例如可舉出丙二醇二甲基醚、丙二醇甲基乙基醚、丙二醇甲基丙基醚、丙二醇甲基異丙基醚、丙二醇甲基丁基醚、丙二醇甲基異丁基醚、丙二醇甲基戊基醚、丙二醇甲基環戊基醚、丙二醇甲基己基醚、丙二醇甲基環己基醚、丙二醇甲基庚基醚、丙二醇甲基辛基醚等。Examples of the compound represented by the formula (1) include propylene glycol dimethyl ether, propylene glycol methyl ethyl ether, propylene glycol methyl propyl ether, propylene glycol methyl isopropyl ether, propylene glycol methyl butyl ether, and propylene glycol. Methyl isobutyl ether, propylene glycol methyl amyl ether, propylene glycol methyl cyclopentyl ether, propylene glycol methyl hexyl ether, propylene glycol methyl cyclohexyl ether, propylene glycol methyl heptyl ether, propylene glycol methyl octyl ether, and the like.

其中較佳為使用丙二醇甲基丙基醚、丙二醇甲基丁基醚、丙二醇甲基戊基醚、丙二醇甲基異丙基醚、丙二醇甲基異丁基醚。Among them, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl amyl ether, propylene glycol methyl isopropyl ether, and propylene glycol methyl isobutyl ether are preferably used.

於本發明的組成物中，除了式(1)所示的溶劑，亦可併用其它溶劑。In the composition of the present invention, in addition to the solvent represented by the formula (1), other solvents may be used in combination.

溶劑中的式(1)所示化合物之含量，相對於全部溶劑量而言，較佳為10重量%以上，尤佳為15重量%以上，更佳為在20重量%以上的範圍。The content of the compound represented by the formula (1) in the solvent is preferably 10% by weight or more, particularly preferably 15% by weight or more, and more preferably 20% by weight or more based on the total amount of the solvent.

作為與式(1)所示化合物不同的其它溶劑，較佳為使用將組成物的各成分溶解或分散，而不與各成分反應者。As another solvent different from the compound represented by the formula (1), it is preferred to use a component which dissolves or disperses each component of the composition without reacting with each component.

作為如此的其它溶劑，例如可舉出醇、醚、二醇醚、乙二醇烷基醚醋酸酯、二乙二醇單烷基醚、二乙二醇二烷基醚、丙二醇單烷基醚、丙二醇烷基醚醋酸酯、丙二醇烷基醚丙酸酯、芳香族烴、酮、酯等。Examples of such other solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, and propylene glycol monoalkyl ethers. , propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, ester, and the like.

作為此等其它溶劑的具體例，例如可舉出作為醇的甲醇、乙醇、苯甲醇等；作為醚的四氫呋喃等；作為二醇醚的乙二醇單甲基醚、乙二醇單乙基醚等；作為乙二醇烷基醚醋酸酯的甲基溶纖劑醋酸酯、乙基溶纖劑醋酸酯、乙二醇單丁基醚醋酸酯、二乙二醇單乙基醚醋酸酯等；作為二乙二醇單烷基醚的二乙二醇單甲基醚、二乙二醇單乙基醚等；作為二乙二醇二烷基醚的二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇乙基甲基醚等；作為丙二醇單烷基醚的丙二醇甲基醚、丙二醇乙基醚、丙二醇丙基醚、丙二醇丁基醚等；作為丙二醇烷基醚醋酸酯的丙二醇甲基醚醋酸酯、丙二醇乙基醚醋酸酯、丙二醇丙基醚醋酸酯、丙二醇丁基醚醋酸酯等；作為丙二醇烷基醚丙酸酯的丙二醇甲基醚丙酸酯、丙二醇乙基醚丙酸酯、丙二醇丙基醚丙酸酯、丙二醇丁基醚丙酸酯等；作為芳香族烴的甲苯、二甲苯等；作為酮的甲基乙基酮、環己酮、4-羥基-4-甲基-2-戊酮、甲基異戊基酮等；作為酯的醋酸甲酯、醋酸乙酯、醋酸丙酯、醋酸丁酯、醋酸環己酯、醋酸2-甲基環己酯、2-羥基丙酸乙酯、2-羥基-2-甲基丙酸甲酯、2-羥基-2-甲基 丙酸乙酯、羥基醋酸甲酯、羥基醋酸乙酯、羥基醋酸丁酯、乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸丁酯、3-羥基丙酸甲酯、3-羥基丙酸乙酯、3-羥基丙酸丙酯、3-羥基丙酸丁酯、2-羥基-3-甲基丁酸甲酯、甲氧基醋酸甲酯、甲氧基醋酸乙酯、甲氧基醋酸丙酯、甲氧基醋酸丁酯、乙氧基醋酸甲酯、乙氧基醋酸乙酯、乙氧基醋酸丙酯、乙氧基醋酸丁酯、丙氧基醋酸甲酯、丙氧基醋酸乙酯、丙氧基醋酸丙酯、丙氧基醋酸丁酯、丁氧基醋酸甲酯、丁氧基醋酸乙酯、丁氧基醋酸丙酯、丁氧基醋酸丁酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、2-乙氧基丙酸丁酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、2-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙酯、3-丙氧基丙酸丁酯、3-丁氧基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯等。Specific examples of such other solvents include methanol, ethanol, benzyl alcohol and the like as an alcohol; tetrahydrofuran as an ether; ethylene glycol monomethyl ether as a glycol ether, and ethylene glycol monoethyl ether. Et.; methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, etc. as ethylene glycol alkyl ether acetate; Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc. as diethylene glycol monoalkyl ether; diethylene glycol dimethyl ether as diethylene glycol dialkyl ether, diethyl Glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.; as propylene glycol monoalkyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc.; as propylene glycol alkyl Propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc. of ether acetate; propylene glycol methyl ether propionate as propylene glycol alkyl ether propionate, Propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate ; toluene, xylene, etc. as an aromatic hydrocarbon; methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, etc. as a ketone; Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate 2-hydroxy-2-methyl Ethyl propionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxypropionic acid Ester, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate Ester, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate , propoxy propyl acetate, butyl propyl acetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2-methoxypropionic acid Methyl ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid Ethyl ester, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropionic acid Propyl ester, butyl 2-butoxypropionate, methyl 3-methoxypropionate, 3-methoxypropane Ethyl ester, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropionic acid Propyl ester, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxypropionic acid Butyl ester, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 2-butoxypropionate, and the like.

於此等之中，較佳為醇、二乙二醇、丙二醇烷基醋酸酯、乙二醇烷基醚醋酸酯、二乙二醇二烷基醚，特佳為苯甲醇、二乙二醇乙基甲基醚、丙二醇甲基醚醋酸酯、丙二醇乙基醚醋酸酯、二乙二醇二甲基醚、乙二醇單丁基醚醋酸酯、二乙二醇單乙基醚醋酸酯、二乙二醇二乙基醚。Among them, preferred are alcohol, diethylene glycol, propylene glycol alkyl acetate, ethylene glycol alkyl ether acetate, diethylene glycol dialkyl ether, particularly preferably benzyl alcohol, diethylene glycol. Ethyl methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol diethyl ether.

[D]溶劑(併用其它溶劑時，含有該其它溶劑)的使用量，較佳係使本發明的組成物中的全部固體成分(由含溶劑的組成物之總量去除溶劑量後的量)的含量成為在5~50重量%的範圍、更佳成為在10~50重量%的範圍。The amount of the [D] solvent (containing the other solvent in combination with other solvents) is preferably such that all the solid components in the composition of the present invention (the amount after removing the solvent amount from the total amount of the solvent-containing composition) The content is in the range of 5 to 50% by weight, more preferably in the range of 10 to 50% by weight.

可併用上述[D]溶劑(含其它溶劑)以及高沸點溶劑。此處，作為可併用的高沸點溶劑，例如可舉出N-甲基甲醯胺、N,N-二甲基甲醯胺、N-甲基甲醯苯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮、二甲亞碸、苄基乙基醚、二己基醚、丙酮基丙酮、異佛爾酮、己酸、辛酸、1-辛醇、1-壬醇、醋酸苄酯、苯甲酸乙酯、草酸二乙酯、馬來酸二乙酯、γ-丁內酯、碳酸伸乙酯、碳酸伸丙酯、苯基溶纖劑醋酸酯等。The above [D] solvent (including other solvents) and a high boiling point solvent may be used in combination. Here, examples of the high-boiling solvent which can be used together include N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1- Octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethyl carbonate, propyl carbonate, phenyl cellosolve Acetate and the like.

作為併用高沸點溶劑時的使用量，相對於全部溶劑量而言，較佳為70重量%以下，更佳為60重量%以下。The amount of use in the case of using a high boiling point solvent in combination is preferably 70% by weight or less, and more preferably 60% by weight or less based on the total amount of the solvent.

[E]界面活性劑[E] surfactant

本發明的感放射線性樹脂組成物較佳為含有[E]界面活性劑。作為界面活性劑，較佳可舉出氟系界面活性劑、聚矽氧系界面活性劑等。The radiation sensitive resin composition of the present invention preferably contains [E] a surfactant. The surfactant is preferably a fluorine-based surfactant or a polyoxyn-based surfactant.

作為上述氟系界面活性劑，較佳為在末端、主鏈及側鏈中至少任一部位具有氟烷基及/或氟伸烷基的化合物，作為其例，可舉出1,1,2,2-四氟正辛基(1,1,2,2-四氟正丙基)醚、1,1,2,2-四氟正辛基(正己基)醚、六乙二醇二(1,1,2,2,3,3-六氟正戊基)醚、八乙二醇二(1,1,2,2-四氟正丁基)醚、六丙二醇二(1,1,2,2,3,3-六氟正戊基)醚、八丙 二醇二(1,1,2,2-四氟正丁基)醚、全氟正十二烷磺酸鈉、1,1,2,2,3,3-六氟正癸烷、1,1,2,2,8,8,9,9,10,10-十氟正十二烷、或氟烷基苯磺酸鈉、氟烷基磷酸鈉、氟烷基羧酸鈉、二甘油四(氟烷基聚氧乙烯醚)、氟烷基銨碘化物、氟烷基甜菜鹼、其它氟烷基聚氧乙烯醚、全氟烷基聚氧乙醇、全氟烷基烷氧化物、羧酸氟烷基酯等。The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and/or a fluorine-extended alkyl group in at least one of a terminal group, a main chain and a side chain, and examples thereof include 1, 1, and 2. , 2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl)ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl)ether, hexaethylene glycol di( 1,1,2,2,3,3-hexafluoro-n-pentyl)ether, octaethylene glycol bis(1,1,2,2-tetrafluoro-n-butyl)ether, hexapropanediol bis (1,1, 2,2,3,3-hexafluoro-n-pentyl)ether, eight C Diol (1,1,2,2-tetrafluoro-n-butyl)ether, sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1, 1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, or sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerol (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethylene, perfluoroalkyl alkoxide, carboxylic acid Fluoroalkyl esters and the like.

又，作為上述氟系界面活性劑的市售品，例如可舉出BM-1000、BM-1100(以上為BM CHEMIE公司製)、Megafac F142D、同F172、同F173、同F183、同F178、同F191、同F471、同F476(以上為大日本油墨化學工業(股)製)、Fluorad FC-170C、同-171、同-430、同-431(以上為住友3M(股)製)、Surflon S-112、同-113、同-131、同-141、同-145、同-382、Surflon SC-101、同-102、同-103、同-104、同-105、同-106(以上為旭硝子(股)製)、Eftop EF301、同303、同352(以上為新秋田化成(股)製)、Ftergent FT-100、同-110、同-140A、同-150、同-250、同-251、同-300、同-310、同-400S、Ftergent FTX-218、同-251(以上為(股)Neos製)等。In addition, as a commercial item of the fluorine-based surfactant, for example, BM-1000, BM-1100 (above, BM CHEMIE), Megafac F142D, F172, F173, F183, F178, and the like are mentioned. F191, the same F471, the same F476 (above is the Dainippon Ink Chemical Industry Co., Ltd.), Fluorad FC-170C, the same -171, the same -430, the same -431 (above the Sumitomo 3M (share) system), Surflon S -112, the same -113, the same -131, the same -141, the same -145, the same -382, Surflon SC-101, the same -102, the same -103, the same -104, the same -105, the same -106 (above Asahi Glass Co., Ltd., Eftop EF301, 303, 352 (the above is the new Akita Chemicals Co., Ltd.), Ftergent FT-100, the same -110, the same -140A, the same -150, the same -250, the same - 251, the same -300, the same -310, the same -400S, Ftergent FTX-218, the same -251 (above the "stock" Neos system) and the like.

作為上述聚矽氧系界面活性劑，例如可舉出以東麗聚矽氧DC3PA、同DC7PA、同SH11PA、同SH21PA、同SH28PA、同SH29PA、同SH30PA、同SH-190、同SH-193、同SZ-6032、同SF-8428、同DC-57、同DC-190(以上為東麗．道康寧．聚矽氧(股)製)、TSF-4440、TSF-4300、TSF-4445、TSF-4446、TSF-4460、TSF-4452(以上為GE 東芝聚矽氧(股)製)等的商品名所市售者。Examples of the polyfluorene-based surfactant include Toray Polyoxygen DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, and SH-193. Same as SZ-6032, same as SF-8428, same DC-57, same DC-190 (above is Toray. Dow Corning. Polyoxyl (manufacturing)), TSF-4440, TSF-4300, TSF-4445, TSF- 4446, TSF-4460, TSF-4452 (above GE The product name of the product name such as Toshiba Poly Oxide Co., Ltd.).

又，作為上述以外的界面活性劑，可舉出聚氧乙烯月桂基醚、聚氧乙烯硫脂基醚、聚氧乙烯油基醚等的聚氧乙烯烷基醚；聚氧乙烯正辛基苯基醚、聚氧乙烯正壬基苯基醚等的聚氧乙烯芳基醚；聚氧乙烯二月桂酸酯、聚氧乙烯二硬脂酸酯等的聚氧乙烯二烷基酯等的非離子系界面活性劑、或有機矽氧烷聚合物KP341(信越化學工業(股)製)、(甲基)丙烯酸系共聚物Polyflow No.57、同No.95(以上為共榮公司化學(股)製)等。Further, examples of the surfactant other than the above include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene thioester, and polyoxyethylene oleyl ether; and polyoxyethylene n-octylbenzene; a polyoxyethylene aryl ether such as a phenyl ether or a polyoxyethylene n-decyl phenyl ether; a nonionic ionic acid such as a polyoxyethylene dialkyl ester such as polyoxyethylene dilaurate or polyoxyethylene distearate; It is a surfactant, or an organic siloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic copolymer Polyflow No. 57, and the same No. 95 (above is Co-Pro Chemical Co., Ltd.) System) and so on.

此等界面活性劑可為單獨或混合2種以上來使用。These surfactants can be used singly or in combination of two or more.

界面活性劑的配合量，相對於100重量份的[A]共聚物而言，較佳為1.0重量份以下，更佳為0.5重量份以下。界面活性劑的配合量若超過1.0重量份，則有容易發生膜瑕疵的傾向。The blending amount of the surfactant is preferably 1.0 part by weight or less, more preferably 0.5 part by weight or less based on 100 parts by weight of the [A] copolymer. When the amount of the surfactant is more than 1.0 part by weight, the film tends to be likely to occur.

其它任意添加劑Any other additives

於本發明的感放射線性樹脂組成物中，按照需要，在不損害本發明的效果之範圍內，亦可配合上述以外的任意添加劑，例如黏接輔助劑、保存安定劑、耐熱性提高劑等。In the radiation sensitive resin composition of the present invention, any additives other than the above may be blended as needed, such as a bonding aid, a storage stabilizer, a heat resistance improving agent, etc., as long as the effects of the present invention are not impaired. .

上述黏接輔助劑係用於提高所形成的圖案與基板的接著性而使用的成分。The adhesion aid is a component used to improve the adhesion between the formed pattern and the substrate.

作為如此的黏接輔助劑，例如較佳為具有羧基、甲基丙烯醯基、乙烯基、異氰酸酯基、環氧基等的反應性官能基之官能性矽烷偶合劑。作為其例，可舉出三甲氧基矽烷 基苯甲酸、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、乙烯基三甲氧基矽烷、γ-異氰酸酯丙基三乙氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、β-(3,4-環氧基環己基)乙基三甲氧基矽烷等。As such an adhesion aid, for example, a functional decane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group or an epoxy group is preferable. Trimethoxy decane is exemplified as an example thereof Benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ-isocyanate propyl triethoxy decane, γ-glycidol Oxypropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like.

此等黏接輔助劑可為單獨或混合2種以上來使用。These adhesion aids may be used alone or in combination of two or more.

黏接輔助劑的配合量，相對於100重量份的[A]共聚物而言，較佳為20重量份以下，更佳為15重量份以下。黏接輔助劑的配合量若超過20重量份，則有容易發生顯像殘渣的傾向。The compounding amount of the adhesion aid is preferably 20 parts by weight or less, more preferably 15 parts by weight or less based on 100 parts by weight of the [A] copolymer. When the amount of the adhesion aid is more than 20 parts by weight, the development residue tends to occur.

作為上述保存安定劑，例如可舉出硫、醌類、氫醌類、多氧化合物、胺類、硝基亞硝基化合物等，更具體地可舉出4-甲氧基苯酚、N-亞硝基-N-苯基羥基胺鋁等。Examples of the storage stabilizer include sulfur, anthraquinone, hydroquinone, a polyoxy compound, an amine, and a nitronitroso compound. More specifically, 4-methoxyphenol and N-Asia are mentioned. Nitro-N-phenylhydroxylamine aluminum and the like.

此等保存安定劑可為單獨或混合2種以上來使用。These storage stabilizers can be used singly or in combination of two or more.

保存安定劑的配合量，相對於100重量份的[A]共聚物而言，較佳為3.0重量份以下，更佳為0.5重量份以下。保存安定劑的配合量若超過3.0重量份，則有感度降低、圖案形狀變差之虞。The amount of the stabilizer to be added is preferably 3.0 parts by weight or less, more preferably 0.5 parts by weight or less based on 100 parts by weight of the [A] copolymer. When the amount of the stabilizer is more than 3.0 parts by weight, the sensitivity is lowered and the pattern shape is deteriorated.

又，作為上述耐熱性提高劑，例如可舉出N-(烷氧基甲基)甘脲化合物、N-(烷氧基甲基)蜜胺化合物等。In addition, examples of the heat resistance improving agent include an N-(alkoxymethyl)glycolide compound and an N-(alkoxymethyl)melamine compound.

作為上述N-(烷氧基甲基)甘脲化合物，例如可舉出N,N,N',N'-四(甲氧基甲基)甘脲、N,N,N',N'-四(乙氧基甲基)甘脲、N,N,N',N'-四(正丙氧基甲基)甘脲、N,N,N',N'-四(異丙氧基甲基)甘脲、N,N,N',N'-四(正丁氧基甲基)甘脲、N,N,N',N'-四(第三丁氧基甲基)甘脲等。Examples of the N-(alkoxymethyl)glycoluric compound include N,N,N',N'-tetrakis(methoxymethyl)glycoluril, N,N,N',N'- Tetrakis(ethoxymethyl)glycoluril, N,N,N',N'-tetrakis(n-propoxymethyl)glycoluril, N,N,N',N'-tetra(isopropoxymethyl) Glycoluril, N, N, N', N'-tetrakis (n-butoxymethyl) glycoluril, N, N, N', N'-tetrakis (t-butoxymethyl) glycoluril, etc. .

於此等N-(烷氧基甲基)甘脲化合物之中，較佳為N,N,N',N'-四(甲氧基甲基)甘脲。Among these N-(alkoxymethyl)glycoluric compounds, N,N,N',N'-tetrakis(methoxymethyl)glycolil is preferred.

作為上述N-(烷氧基甲基)蜜胺化合物，例如可舉出N,N,N',N',N",N"-六(甲氧基甲基)蜜胺、N,N,N',N',N",N"-六(乙氧基甲基)蜜胺、N,N,N',N',N",N"-六(正丙氧基甲基)蜜胺、N,N,N',N',N",N"-六(異丙氧基甲基)蜜胺、N,N,N',N',N",N"-六(正丁氧基甲基)蜜胺、N,N,N',N',N",N"-六(第三丁氧基甲基)蜜胺等。Examples of the N-(alkoxymethyl)melamine compound include N,N,N',N',N",N"-hexa(methoxymethyl)melamine, N,N, N',N',N",N"-hexa(ethoxymethyl)melamine, N,N,N',N',N",N"-hexa(n-propoxymethyl)melamine ,N,N,N',N',N",N"-hexa(isopropoxymethyl)melamine, N,N,N',N',N",N"-hexa(n-butoxy Methyl) melamine, N, N, N', N', N", N"-hexa(t-butoxymethyl) melamine, and the like.

於此等N-(烷氧基甲基)蜜胺化合物之中，較佳為N,N,N',N',N",N"-六(甲氧基甲基)蜜胺，作為其市售品，例如可舉出Nikalac N-2702、同MW-30M(以上為三和化學(股)製)等。Among these N-(alkoxymethyl)melamine compounds, N,N,N',N',N",N"-hexa(methoxymethyl)melamine is preferred as Commercially available products include, for example, Nikalac N-2702 and the same MW-30M (the above is manufactured by Sanwa Chemical Co., Ltd.).

本發明的感放射線性樹脂組成物係可藉由將上述[A]共聚物、[B]成分、[C]成分、[D]成分及[E]成分以及如上述任意添加的其它成分均勻混合而調製。本發明的感放射線性樹脂組成物係可藉由將[A]共聚物、[B]成分、[C]成分、[D]成分及[E]成分以及任意添加的其它成分以指定的比例混合，調製溶液狀態的感放射線性樹脂組成物。The radiation sensitive resin composition of the present invention can be uniformly mixed by the above [A] copolymer, [B] component, [C] component, [D] component, and [E] component, and other components added as described above. And modulation. The radiation sensitive resin composition of the present invention can be mixed in a specified ratio by [A] copolymer, [B] component, [C] component, [D] component, and [E] component, and any other component added arbitrarily. A radiation sensitive resin composition in a solution state is prepared.

如此所調製的組成物溶液亦可在使用孔徑0.5μm左右的微孔過濾器等來過濾後，供使用。The composition solution thus prepared may be used after being filtered using a micropore filter having a pore diameter of about 0.5 μm or the like.

＜間隔物及保護膜的形成方法＞<Method for Forming Spacer and Protective Film>

其次，說明使用本發明的感放射線性樹脂組成物來形成間隔物或保護膜的方法。Next, a method of forming a spacer or a protective film using the radiation sensitive resin composition of the present invention will be described.

本發明的間隔物或保護膜的形成方法係可依照以下記 載的順序來實施以下的步驟。The method for forming the spacer or the protective film of the present invention can be as follows The following steps are carried out in the order of loading.

(1)於基板上形成本發明的感放射線性樹脂組成物之被膜的步驟。(1) A step of forming a film of the radiation sensitive resin composition of the present invention on a substrate.

(2)對該被膜的至少一部分照射放射線之步驟。(2) a step of irradiating at least a part of the film with radiation.

(3)將放射線照射後的被膜顯像之步驟。(3) A step of developing a film after radiation irradiation.

(4)將顯像後的被膜加熱之步驟。(4) A step of heating the film after development.

以下依順序說明此等各步驟。These steps are described below in order.

(1)於基板上形成本發明的感放射線性樹脂組成物之被膜的步驟(1) Step of forming a film of the radiation sensitive resin composition of the present invention on a substrate

在透明基板的一面上形成透明導電膜，在該透明導電膜之上形成本發明的感放射線性樹脂組成物的被膜。A transparent conductive film is formed on one surface of the transparent substrate, and a film of the radiation sensitive resin composition of the present invention is formed on the transparent conductive film.

作為此處所用的透明基板，例如可舉出玻璃基板、樹脂基板等，更具體地可舉出鈉鈣玻璃、無鹼玻璃等的玻璃基板；由聚對酞酸乙二酯、聚對酞酸丁二酯、聚醚碸、聚碳酸酯、聚醯亞胺等的塑膠所成的樹脂基板。Examples of the transparent substrate used herein include a glass substrate and a resin substrate, and more specifically, a glass substrate such as soda lime glass or alkali-free glass; and polyethylene terephthalate or polyparaic acid; A resin substrate made of a plastic such as butadiene ester, polyether oxime, polycarbonate, or polyimide.

作為於透明基板的一面所設置的透明導電膜，例如可舉出由氧化錫(SnO₂ )所成的NESA膜(美國PPG公司的註冊商標)、由氧化銦-氧化錫(In₂ O₃ -SnO₂ )所成的ITO膜等。作為被膜的形成方法，可為塗布法或乾膜法。Examples of the transparent conductive film provided on one surface of the transparent substrate include a NESA film made of tin oxide (SnO ₂ ) (registered trademark of PPG, USA), and indium oxide-tin oxide (In ₂ O ₃ - ITO film formed by SnO ₂ ). As a method of forming the film, a coating method or a dry film method can be used.

於藉由塗布法來形成被膜時，在上述透明導電膜之上塗布本發明的感放射線性樹脂組成物的溶液之後，藉由將塗布面加熱(預烘烤)，可形成被膜。塗布法所用的組成物溶液之固體成分濃度較佳為5~50重量%，更佳為10~40重量%，特佳為15~35重量%。作為組成物溶液的塗布方 法，並沒有特別的限定，例如可採用噴霧法、輥塗法、旋轉塗布法(旋塗法)、縫模塗布法、桿塗法、噴墨塗布法等適宜的方法，特佳為旋塗法或縫模塗布法。When a film is formed by a coating method, a solution of the radiation sensitive resin composition of the present invention is applied onto the transparent conductive film, and then the coated surface is heated (prebaked) to form a film. The solid content concentration of the composition solution used in the coating method is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight, particularly preferably from 15 to 35% by weight. As a coating solution of the composition solution The method is not particularly limited, and for example, a suitable method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a rod coating method, or an inkjet coating method may be employed, and particularly preferably a spin coating method. Method or slot die coating method.

另一方面，於藉由乾膜法來形成被膜時，所使用的乾膜係於基礎薄膜上，較佳於可撓性的基礎薄膜上，層合由本發明的感放射線性樹脂組成物所成的感放射線性層所成者(以下稱為「感放射線性乾膜」)。On the other hand, when the film is formed by the dry film method, the dry film used is applied to the base film, preferably on the flexible base film, and laminated by the radiation sensitive resin composition of the present invention. The sensory radiation layer is formed (hereinafter referred to as "radial radiation dry film").

上述感放射線性乾膜係可藉由在基礎薄膜上，以本發明的感放射線性樹脂組成物當作較佳的組成物溶液來塗布後，去除溶劑，層合感放射線性層而形成。層合感放射線性乾膜的感放射線性層用的組成物溶液之固體成分濃度，較佳為5~50重量%，更佳為10~50重量%，尤佳為20~50重量%，特佳為30~50重量%。作為感放射線性乾膜的基礎薄膜，例如可使用聚對酞酸乙二酯(PET)、聚乙烯、聚丙烯、聚碳酸酯、聚氯乙烯等的合成樹脂之薄膜。基礎薄膜的厚度在15~125μm的範圍係適當。感放射線性層的厚度較佳為1~30μm左右。The radiation sensitive dry film system can be formed by applying a radiation sensitive resin composition of the present invention as a preferred composition solution on a base film, removing the solvent, and laminating the radiation sensitive layer. The solid content concentration of the composition solution for the radiation sensitive layer of the laminated radiation sensitive dry film is preferably 5 to 50% by weight, more preferably 10 to 50% by weight, still more preferably 20 to 50% by weight. Good is 30~50% by weight. As the base film of the radiation-sensitive dry film, for example, a film of a synthetic resin such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, or polyvinyl chloride can be used. The thickness of the base film is suitably in the range of 15 to 125 μm. The thickness of the radiation sensitive layer is preferably about 1 to 30 μm.

感放射線性乾膜於未使用時亦可在其感放射線性層上層合覆蓋膜而保存。該覆蓋膜較佳為在未使用時不剝離，而在使用時可容易地剝離，具有適度的脫模性者。作為滿足如此條件的覆蓋膜，例如可使用於PET薄膜、聚丙烯薄膜、聚乙烯薄膜、聚氯乙烯薄膜、聚胺甲酸酯薄膜等的合成樹脂薄膜之表面上塗布或烘烤有聚矽氧系脫模劑的薄膜。覆蓋膜的厚度較佳為5~30μm左右。此等覆蓋膜亦可 為層合有2層或3層的積層型覆蓋膜。The radiation-sensitive linear dry film may be deposited on the radiation sensitive layer by laminating the cover film when not in use. The cover film is preferably not peeled off when not in use, and can be easily peeled off during use, and has a moderate mold release property. As a cover film satisfying such conditions, for example, a surface of a synthetic resin film for a PET film, a polypropylene film, a polyethylene film, a polyvinyl chloride film, a polyurethane film or the like can be coated or baked with polyoxyl A film of a release agent. The thickness of the cover film is preferably about 5 to 30 μm. These cover films can also A laminated type cover film having two or three layers laminated.

可藉由熱壓黏法等適宜的方法，將乾膜層合在透明基板的透明導電膜上，而形成被膜。The dry film may be laminated on the transparent conductive film of the transparent substrate by a suitable method such as hot press bonding to form a film.

如此所形成的被膜接著較佳為經過預烘烤。預烘烤的條件雖然亦隨著各成分的種類、配合比例等而不同，但較佳為在70~120℃進行1~15分鐘左右。The film thus formed is then preferably pre-baked. The pre-baking conditions vary depending on the type and blending ratio of each component, but it is preferably about 1 to 15 minutes at 70 to 120 °C.

被膜的預烘烤後之膜厚較佳為0.5~10μm，更佳為1.0~7.0μm左右。The film thickness after prebaking of the film is preferably from 0.5 to 10 μm, more preferably from about 1.0 to 7.0 μm.

(2)對該被膜的至少一部分照射放射線的步驟(2) a step of irradiating at least a part of the film with radiation

其次，對所形成的被膜之至少一部分照射放射線。此時，於僅照射被膜的一部分時，例如可為隔著具有指定圖案的光罩進行照射的方法。Next, at least a part of the formed film is irradiated with radiation. At this time, when only a part of the film is irradiated, for example, a method of irradiating with a mask having a predetermined pattern may be employed.

作為照射所使用的放射線，例如可舉出可見光線、紫外線、遠紫外線等。其中較佳為波長在250~550nm的範圍之放射線，特佳含365nm的紫外線之放射線。Examples of the radiation used for the irradiation include visible light, ultraviolet light, and far ultraviolet light. Among them, radiation having a wavelength in the range of 250 to 550 nm is preferable, and radiation having ultraviolet rays of 365 nm is particularly preferable.

放射線照射量(曝光量)係以照度計(OAI model 356, OAI Optical Associates Inc.製)測定所照射的放射線在波長365nm的強度之值，較佳為100~5,000J/m² ，更佳為200~3,000J/m² 。The amount of radiation (exposure amount) is measured by an illuminance meter (OAI model 356, manufactured by OAI Optical Associates Inc.) at a wavelength of 365 nm, preferably 100 to 5,000 J/m ² , more preferably 200 ~ 3,000J / m ^2.

(3)將放射線照射後的被膜顯像之步驟(3) Step of developing the film after radiation irradiation

接著，藉由將放射線照射後的被膜顯像，去除不要的部分，形成指定的圖案。Next, the film after the irradiation of the radiation is developed to remove unnecessary portions, thereby forming a predetermined pattern.

作為顯像所使用的顯像液，例如可使用氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨等的無機鹼；乙 胺、正丙胺等的脂肪族1級胺；二乙胺、二正丙胺等的脂肪族2級胺；三甲胺、甲基二乙基胺、二甲基乙基胺、三乙胺等的脂肪族3級胺；吡咯、哌啶、N-甲基哌啶、N-甲基吡咯啶、1,8-二氮雜雙環[5.4.0]-7-十一烯、1,5-二氮雜雙環[4.3.0]-5-壬烯等的脂環族3級胺；吡啶、三甲基吡啶、二甲基吡啶、喹啉等的芳香族3級胺；二甲基乙醇胺、甲基二乙醇胺、三乙醇胺等的烷醇胺；氫氧化四甲銨、氫氧化四乙銨等的4級銨鹽等的鹼性化合物之水溶液。於上述鹼性化合物的水溶液中，亦適量添加甲醇、乙醇等的水溶性有機溶劑及/或界面活性劑而使用。As the developing solution used for development, for example, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, or ammonia can be used; An aliphatic primary amine such as an amine or n-propylamine; an aliphatic secondary amine such as diethylamine or di-n-propylamine; or a fat such as trimethylamine, methyldiethylamine, dimethylethylamine or triethylamine. Group 3 amine; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diaza An alicyclic tertiary amine such as heterobicyclo[4.3.0]-5-nonene; an aromatic tertiary amine such as pyridine, trimethylpyridine, lutidine or quinoline; dimethylethanolamine, methyl An alkanolamine such as diethanolamine or triethanolamine; or an aqueous solution of a basic compound such as a tetra-ammonium salt such as tetramethylammonium hydroxide or tetraethylammonium hydroxide. An aqueous solution of the above basic compound is added in an appropriate amount to a water-soluble organic solvent such as methanol or ethanol and/or a surfactant.

作為顯像方法，可為滿液法、浸漬法、噴淋法等中任一種，顯像時間較佳為在常溫10~180秒左右。The development method may be any one of a full liquid method, a dipping method, and a shower method, and the development time is preferably about 10 to 180 seconds at a normal temperature.

於顯像後，例如在進行30~90秒的流水洗淨之後，例如藉由壓縮空氣或壓縮氮氣來風乾，可得到所欲的圖案。After development, for example, after performing a running water wash for 30 to 90 seconds, for example, by air drying with compressed air or compressed nitrogen, a desired pattern can be obtained.

(4)將顯像後的被膜加熱之步驟(4) Step of heating the film after development

然後，將所得到的圖案狀被膜，例如藉由加熱板、烘箱等的適當加熱裝置，在指定溫度，例如100~250℃，在指定時間，例如在加熱板上5~30分鐘，在烘箱中30~180分鐘，進行加熱(後烘烤)，可得到所欲的間隔物或保護膜。Then, the obtained pattern-like film is placed in an oven at a predetermined temperature, for example, 100 to 250 ° C at a predetermined temperature, for example, on a hot plate for 5 to 30 minutes, by a suitable heating means such as a hot plate or an oven. After 30 to 180 minutes, heating (post-baking) is performed to obtain a desired spacer or protective film.

如以上地，可得到壓縮強度、對於液晶配向膜的摩擦步驟之耐性、與基板的密合性等諸性能優異之間隔物或保護膜。As described above, a spacer or a protective film excellent in properties such as compressive strength, resistance to a rubbing step of a liquid crystal alignment film, and adhesion to a substrate can be obtained.

＜液晶顯示元件＞<Liquid crystal display element>

本發明的液晶顯示元件例如可藉由以下的方法(a)或(b)來製作。The liquid crystal display element of the present invention can be produced, for example, by the following method (a) or (b).

(a)首先，準備於單面上具有透明導電膜(電極)的一對透明基板(2片)，於其中一片基板的透明導電膜上，使用本發明的感放射線性樹脂組成物依照上述方法來形成間隔物或保護膜或其兩者。接著，於此等基板的透明導電膜及間隔物或保護膜上形成具有液晶配向能力的配向膜。以形成有配向膜側之面當作內側，將各配向膜的液晶配向方向成為正交或反平行的方式，隔著一定的間隙(晶胞間隙)相對配置該等基板，於基板的表面(配向膜)與間隔物所劃分的晶胞間隙內填充液晶，將填充孔封閉以構成液晶胞。然後，於液晶胞的兩外表面上，貼合偏光板，使其偏光方向與該基板的一面上所形成的配向膜之液晶配向方向成一致或正交，可得到本發明的液晶顯示元件。(a) First, a pair of transparent substrates (two sheets) having a transparent conductive film (electrode) on one surface are prepared, and the radiation-sensitive resin composition of the present invention is used on the transparent conductive film of one of the substrates in accordance with the above method. To form a spacer or a protective film or both. Next, an alignment film having a liquid crystal alignment ability is formed on the transparent conductive film of the substrate and the spacer or the protective film. The surface on which the alignment film side is formed is referred to as the inner side, and the liquid crystal alignment directions of the respective alignment films are orthogonal or anti-parallel, and the substrates are disposed opposite to each other with a predetermined gap (cell gap) on the surface of the substrate ( The alignment film is filled with liquid crystal in the cell gap divided by the spacer, and the filling hole is closed to constitute a liquid crystal cell. Then, the polarizing plate is bonded to both outer surfaces of the liquid crystal cell so that the polarizing direction thereof coincides with or is orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate, whereby the liquid crystal display element of the present invention can be obtained.

(b)首先，與上述第一方法同樣地，準備形成有透明導電膜、間隔物或保護膜或其兩者及配向膜的一對透明基板。然後沿著一方的基板之端部，用分配器來塗布紫外線硬化型密封劑，接著使用液晶分配器將微小液滴狀的液晶滴下，在真空下進行兩基板的貼合。然後，使用高壓水銀燈對前述密封劑部照射紫外線，以將兩基板封閉。最後，藉由在液晶胞的兩外表面上貼合偏光板，可得到本發明的液晶顯示元件。(b) First, in the same manner as the first method described above, a pair of transparent substrates on which a transparent conductive film, a spacer or a protective film, or both, and an alignment film are formed are prepared. Then, the ultraviolet curable sealant was applied to the end portion of one of the substrates by a dispenser, and then the liquid droplets were dropped by using a liquid crystal dispenser, and the two substrates were bonded under vacuum. Then, the sealant portion is irradiated with ultraviolet rays using a high pressure mercury lamp to close the two substrates. Finally, the liquid crystal display element of the present invention can be obtained by laminating a polarizing plate on both outer surfaces of the liquid crystal cell.

作為上述各方法所使用的液晶，例如可使用向列型液 晶、層列型液晶。其中較佳為向列型液晶，例如希夫鹼系液晶、氧化偶氮系液晶、聯苯系液晶、苯基環己烷系液晶、酯系液晶、聯三苯系液晶、聯苯基環己烷系液晶、嘧啶系液晶、二烷系液晶、雙環辛烷系液晶、立方烷系液晶等。又，於此等液晶中，例如亦可添加膽固醇氯化物、膽固醇壬酸酯、膽固醇碳酸酯等的膽固醇液晶或當作商品名「C-15」、「CB-15」(以上為Merck公司製)所販售的對掌劑等來使用。再者，亦可使用p-癸氧基亞苄基-p-胺基-2-甲基丁基肉桂酸酯等的鐵電性液晶。As the liquid crystal used in each of the above methods, for example, a nematic liquid crystal or a smectic liquid crystal can be used. Among them, a nematic liquid crystal is preferable, such as a Schiff base liquid crystal, an oxidized azo liquid crystal, a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, or a biphenyl ring. Alkane liquid crystal, pyrimidine liquid crystal, two An alkane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, or the like. Further, in such liquid crystals, for example, cholesterol liquid crystals such as cholesterol chloride, cholesterol phthalate, and cholesterol carbonate may be added or used as trade names "C-15" and "CB-15" (the above is manufactured by Merck Co., Ltd.). It is used for palm powder and the like. Further, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may also be used.

又，作為液晶胞的外側所使用的偏光板，可舉出將聚乙烯醇邊延伸配向，邊使吸收碘的稱為H膜的偏光膜，以醋酸纖維素保護膜所夾持的偏光板或由H膜本身所成的偏光板等。In addition, the polarizing plate used for the outer side of the liquid crystal cell may be a polarizing film called an H film which absorbs iodine while extending the polyvinyl alcohol, and a polarizing plate sandwiched by a cellulose acetate protective film or A polarizing plate or the like formed of the H film itself.

【實施例】[Examples]

以下顯示合成例、實施例來更具體說明本發明，惟本發明不受以下的實施例所限定。The present invention will be more specifically described by the following examples and examples, but the present invention is not limited by the following examples.

於以下的合成例中，共聚物的重量平均分子量Mw之測定係在下述的裝置及條件下，藉由凝膠滲透層析術(GPC)來測定。In the following synthesis examples, the measurement of the weight average molecular weight Mw of the copolymer was carried out by gel permeation chromatography (GPC) under the following apparatus and conditions.

＜藉由凝膠滲透層析術來測定共聚物的分子量＞<Measurement of Molecular Weight of Copolymer by Gel Permeation Chromatography>

裝置：GPC-101(昭和電工(股)製)Device: GPC-101 (Showa Denko Electric Co., Ltd.)

管柱：結合GPC-KF-801、GPC-KF-802、GPC-KF-803及GPC-KF-804Pipe column: combined with GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

移動相：含0.5重量%磷酸的四氫呋喃Mobile phase: tetrahydrofuran containing 0.5% by weight of phosphoric acid

＜(A)共聚物的合成例＞<Synthesis Example of (A) Copolymer> 合成例1Synthesis Example 1

於具備冷卻管及攪拌機的燒瓶內，投入4重量份的2,2'-偶氮雙(異丁腈)及220重量份的二乙二醇二甲基醚，接著投入5重量份的苯乙烯、20重量份的甲基丙烯酸、30重量份的甲基丙烯酸苄酯、20重量份的甲基丙烯酸正丁酯及20重量份的3-(甲基丙烯醯氧基甲基)-3-乙基氧雜環丁烷，進行氮氣置換後，再投入5重量份的1,3-丁二烯，邊徐徐攪拌，邊使溶液的溫度上升到80℃，將此溫度保持4小時以進行聚合，得到固體成分濃度29.9重量%的(A)共聚物溶液。將此當作[A-1]聚合物。4 parts by weight of 2,2'-azobis(isobutyronitrile) and 220 parts by weight of diethylene glycol dimethyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by 5 parts by weight of styrene. 20 parts by weight of methacrylic acid, 30 parts by weight of benzyl methacrylate, 20 parts by weight of n-butyl methacrylate and 20 parts by weight of 3-(methacryloxymethyl)-3-B After the oxetane was replaced with nitrogen, 5 parts by weight of 1,3-butadiene was further added, and the temperature of the solution was raised to 80 ° C while stirring, and the temperature was maintained for 4 hours to carry out polymerization. A (A) copolymer solution having a solid concentration of 29.9 wt% was obtained. This was taken as the [A-1] polymer.

對所得到的[A-1]聚合物，使用GPC來測定Mw，結果為12,400。The Mw of the obtained [A-1] polymer was measured by GPC and found to be 12,400.

合成例2Synthesis Example 2

於具備冷卻管及攪拌機的燒瓶內，投入5重量份的2,2'-偶氮雙(2,4-二甲基戊腈)及220重量份的二乙二醇乙基甲基醚，接著投入20重量份的甲基丙烯酸、35重量份的甲基丙烯酸縮水甘油酯、5重量份的苯乙烯及35重量份的甲基丙烯酸三環[5.2.1.0^2,6 ]癸烷-8-基酯，進行氮氣置換後，再投入5重量份的1,3-丁二烯，邊徐徐攪拌，邊使溶液的溫度上升到70℃，將此溫度保持4小時以進行聚合，得到含[A]共聚物的樹脂溶液(固體成分濃度=29.5重量%)。將此當作[A-2]聚合物。所得到的[A]共聚物之Mw為13,000。5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by 20 parts by weight of methacrylic acid, 35 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, and 35 parts by weight of tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate After the ester was replaced with nitrogen, 5 parts by weight of 1,3-butadiene was further added, and the temperature of the solution was gradually increased to 70 ° C while stirring, and the temperature was maintained for 4 hours to carry out polymerization to obtain [A]. Resin solution of copolymer (solid content concentration = 29.5% by weight). This was taken as the [A-2] polymer. The Mw of the obtained [A] copolymer was 13,000.

合成例3Synthesis Example 3

於具備冷卻管及攪拌機的燒瓶內，投入4重量份的2,2'-偶氮雙(異丁腈)及220重量份的丙二醇單甲基醚醋酸酯，接著投入15重量份的丙烯酸、35重量份的甲基丙烯酸苄酯、5重量份的苯乙烯及40重量份的甲基丙烯酸丁酯，進行氮氣置換後，再投入5重量份的1,3-丁二烯，邊徐徐攪拌，邊使溶液的溫度上升到80℃，將此溫度保持5小時以進行聚合，得到含[A]共聚物的樹脂溶液(固體成分濃度=28.6重量%)。將此當作[A-3]聚合物。所得到的[A]共聚物之Mw為12,000。4 parts by weight of 2,2'-azobis(isobutyronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by 15 parts by weight of acrylic acid, 35 5% by weight of benzyl methacrylate, 5 parts by weight of styrene, and 40 parts by weight of butyl methacrylate were replaced with nitrogen, and then 5 parts by weight of 1,3-butadiene was added thereto while stirring. The temperature of the solution was raised to 80 ° C, and the temperature was maintained for 5 hours to carry out polymerization to obtain a resin solution containing a [A] copolymer (solid content concentration = 28.6% by weight). This was taken as the [A-3] polymer. The Mw of the obtained [A] copolymer was 12,000.

合成例4Synthesis Example 4

於具備冷卻管及攪拌機的燒瓶內，投入4重量份的2,2'-偶氮雙(異丁腈)、110重量份的丙二醇甲基丁基醚及110重量份的二乙二醇乙基甲基醚，接著投入20重量份的甲基丙烯酸、20重量份的甲基丙烯酸四氫糠酯、5重量份的苯乙烯及50重量份的甲基丙烯酸苄酯，進行氮氣置換後，再投入5重量份的1,3-丁二烯，邊徐徐攪拌，邊使溶液的溫度上升到80℃，將此溫度保持5小時以進行聚合，得到含[A]共聚物的樹脂溶液(固體成分濃度=29.2重量%)。將此當作[A-4]聚合物。所得到的[A]共聚物之Mw為13,200。4 parts by weight of 2,2'-azobis(isobutyronitrile), 110 parts by weight of propylene glycol methyl butyl ether and 110 parts by weight of diethylene glycol ethyl group were placed in a flask equipped with a cooling tube and a stirrer. Methyl ether, followed by 20 parts by weight of methacrylic acid, 20 parts by weight of tetrahydrofurfuryl methacrylate, 5 parts by weight of styrene, and 50 parts by weight of benzyl methacrylate, after nitrogen substitution, and then charged 5 parts by weight of 1,3-butadiene, while slowly stirring, the temperature of the solution was raised to 80 ° C, and the temperature was maintained for 5 hours to carry out polymerization to obtain a resin solution containing the [A] copolymer (solid content concentration) = 29.2% by weight). This was taken as the [A-4] polymer. The Mw of the obtained [A] copolymer was 13,200.

實施例1~7及比較例1~2Examples 1 to 7 and Comparative Examples 1 to 2 (I)感放射線性樹脂組成物的調製(I) Modulation of radiation sensitive linear resin composition

混合上述合成例1~4所得之聚合物(A)及下述的(B) 、(C)及(E)成分、以及5重量份當作黏接輔助劑的γ-縮水甘油氧基丙基三甲氧基矽烷、0.5重量份當作保存安定劑的4-甲氧基苯酚，以固體成分濃度成為23重量%的方式溶解於(D)成分中之後，藉由孔徑0.2μm的微孔過濾器來過濾，調製組成物溶液。表1中顯示各成分的量。The polymer (A) obtained in the above Synthesis Examples 1 to 4 and the following (B) were mixed. , (C) and (E) components, and 5 parts by weight of γ-glycidoxypropyltrimethoxydecane as an adhesion aid, and 0.5 parts by weight of 4-methoxyphenol as a stabilizer. After dissolving in the component (D) so that the solid content concentration was 23% by weight, it was filtered through a micropore filter having a pore size of 0.2 μm to prepare a composition solution. The amounts of the respective components are shown in Table 1.

(B)成分(B) component

B-1：二季戊四醇六丙烯酸酯B-1: dipentaerythritol hexaacrylate

B-2:1,9-壬二醇二丙烯酸酯B-2: 1,9-nonanediol diacrylate

B-3:ω-羧基聚己內酯單丙烯酸酯(商品名Aronix M-5300(東亞合成(股)製)B-3: ω-carboxypolycaprolactone monoacrylate (trade name: Aronix M-5300 (manufactured by Toago Corporation)

(C)成分(C) component

C-1：乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)(商品名Irgacure OXE02,汽巴特殊化學品公司製)C-1: ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl) ( Trade name Irgacure OXE02, Ciba Specialty Chemicals Co., Ltd.)

C-2:2-(4-甲基苄基)-2-(二甲基胺基)-1-(4-嗎啉基苯基)-丁烷-1-酮(商品名Irgacure 379,汽巴特殊化學品公司製)C-2: 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one (trade name Irgacure 379, steam Ba special chemical company)

C-3:2,2'-雙(2-氯苯基)-4,4',5,5'-四苯基-1,2'-雙咪唑C-3: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-bisimidazole

C-4：乙酮,1-[9-乙基-6-[2-甲基-4-(2,2-二甲基-1,3-二噁茂烷基)甲氧基苯甲醯基]-9.H.-咔唑-3-基1-,1-(O-乙醯基肟)(ADEKA公司製N-1919)C-4: ethyl ketone, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzyl hydrazine Base]-9.H.-carbazol-3-yl 1-,1-(O-ethylindenyl) (N-1919, manufactured by ADEKA)

(D)成分(D) component

D-1：丙二醇甲基丙基醚D-1: propylene glycol methyl propyl ether

D-2：丙二醇甲基丁基醚D-2: propylene glycol methyl butyl ether

D-3：二乙二醇二甲基醚D-3: Diethylene glycol dimethyl ether

D-4：二乙二醇乙基甲基醚D-4: Diethylene glycol ethyl methyl ether

D-5：丙二醇單甲基醚醋酸酯D-5: propylene glycol monomethyl ether acetate

(E)成分(E) component

E-1:Megafac F178(大日本油墨化學工業(股)製)E-1: Megafac F178 (Daily Ink Chemical Industry Co., Ltd.)

E-2:Toray silicone SH28PA(東麗‧道康寧‧聚矽氧(股)製)E-2: Toray silicone SH28PA (Dongli ‧ Dow Corning ‧ Polyoxane (share) system)

E-3:TSF-4460(GE東芝聚矽氧(股)製)E-3: TSF-4460 (GE Toshiba Poly Oxide Co., Ltd.)

評價Evaluation

如以下地實施如上述所示地調製之組成物的評價。表2中顯示評價結果。The evaluation of the composition prepared as described above was carried out as follows. The evaluation results are shown in Table 2.

(I)塗布性(筋瑕疵、莫阿瑕疵、針跡)的評價(I) Evaluation of coating properties (ribs, mo Aya, stitches)

於550×650mm的鉻成膜玻璃上，使用縫模塗布機來塗布所調製的組成物溶液。減壓乾燥到0.5Torr為止後，在加熱板上於100℃預烘烤2分鐘以形成塗膜，再以2,000J/m² 的曝光量進行曝光，形成自鉻成膜玻璃的上面起4μm的膜厚之膜。The prepared composition solution was applied onto a 550 x 650 mm chromium film-forming glass using a slot die coater. After drying under reduced pressure to 0.5 Torr, it was prebaked on a hot plate at 100 ° C for 2 minutes to form a coating film, and exposed to an exposure amount of 2,000 J/m ² to form 4 μm from the top of the chromium film-forming glass. Film of film thickness.

以鈉燈來照射膜表面，目視確認塗布膜面。可清楚地看到筋瑕疵(塗布方向或與其交叉的方向中所發生的一條或數條的直線瑕疵)、莫阿瑕疵(雲狀瑕疵)、針跡(基板支持針上所發生的點狀瑕疵)時為×、可稍微看到時為△，幾乎沒有看到時為○，完全沒有看到筋瑕疵、莫阿瑕疵、針跡時為◎。The surface of the film was irradiated with a sodium lamp, and the surface of the coated film was visually confirmed. It can clearly see the tendons (one or several straight lines that occur in the direction of coating or the direction in which they intersect), Mo Ai (clouds), stitches (points that occur on the substrate support pins) When it is ×, it can be △ when it is slightly seen, ○ when it is hardly seen, and ◎ when it is not seen at all.

(II)塗布性(均勻度)的評價(II) Evaluation of coatability (uniformity)

使用針接觸式測定機(KLA Tencor公司製AS200)來測定如上述所製作的鉻成膜玻璃上之塗膜的膜厚。The film thickness of the coating film on the chromium film-forming glass produced as described above was measured using a needle contact measuring machine (AS200 manufactured by KLA Tencor Co., Ltd.).

由9個測定點的膜厚來計算均勻度。9個測定點係指若以基板的短軸方向當作X，以長軸方向當作Y，則(X[mm], Y[mm])為(275, 20)、(275, 30)、(275, 60)、(275, 100)、(275, 325)、(275, 550)、(275, 590)、(275, 620)、(275, 630)。The uniformity was calculated from the film thicknesses of the nine measurement points. The nine measurement points mean that (X[mm], Y[mm]) is (275, 20), (275, 30) if X is the short axis direction of the substrate and Y is the long axis direction. (275, 60), (275, 100), (275, 325), (275, 550), (275, 590), (275, 620), (275, 630).

均勻度的計算式係由下述數式(3)所表示。下述數式(3)的FT(X, Y)max係9個測定點的膜厚中之最大值，FT(X, Y)min係9個測定點的膜厚中之最小值，FT(X, Y)avg係9個測定點的膜厚中之平均值。均勻度低於2%時為◎，2%以上且低於3%時為○，3%以上且低於5%時為△，5%以上時為×。The calculation formula of the uniformity is represented by the following formula (3). The FT(X, Y)max of the following formula (3) is the maximum of the film thicknesses of the nine measurement points, and FT(X, Y)min is the minimum of the film thicknesses of the nine measurement points, FT ( X, Y) avg is the average of the film thicknesses of the nine measurement points. When the uniformity is less than 2%, it is ◎, when it is 2% or more and less than 3%, it is ○, when it is 3% or more, it is Δ when it is less than 5%, and when it is 5% or more, it is ×.

均勻度(%)={FT(X, Y)max-FT(X, Y)min}×100/{2×FT(X, Y)avg}　　　(3)Uniformity (%)={FT(X, Y)max-FT(X, Y)min}×100/{2×FT(X, Y)avg} (3)

(III)黏度的測定(III) Determination of viscosity

使用E型黏度計(東機產業(股)製VISCONIC ELD.R)在25℃進行測定。The measurement was carried out at 25 ° C using an E-type viscometer (VISCONIC ELD.R manufactured by Toki Sangyo Co., Ltd.).

Claims (6)

一種感放射線性樹脂組成物，其特徵為含有：(A)(a1)與(a2)的共聚物，該(a1)係由不飽和羧酸及不飽和羧酸酐所組成之族群所選出的至少1種，該(a2)係與前述(a1)不同的其它不飽和化合物，(B)聚合性不飽和化合物，(C)感放射線性聚合引發劑，及(D)下述式(1)所示的溶劑，相對於全部溶劑而言，下述式(1)所示的溶劑之含量為至少10重量%， [式(1)中，R₁ 係碳數1~9的烷基]。A radiation sensitive resin composition characterized by comprising: (A) a copolymer of (a1) and (a2), wherein (a1) is at least selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides One type, the (a2) is another unsaturated compound different from the above (a1), (B) a polymerizable unsaturated compound, (C) a radiation-sensitive polymerization initiator, and (D) the following formula (1) The solvent shown in the following formula (1) is at least 10% by weight based on the total solvent. [In the formula (1), R ₁ is an alkyl group having 1 to 9 carbon atoms]. 如申請專利範圍第1項之感放射線性樹脂組成物，其中(A)成分係從(A1)使前述(a1)和(a2-1)1分子中具有至少1個羥基的不飽和化合物之共聚物與不飽和異氰酸酯化合物反應而得之聚合物、及(A2)前述(a1)和(a2-2)具有環氧乙烷基或氧雜環丁烷基的不飽和化合物之共聚物所組成之族群所選出的至少1種。 The radiation sensitive linear resin composition according to claim 1, wherein the component (A) is obtained by copolymerizing an unsaturated compound having at least one hydroxyl group in the above (a1) and (a2-1)1 molecules from (A1). a polymer obtained by reacting an unsaturated isocyanate compound, and (A2) a copolymer of (a1) and (a2-2) an unsaturated compound having an oxiranyl group or an oxetanyl group. At least one of the ethnic groups selected. 如申請專利範圍第1或2項之感放射線性樹脂組成物，其中上述式(1)所示的溶劑係從丙二醇甲基丙基醚、丙二醇甲基丁基醚、丙二醇甲基戊基醚、丙二醇甲基異丙基 醚及丙二醇甲基異丁基醚所組成之族群所選出的至少1種。 The radiation sensitive resin composition according to claim 1 or 2, wherein the solvent represented by the above formula (1) is propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl amyl ether, Propylene glycol methyl isopropyl At least one selected from the group consisting of ether and propylene glycol methyl isobutyl ether. 如申請專利範圍第1或2項之感放射線性樹脂組成物，其係用於液晶顯示元件的間隔物或保護膜的形成。 The radiation sensitive resin composition of claim 1 or 2 is used for the formation of a spacer or a protective film of a liquid crystal display element. 一種液晶顯示元件的間隔物或保護膜，其係由如申請專利範圍第4項之感放射線性樹脂組成物所形成。 A spacer or protective film for a liquid crystal display element formed of a radiation sensitive resin composition as in the fourth aspect of the patent application. 一種液晶顯示元件，其具備如申請專利範圍第5項之間隔物或保護膜。 A liquid crystal display element comprising a spacer or a protective film as in claim 5 of the patent application.