TWI396715B - Resin composition, protection film of color filter and producing thereof - Google Patents
Resin composition, protection film of color filter and producing thereof Download PDFInfo
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- TWI396715B TWI396715B TW095129464A TW95129464A TWI396715B TW I396715 B TWI396715 B TW I396715B TW 095129464 A TW095129464 A TW 095129464A TW 95129464 A TW95129464 A TW 95129464A TW I396715 B TWI396715 B TW I396715B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- Optical Filters (AREA)
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- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本發明涉及樹脂組成物、由該樹脂組成物形成彩色濾光片用保護膜的方法以及彩色濾光片保護膜。更具體地說,涉及適合作為形成液晶顯示元件(LCD)用彩色濾光片和電荷偶合元件(CCD)用彩色濾光片中所用保護膜的材料的樹脂組成物、使用該樹脂組成物的保護膜形成方法以及由該組成物形成的保護膜。The present invention relates to a resin composition, a method of forming a protective film for a color filter from the resin composition, and a color filter protective film. More specifically, it relates to a resin composition suitable as a material for forming a protective film for a color filter for a liquid crystal display element (LCD) and a color filter for a charge coupled device (CCD), and protection using the resin composition A film forming method and a protective film formed of the composition.
LCD或CCD等放射線器件在其製造步驟中用溶劑、酸或者鹼溶液等對顯示元件進行浸漬處理,並且,在通過濺射形成佈線電極層時,元件表面將局部地遭受高溫。於是,為了防止這種處理導致的元件劣化或損傷,便在元件表面上設置由對這些處理具有耐受性的薄膜形成的保護膜。The radiation device such as an LCD or a CCD is subjected to immersion treatment of the display element with a solvent, an acid or an alkali solution or the like in the manufacturing step thereof, and when the wiring electrode layer is formed by sputtering, the surface of the element is locally subjected to a high temperature. Thus, in order to prevent deterioration or damage of the components caused by such treatment, a protective film formed of a film resistant to these treatments is provided on the surface of the member.
這種保護膜要求具有以下性能:為形成該保護膜而與基體或下層以及保護膜上形成的層的密合性高;膜本身平滑且強度高;具有透明性;耐熱性和耐光性高;經過長時間也不會發生著色、變黃、白化等變質;耐水性、耐溶劑性、耐酸性和耐鹼性方面優良等。作為形成滿足諸特性的保護膜的材料,已知例如包含具有縮水甘油基的聚合物的熱固化性組成物(參見專利文獻1和專利文獻2)。Such a protective film is required to have the following properties: high adhesion to a substrate or a lower layer and a layer formed on the protective film for forming the protective film; the film itself is smooth and high in strength; has transparency; high heat resistance and light resistance; After a long period of time, coloring, yellowing, whitening, and the like are not deteriorated, and water resistance, solvent resistance, acid resistance, and alkali resistance are excellent. As a material which forms a protective film satisfying various characteristics, for example, a thermosetting composition containing a polymer having a glycidyl group is known (see Patent Document 1 and Patent Document 2).
並且,當這種保護膜作為彩色液晶顯示裝置和電荷偶合元件的彩色濾光片的保護膜使用時,通常要求能夠使襯底基板上形成的彩色濾光片梯層平坦化。Further, when such a protective film is used as a protective film for a color filter of a color liquid crystal display device and a charge coupling element, it is generally required to planarize a color filter step layer formed on the base substrate.
另外,在彩色液晶顯示裝置例如STN(超扭曲向列)式或者TFT(薄膜電晶體)式的彩色液晶顯示元件中,為了使液晶層單元間隙保持均勻,在保護膜上散佈有珠狀分隔物的基礎上,將面板貼合。然後通過熱壓合密封材料將液晶盒密封,但此時在這種熱和壓力下,存在珠子部分的保護膜出現凹陷現象,導致盒間隙不準確的問題。Further, in a color liquid crystal display device such as an STN (Super Twisted Nematic) type or a TFT (Thin Film Transistor) type color liquid crystal display element, in order to keep the gap of the liquid crystal layer unit uniform, a bead-shaped separator is spread on the protective film. Based on the fit, the panel is attached. Then, the liquid crystal cell is sealed by thermocompression sealing material, but at this time, under such heat and pressure, there is a problem that the protective film of the bead portion is dented, resulting in inaccurate cell gap.
特別是在製造STN式彩色液晶顯示元件時,彩色濾光片與相對向的基板的貼合精度必須非常嚴密,因而保護膜需要有非常高的梯層平坦化性能和耐熱耐壓性能。In particular, when manufacturing an STN type color liquid crystal display element, the bonding precision of the color filter and the opposite substrate must be very strict, and thus the protective film needs to have a very high level of planarization performance and heat resistance and withstand voltage.
在這種保護膜的形成中,使用具有下述優點的熱固化性組成物很便利,該優點為通過簡易的方法可形成硬度優良的保護膜,但是,為表現上述各種特性的保護膜樹脂組成物具有使其形成堅固交聯的高反應***聯基團或者催化劑,因而存在組成物本身的保存期限非常短的問題,處理非常麻煩。也就是說,組成物的塗敷性能本身不僅隨時間而劣化,塗敷機也必須經常地維護、清洗等,在操作上很繁瑣。In the formation of such a protective film, it is convenient to use a thermosetting composition which has the advantage that a protective film excellent in hardness can be formed by a simple method, but a protective film resin composition for expressing the above various characteristics The substance has a highly reactive crosslinking group or a catalyst which makes it form a strong crosslink, and thus there is a problem that the shelf life of the composition itself is very short, and the treatment is very troublesome. That is to say, the coating property of the composition itself is not only deteriorated with time, but also the coating machine must be frequently maintained, cleaned, etc., which is cumbersome in operation.
還未獲知能夠簡便地形成滿足透明性等保護膜的一般性要求性能且滿足上述各種性能的保護膜、並且作為組成物的保存穩定性優良的材料。It has not been known that a protective film which satisfies the above-described various performances and which satisfies the above-described various performances of the protective film such as transparency can be easily formed, and which is excellent in storage stability of the composition.
此外,專利文獻3中,公開了包括塗料、油墨、黏合劑和成形品中使用的潛在化羧基化合物的熱固性組成物,但是沒有公開任何有關彩色濾光片保護膜方面的內容。Further, Patent Document 3 discloses a thermosetting composition including a latent carboxyl compound used in a coating, an ink, a binder, and a molded article, but does not disclose any aspect relating to a color filter protective film.
【專利文獻1】特開平5-78453號公報【專利文獻2】特開2001-91732號公報【專利文獻3】特開平4-218561號公報[Patent Document 1] JP-A-2001-91732 (Patent Document 3)
本發明是基於上述情況而作出的,其目的是提供一種組成物,即使是表面平坦性低的基體,其也能夠在該基體上形成平坦性高的固化膜,而且,適合用於形成透明性和表面硬度高、耐熱耐壓性、耐酸性、耐鹼性、耐濺射性等各種耐受性優良的光學器件用保護膜,並且作為組成物的保存穩定性優良;並提供採用上述組成物形成保護膜的方法,以及由上述組成物形成的保護膜。The present invention has been made in view of the above circumstances, and an object thereof is to provide a composition capable of forming a cured film having high flatness on a substrate even if it has a low surface flatness, and is suitable for forming transparency. And a protective film for an optical device having excellent surface hardness, heat resistance, pressure resistance, acid resistance, alkali resistance, and sputtering resistance, and excellent in storage stability as a composition; and providing the above composition A method of forming a protective film, and a protective film formed of the above composition.
本發明涉及一種樹脂組成物,其特徵在於相對於100重量份(A):(a1)具有環氧乙烷基(oxiranyl)或環氧丙烷基(oxetanyl)的聚合性不飽和化合物與(a2)上述(a1)以外的聚合性不飽和化合物的共聚物,含有0.01-50重量份(B)具有下述式(1)表示的結構的磷酸類酯。The present invention relates to a resin composition characterized by being polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group with respect to 100 parts by weight of (A): (a1) and (a2) The copolymer of the polymerizable unsaturated compound other than the above (a1) contains 0.01 to 50 parts by weight of (B) a phosphate ester having a structure represented by the following formula (1).
[式(1)中的X代表0-2的整數。R1 代表氫原子或者與磷原子相鄰的原子為碳原子的有機基團。R2 代表與氧原子相鄰的原子為碳原子的有機基團。][X in the formula (1) represents an integer of 0-2. R 1 represents a hydrogen atom or an organic group in which an atom adjacent to the phosphorus atom is a carbon atom. R 2 represents an organic group in which an atom adjacent to an oxygen atom is a carbon atom. ]
其中,上述(B)成分較佳為式(1)中的R1 是碳原子數為1-18的烷基、芳基、苄基或者烷基末端或側鏈上具有碳原子數為1-4的烷氧基的碳原子數為1-8的烷基,或者是乙酸酯基,R2 是碳原子數為1-18的烷基或者芳基或苄基。Wherein the component (B) is preferably an alkyl group, an aryl group, a benzyl group having 1 to 18 carbon atoms or a terminal or side chain having 1 to 10 carbon atoms in the formula (1) The alkoxy group of 4 has an alkyl group having 1 to 8 carbon atoms or an acetate group, and R 2 is an alkyl group having 1 to 18 carbon atoms or an aryl group or a benzyl group.
此外,作為(B)成分的具體例子,可以列舉三甲基磷酸酯和/或三乙基磷酸酯。Further, specific examples of the component (B) include trimethyl phosphate and/or triethyl phosphate.
本發明的樹脂組成物,相對於100重量份(A)成分,還可以進一步含有0.0001-20重量份(C)路易士酸催化劑。The resin composition of the present invention may further contain 0.0001 to 20 parts by weight of a (C) Lewis acid catalyst per 100 parts by weight of the component (A).
並且,本發明的樹脂組成物,相對於100重量份(A)成分,還可以進一步含有3-200重量份(D)陽離子聚合性化合物(其中,上述(A)成分除外)。Furthermore, the resin composition of the present invention may further contain 3 to 200 parts by weight of (D) a cationically polymerizable compound (excluding the component (A) above) with respect to 100 parts by weight of the component (A).
本發明的樹脂組成物可用於形成彩色濾光片的保護膜。The resin composition of the present invention can be used to form a protective film of a color filter.
其次,本發明涉及彩色濾光片保護膜的形成方法,其特徵在於採用上述樹脂組成物形成塗膜,然後進行加熱處理。Next, the present invention relates to a method of forming a color filter protective film, which is characterized in that a coating film is formed by using the above resin composition, followed by heat treatment.
再次,本發明涉及由上述樹脂組成物形成的彩色濾光片的保護膜。Further, the present invention relates to a protective film of a color filter formed of the above resin composition.
根據本發明,可以提供一種樹脂組成物,即使是表面平坦性低的基體,其也能夠在該基體上形成平坦性高的固化膜,而且,適合用於形成透明性和表面硬度高、耐熱耐壓性、耐酸性、耐鹼性、耐濺射性等各種耐受性優良的光學器件用保護膜,且該組成物的保存穩定性優良;並可提供採用該樹脂組成物形成保護膜的方法,以及由上述組成物形成的保護膜。According to the present invention, it is possible to provide a resin composition capable of forming a cured film having high flatness on the substrate even in a substrate having a low surface flatness, and is suitable for forming transparency, surface hardness, and heat resistance. A protective film for an optical device excellent in various resistances such as pressure resistance, acid resistance, alkali resistance, and sputtering resistance, and excellent in storage stability of the composition; and a method of forming a protective film using the resin composition And a protective film formed of the above composition.
以下,對本發明的樹脂組成物的各成分進行說明。Hereinafter, each component of the resin composition of the present invention will be described.
(A)共聚物(A) copolymer
本發明的(A)共聚物含有來源於(a1)具有環氧乙烷基或環氧丙烷基的聚合性不飽和化合物的聚合單元,以及來源於(a2)上述(a1)的聚合單元以外的聚合性不飽和化合物的 聚合單元。The (A) copolymer of the present invention contains a polymerized unit derived from (a1) a polymerizable unsaturated compound having an oxiranyl group or an oxypropylene group, and a polymerization unit derived from (a2) the above (a1). Polymeric unsaturated compound Aggregation unit.
在(A)共聚物中,作為(a1)聚合性不飽和化合物,只要具有環氧乙烷基或環氧丙烷基及聚合性不飽和基團,則對其沒有特別的限製。In the (A) copolymer, the (a1) polymerizable unsaturated compound is not particularly limited as long as it has an oxiranyl group or an propylene oxide group and a polymerizable unsaturated group.
例如,作為含有環氧乙烷基的聚合性不飽和化合物,可以列舉丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯、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、丙烯酸-3,4-環氧丁基酯、甲基丙烯酸-3,4-環氧丁基酯、丙烯酸-6,7-環氧庚基酯、甲基丙烯酸-6,7-環氧庚基酯、α-乙基丙烯酸-6,7-環氧庚基酯、鄰-乙烯基苄基縮水甘油醚、間-乙烯基苄基縮水甘油醚、對-乙烯基苄基縮水甘油醚等。For example, examples of the polymerizable unsaturated compound containing an oxirane group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, and α. - glycidyl butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, methacrylic acid -6,7-epoxyheptyl ester, α-ethyl acrylate-6,7-epoxyheptyl ester, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-ethylene Glycidyl glycidyl ether and the like.
並且,作為含有環氧丙烷基的聚合性不飽和化合物,可以列舉例如3-甲基-3-(甲基)丙烯醯氧基甲基環氧丙烷、3-乙基-3-(甲基)丙烯醯氧基甲基環氧丙烷等。Further, examples of the polymerizable unsaturated compound containing an oxypropylene group include 3-methyl-3-(methyl)propenyloxymethyl propylene oxide and 3-ethyl-3-(methyl). Propylene methoxymethyl propylene oxide and the like.
其中,從提高共聚反應性和所得保護膜或絕緣膜的耐熱性、表面硬度等角度出發,較佳使用甲基丙烯酸縮水甘油酯、甲基丙烯酸-6,7-環氧庚基酯、鄰-乙烯基苄基縮水甘油醚、間-乙烯基苄基縮水甘油醚、對-乙烯基苄基縮水甘油醚等。Among them, from the viewpoint of improving the copolymerization reactivity and the heat resistance and surface hardness of the obtained protective film or insulating film, it is preferred to use glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl ester, ortho- Vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.
(A)共聚物除了(a1)成分外,還含有來源於(a2)上述(a1)以外的聚合性不飽和化合物的聚合單元。(a2)聚合性不飽和化合物可以列舉例如(甲基)丙烯酸烷基酯、(甲基)丙烯酸環烷基酯、(甲基)丙烯酸芳基酯、不飽和二羧酸二酯、雙環不飽和化合物類、馬來醯亞胺化合物類、不飽和芳香族化合物、共軛二烯類化合物、不飽和一元羧酸、不飽和二元羧酸、不飽和二元羧酸酐、具有縮醛、縮酮結構的不飽和化合物等。(A) The copolymer contains, in addition to the component (a1), a polymer unit derived from (a2) a polymerizable unsaturated compound other than the above (a1). (a2) The polymerizable unsaturated compound may, for example, be an alkyl (meth)acrylate, a cycloalkyl (meth)acrylate, an aryl (meth)acrylate, an unsaturated dicarboxylic acid diester, or a bicyclic unsaturated group. a compound, a maleimide compound, an unsaturated aromatic compound, a conjugated diene compound, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride, an acetal, a ketal Structure of unsaturated compounds, etc.
作為這些(a2)聚合性不飽和化合物的具體例子,例如,(甲基)丙烯酸烷基酯可以列舉(甲基)丙烯酸羥基甲酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、二甘醇單(甲基)丙烯酸酯、(甲基)丙烯酸2,3-二羥基丙酯、2-甲基丙烯醯氧基乙基糖苷、(甲基)丙烯酸4-羥基苯酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁基酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異癸基酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸十三烷基酯、(甲基)丙烯酸正十八烷基酯、(甲基)丙烯酸第三丁氧基酯、1-二甲基(異)丙基(甲基)丙烯酸酯、1-二甲基(異)丁基(甲基)丙烯酸酯、1-二甲基(異)辛基(甲基)丙烯酸酯、1-甲基-1-乙基乙基(甲基)丙烯酸酯、1-甲基-1-乙基(異)丙基(甲基)丙烯酸酯、1-甲基-1-乙基(異)丁基(甲基)丙烯酸酯、1-甲基-1-乙基(異)辛基丙烯酸酯、1-二乙基(異)丙基(甲基)丙烯酸酯、1-二乙基(異)丁基(甲基)丙烯酸酯、1-二乙基(異)辛基(甲基)丙烯酸酯等;(甲基)丙烯酸環烷基酯可以列舉(甲基)丙烯酸環己基酯、(甲基)丙烯酸2-甲基環己基酯、(甲基)丙烯酸三環[5.2.1.02 , 6 ]癸烷-8-基酯、(甲基)丙烯酸三環[5.2.1.02 , 6 ]癸烷-8-基氧基乙酯、(甲基)丙烯酸異冰片基酯、(甲基)丙烯酸1-甲基環丙烷基酯、(甲基)丙烯酸1-甲基環丁烷基酯、(甲基)丙烯酸1-甲基環戊烷基酯、(甲基)丙烯酸1-甲基環己烷基酯、(甲基)丙烯酸1-甲基環庚烷基酯、(甲基)丙烯酸1-甲基環辛烷基酯、(甲基)丙烯酸1-甲基環壬烷基酯、(甲基)丙烯酸1-乙基環癸烷基酯、(甲基)丙烯酸1-乙基環丙烷基酯、(甲基)丙烯酸1-乙基環丁烷基酯、(甲基)丙烯酸1-乙基環戊烷基酯、(甲基)丙烯酸1-乙基環己烷基酯、(甲基)丙烯酸1-乙基環庚烷基酯、(甲基)丙烯酸1-乙基環辛烷基酯、(甲基)丙烯酸1-乙基環壬烷基酯、(甲基)丙烯酸1-乙基環癸烷基酯、(甲基)丙烯酸1-(異)丙基環丙烷基酯、(甲基)丙烯酸1-(異)丙基環丁烷基酯、(甲基)丙烯酸1-(異)丙基環戊烷基酯、(甲基)丙烯酸1-(異)丙基環己烷基酯、(甲基)丙烯酸1-(異)丙基環庚烷基酯、(甲基)丙烯酸1-(異)丙基環辛烷基酯、(甲基)丙烯酸1-(異)丙基環壬烷基酯、(甲基)丙烯酸1-(異)丙基環癸烷基酯、(甲基)丙烯酸1-(異)丁基環丙烷基酯、(甲基)丙烯酸1-(異)丁基環丁烷基酯、(甲基)丙烯酸1-(異)丁基環戊烷基酯、(甲基)丙烯酸1-(異)丁基環己烷基酯、(甲基)丙烯酸1-(異)丁基環庚烷基酯、(甲基)丙烯酸1-(異)丁基環辛烷基酯、(甲基)丙烯酸1-(異)丁基環壬烷基酯、(甲基)丙烯酸1-(異)丁基環癸烷基酯、(甲基)丙烯酸1-(異)戊基環丙烷基酯、(甲基)丙烯酸1-(異)戊基環丁烷基酯、(甲基)丙烯酸1-(異)戊基環戊烷基酯、(甲基)丙烯酸1-(異)戊基環己烷基酯、(甲基)丙烯酸1-(異)戊基環庚烷基酯、(甲基)丙烯酸1-(異)戊基環辛烷基酯、(甲基)丙烯酸1-(異)戊基環壬烷基酯、(甲基)丙烯酸1-(異)戊基環癸烷基酯、(甲基)丙烯酸1-(異)己基環丙烷基酯、(甲基)丙烯酸1-(異)己基環丁烷基酯、(甲基)丙烯酸1-(異)己基環己烷基酯、(甲基)丙烯酸1-(異)己基環庚烷基酯、(甲基)丙烯酸1-(異)己基環辛烷基酯、(甲基)丙烯酸1-(異)己基環壬烷基酯、(甲基)丙烯酸1-(異)己基環癸烷基酯、(甲基)丙烯酸1-(異)庚基環丙烷基酯、(甲基)丙烯酸1-(異)庚基環丁烷基酯、(甲基)丙烯酸1-(異)庚基環庚烷基酯、(甲基)丙烯酸1-(異)庚基環辛烷基酯、(甲基)丙烯酸1-(異)庚基環壬烷基酯、(甲基)丙烯酸1-(異)庚基環癸烷基酯、(甲基)丙烯酸1-(異)辛基環丙烷基酯、(甲基)丙烯酸1-(異)辛基環丁烷基酯、(甲基)丙烯酸1-(異)辛基環辛烷基酯、(甲基)丙烯酸1-(異)辛基環庚烷基酯、(甲基)丙烯酸1-(異)辛基環壬烷基酯、(甲基)丙烯酸1-(異)辛基環癸烷基酯、2-乙基三環[3.3.1.13 , 7 ]癸烷-2-基-(甲基)丙烯酸酯、2-甲基三環[3.3.1.13 , 7 ]癸烷-2-基-(甲基)丙烯酸酯、1-乙基三環[3.3.1.13 , 7 ]癸烷-1-基-(甲基)丙烯酸酯、3-羥基三環[3.3.1.13 , 7 ]癸烷-1-基-(甲基)丙烯酸酯等;其中,丙烯酸環烷基酯的烷基部分,還可以是內酯結構、內醯胺結構、縮醛結構。作為例子,包括2-乙基-γ-丁內酯-2-基-(甲基)丙烯酸酯、2-甲基-γ-丁內酯-2-基-(甲基)丙烯酸酯、2-乙基-γ-丁內酯-3-基-(甲基)丙烯酸酯、2-甲基-γ-丁內酯-3-基-(甲基)丙烯酸酯、2-乙基-γ-丁內酯-4-基-(甲基)丙烯酸酯、2-甲基-γ-丁內酯-4-基-(甲基)丙烯酸酯、2-乙基-δ-戊內酯-2-基-(甲基)丙烯酸酯、2-乙基-δ-戊內酯-3-基-(甲基)丙烯酸酯、2-乙基-δ-戊內酯-4-基-(甲基)丙烯酸酯、2-乙基-δ-戊內酯-5-基-(甲基)丙烯酸酯之類的內酯類;2-乙基-γ-丁內醯胺-2-基-(甲基)丙烯酸酯、2-甲基-γ-丁內醯胺-2-基-(甲基)丙烯酸酯、2-乙基-γ-丁內醯胺-3-基-(甲基)丙烯酸酯、2-甲基-γ-丁內醯胺-3-基-(甲基)丙烯酸酯、2-乙基-γ-丁內醯胺-4-基-(甲基)丙烯酸酯、2-甲基-γ-丁內醯胺-4-基-(甲基)丙烯酸酯、2-乙基-δ-戊內醯胺-2-基-(甲基)丙烯酸酯、2-乙基-δ-戊內醯胺-3-基-(甲基)丙烯酸酯、2-乙基-δ-戊內醯胺-4-基-(甲基)丙烯酸酯、2-乙基-δ-戊內醯胺-5-基-(申基)丙烯酸酯之類的內醯胺類等;縮醛結構包括四氫-2H-吡喃-2-基酯等。Specific examples of the (a2) polymerizable unsaturated compound include, for example, hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and (methyl). 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-methyl propylene oxime Ethyl glucoside, 4-hydroxyphenyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, dibutyl (meth) acrylate Ester, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, tridecyl (meth)acrylate, (methyl) ) n-octadecyl acrylate, tert-butoxy (meth) acrylate, 1-dimethyl(iso)propyl (meth) acrylate, 1-dimethyl(iso)butyl (a) Acrylate, 1-dimethyl(iso)octyl (meth) acrylate, 1-methyl-1-ethylethyl (meth) acrylate, 1-methyl-1-ethyl ( Isopropyl (meth) acrylate, 1-methyl-1- Ethyl (iso)butyl (meth) acrylate, 1-methyl-1-ethyl (iso) octyl acrylate, 1-diethyl (isopropyl) propyl (meth) acrylate, 1- Diethyl (iso)butyl (meth) acrylate, 1-diethyl (iso) octyl (meth) acrylate, etc.; (meth) acrylate cycloalkyl ester can be exemplified by (meth)acrylic acid ring hexyl ester, (meth) acrylate, 2-methyl-cyclohexyl ester, (meth) acrylate, tricyclo [5.2.1.0 2, 6] decan-8-yl ester, (meth) acrylate, tricyclo [5.2.1.0 2 , 6 ]decane-8-yloxyethyl ester, isobornyl (meth)acrylate, 1-methylcyclopropyl (meth)acrylate, 1-methylcyclobutyl (meth)acrylate Alkyl ester, 1-methylcyclopentyl (meth)acrylate, 1-methylcyclohexane (meth)acrylate, 1-methylcycloheptyl (meth)acrylate, ( 1-methylcyclooctylalkyl (meth)acrylate, 1-methylcyclononyl (meth)acrylate, 1-ethylcyclodecyl (meth)acrylate, (meth)acrylic acid 1 -ethylcyclopropyl ester, 1-ethylcyclobutyl (meth)acrylate, 1-ethylcyclopentane (meth)acrylate Base ester, 1-ethylcyclohexane (meth)acrylate, 1-ethylcycloheptyl (meth)acrylate, 1-ethylcyclooctyl (meth)acrylate, (A) 1-ethylcyclodecyl acrylate, 1-ethylcyclodecyl (meth) acrylate, 1-(isopropyl)cyclopropyl (meth) acrylate, (meth) acrylate 1-(Isopropyl)cyclobutylalkyl ester, 1-(iso)propylcyclopentyl (meth)acrylate, 1-(iso)propylcyclohexane (meth)acrylate, ( 1-(Isopropyl)cycloheptyl (meth)acrylate, 1-(iso)propylcyclooctyl (meth)acrylate, 1-(iso)propylcyclodecane (meth)acrylate Base ester, 1-(iso)propylcyclodecyl (meth)acrylate, 1-(iso)butylcyclopropane (meth)acrylate, 1-(iso)butyl (meth)acrylate Cyclobutane, 1-(iso)butylcyclopentyl (meth)acrylate, 1-(iso)butylcyclohexyl (meth)acrylate, 1-(meth)acrylate Isobutylcycloheptyl ester, 1-(iso)butylcyclooctyl (meth)acrylate, 1-(iso)butylcycloalkyl (meth)acrylate, (methyl) Propylene 1-(Isobutyl)cyclodecylalkyl ester, 1-(iso)pentylcyclopropane (meth)acrylate, 1-(iso)pentylcyclobutane (meth)acrylate, (A) 1-(iso)pentylcyclopentyl acrylate, 1-(iso)pentylcyclohexyl (meth) acrylate, 1-(iso)pentylcycloheptyl (meth) acrylate Ester, 1-(iso)pentylcyclooctyl (meth)acrylate, 1-(iso)pentylcyclodecyl (meth)acrylate, 1-(iso)pentyl (meth)acrylate Cyclodecylalkyl ester, 1-(iso)hexylcyclopropane (meth)acrylate, 1-(iso)hexylcyclobutyl (meth)acrylate, 1-(iso)hexyl (meth)acrylate Cyclohexane ester, 1-(iso)hexylcycloheptyl (meth)acrylate, 1-(iso)hexylcyclooctyl (meth)acrylate, 1-(iso)(meth)acrylate Hexylcyclodecylalkyl ester, 1-(iso)hexylcyclodecyl (meth)acrylate, 1-(iso)heptylcyclopropyl (meth)acrylate, 1-(iso)(meth)acrylate Heptylcyclobutylalkyl ester, 1-(iso)heptylcycloheptyl (meth)acrylate, 1-(iso)heptylcyclooctyl (meth)acrylate, (meth) propylene 1-(Iso)heptylcyclodecylalkyl ester, 1-(iso)heptylcyclodecyl (meth)acrylate, 1-(iso)octylcyclopropane (meth)acrylate, (A) 1-(iso)octylcyclobutane acrylate, 1-(iso)octylcyclooctyl (meth) acrylate, 1-(iso)octylcycloheptyl (meth) acrylate Ester, 1-(iso)octylcyclodecyl (meth)acrylate, 1-(iso)octylcyclodecyl (meth)acrylate, 2-ethyltricyclo[3.3.1.1 3 , 7 ]decane-2-yl-(meth)acrylate, 2-methyltricyclo[3.3.1.1 3 , 7 ]decane-2-yl-(meth)acrylate, 1-ethyltricyclopropane [3.3.1.1 3 , 7 ]decane-1-yl-(meth)acrylate, 3-hydroxytricyclo[3.3.1.1 3 , 7 ]decane-1-yl-(meth)acrylate, etc.; The alkyl moiety of the cycloalkyl acrylate may also be a lactone structure, an indoleamine structure or an acetal structure. As an example, 2-ethyl-γ-butyrolactone-2-yl-(meth)acrylate, 2-methyl-γ-butyrolactone-2-yl-(meth)acrylate, 2- Ethyl-γ-butyrolactone-3-yl-(meth) acrylate, 2-methyl-γ-butyrolactone-3-yl-(meth) acrylate, 2-ethyl-γ-butyl Lactone-4-yl-(meth) acrylate, 2-methyl-γ-butyrolactone-4-yl-(meth) acrylate, 2-ethyl-δ-valerolactone-2-yl -(Meth)acrylate, 2-ethyl-δ-valerolide-3-yl-(meth)acrylate, 2-ethyl-δ-valerolactone-4-yl-(meth)acrylic acid Lactones, lactones such as 2-ethyl-δ-valerolactone-5-yl-(meth)acrylate; 2-ethyl-γ-butylidene-2-yl-(methyl) Acrylate, 2-methyl-γ-butylidene-2-yl-(meth) acrylate, 2-ethyl-γ-butylidene-3-yl-(meth) acrylate, 2 -Methyl-γ-butylidene-3-yl-(meth) acrylate, 2-ethyl-γ-butylidene-4-yl-(meth) acrylate, 2 -Methyl-γ-butylidene-4-yl-(meth) acrylate, 2-ethyl-δ-pentalin-2-yl-(meth) acrylate, 2-ethyl- Δ-valeroindol-3-yl-(meth) acrylate, 2-ethyl-δ-pentalin-4-yl-(meth) acrylate, 2-ethyl-δ-pentene An indoleamine or the like such as amidoxime-5-yl-(shenyl) acrylate; the acetal structure includes tetrahydro-2H-pyran-2-yl ester and the like.
作為(甲基)丙烯酸芳基酯,可以列舉甲基丙烯酸苯酯、甲基丙烯酸苄基酯等;作為不飽和二元羧酸二酯,可以列舉馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等;作為雙環不飽和化合物類,可以列舉雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-(2’-羥基乙基)雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二(羥基甲基)雙環[2.2.1]庚-2-烯、5,6-二(2’-羥基乙基)雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羥基甲基-5-甲基雙環[2.2.1]庚-2-烯等;作為馬來醯亞胺化合物類,可以列舉苯基馬來醯亞胺、環己基馬來醯亞胺、苄基馬來醯亞胺、N-琥珀醯亞胺基-3-馬來醯亞胺苯甲酸酯、N-琥珀醯亞胺基-4-馬來醯亞胺丁酸酯、N-琥珀醯亞胺基-6-馬來醯亞胺己酸酯、N-琥珀醯亞胺基-3-馬來醯亞胺丙酸酯、N-(9-吖啶基)馬來醯亞胺等;作為不飽和芳香族化合物,可以列舉苯乙烯、α-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、乙烯基甲苯、對-甲氧基苯乙烯等;作為共軛二烯類化合物,可以列舉1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯等;作為不飽和一元羧酸,可以列舉丙烯酸、甲基丙烯酸、巴豆酸等;作為不飽和二元羧酸,可以列舉馬來酸、富馬酸、檸康酸、中康酸、衣康酸等;作為不飽和二元羧酸酐,可以列舉上述各二元羧酸的酸酐;作為其他不飽和化合物,可以列舉丙烯腈、甲基丙烯腈、氯代乙烯、偏二氯乙烯、丙烯醯胺、甲基丙烯醯胺、乙酸乙烯酯等。Examples of the aryl (meth)acrylate include phenyl methacrylate and benzyl methacrylate; and examples of the unsaturated dicarboxylic acid diester include diethyl maleate and diethyl fumarate. Ester, diethyl itaconate, etc.; as bicyclic unsaturated compounds, bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-B Bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6 -dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2 .1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5 ,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5- Ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, etc.; as a maleimide compound, phenyl Maleic imine, cyclohexyl Kamalimide, benzyl maleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide Butyrate, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimide propionate, N-(9-acridinyl) And the like, and the unsaturated aromatic compound may, for example, be styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene or p-methoxy. Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like; as the unsaturated monocarboxylic acid Examples thereof include acrylic acid, methacrylic acid, and crotonic acid; and examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like; and unsaturated dicarboxylic acid; Examples of the acid anhydride include acid anhydrides of the above respective dicarboxylic acids; and examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, chloroethylene, vinylidene chloride, and acrylamide. Methyl acrylamide, and vinyl acetate.
其中,從共聚合反應性、耐熱性等角度出發,較佳苯乙烯、甲基丙烯酸三環[5.2.1.02 , 6 ]癸烷-8-基酯、對甲氧基苯乙烯、丙烯酸2-甲基環己基酯、1,3-丁二烯、雙環[2.2.1]庚-2-烯、N-環己基馬來醯亞胺、甲基丙烯酸、甲基丙烯酸1-乙基環戊烷基酯、2-甲基-2-丙酸、四氫-2H-吡喃-2-基酯等。Among them, styrene, methacrylic acid tricyclo [5.2.1.0 2 , 6 ]decane-8-yl ester, p-methoxystyrene, acrylic acid 2- are preferred from the viewpoints of copolymerization reactivity, heat resistance and the like. Methylcyclohexyl ester, 1,3-butadiene, bicyclo[2.2.1]hept-2-ene, N-cyclohexylmaleimide, methacrylic acid, 1-ethylcyclopentane methacrylate A base ester, 2-methyl-2-propionic acid, tetrahydro-2H-pyran-2-yl ester or the like.
它們可以單獨或者組合使用。They can be used singly or in combination.
(A)共聚物為來源於聚合性不飽和化合物單體的結構單元,較佳含有5-95重量%(a1)、95-5重量%(a2),更佳為20-95重量%(a1),80-5重量%(a2),最佳為30-90重量%(a1),70-10重量%(a2)[其中,(a1)+(a2)=100重量%]。在該範圍的含量下,可以實現良好的平坦化性能和耐熱性。(A) The copolymer is a structural unit derived from a monomer of a polymerizable unsaturated compound, preferably containing 5 to 95% by weight (a1), 95 to 5% by weight (a2), more preferably 20 to 95% by weight (a1) 80% by weight (a2), most preferably 30-90% by weight (a1), 70-10% by weight (a2) [where (a1) + (a2) = 100% by weight]. At the content of this range, good planarization performance and heat resistance can be achieved.
作為(A)共聚物的較佳具體例子,例如,可以列舉苯乙烯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/甲基丙烯酸三環[5.2.1.02 , 6 ]癸烷-8-基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-環己基馬來醯亞胺/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯共聚物、N-環己基馬來醯亞胺/甲基丙烯酸縮水甘油酯共聚物、N-苯基馬來醯亞胺/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/甲基丙烯酸三環[5.2.1.02 , 6 ]癸烷-8-基酯/甲基丙烯酸/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-環己基馬來醯亞胺/甲基丙烯酸/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-苯基馬來醯亞胺/甲基丙烯酸/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/甲基丙烯酸三環[5.2.1.02 , 6 ]癸烷-8-基酯/甲基丙烯酸1-乙基環己烷基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-環己基馬來醯亞胺/甲基丙烯酸1-乙基環己烷基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-苯基馬來醯亞胺/甲基丙烯酸1-乙基環己烷基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/甲基丙烯酸三環[5.2.1.02 , 6 ]癸烷-8-基酯/甲基丙烯酸1-乙基環戊烷基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-環己基馬來醯亞胺/甲基丙烯酸1-乙基環戊烷基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-苯基馬來醯亞胺/甲基丙烯酸1-乙基環戊烷基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/甲基丙烯酸三環[5.2.1.02 , 6 ]癸烷-8-基酯/甲基丙烯酸1-甲基環己烷基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-環己基馬來醯亞胺/甲基丙烯酸1-甲基環己烷基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-苯基馬來醯亞胺/甲基丙烯酸1-甲基環己烷基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/甲基丙烯酸三環[5.2.1.02 , 6 ]癸烷-8-基酯/四氫-2H-吡喃-2-基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-環己基馬來醯亞胺/四氫-2H-吡喃-2-基酯/甲基丙烯酸縮水甘油酯共聚物、苯乙烯/N-苯基馬來醯亞胺/四氫-2H-吡喃-2-基酯/甲基丙烯酸縮水甘油酯共聚物等。As preferred specific examples of the (A) copolymer, for example, a styrene/glycidyl methacrylate copolymer, a styrene/trimethyl methacrylate [5.2.1.0 2 , 6 ]decane-8-yl group can be cited. Ester/glycidyl methacrylate copolymer, styrene/N-cyclohexylmaleimide/glycidyl methacrylate copolymer, styrene/N-phenylmaleimide/methacrylic acid shrinkage Glyceride copolymer, N-cyclohexylmaleimide/glycidyl methacrylate copolymer, N-phenylmaleimide/glycidyl methacrylate copolymer, styrene/methacrylic acid Ring [5.2.1.0 2 , 6 ]decane-8-yl ester/methacrylic acid/glycidyl methacrylate copolymer, styrene/N-cyclohexylmaleimide/methacrylic acid/methacrylic acid Glycidyl ester copolymer, styrene/N-phenylmaleimide/methacrylic acid/glycidyl methacrylate copolymer, styrene/methacrylic acid tricyclo [5.2.1.0 2 , 6 ]decane -8-yl ester/1-ethylcyclohexane methacrylate/glycidyl methacrylate copolymer, styrene/N Cyclohexylmaleimide/1-ethylcyclohexane methacrylate/glycidyl methacrylate copolymer, styrene/N-phenylmaleimide/1-ethyl methacrylate Cyclohexane ester/glycidyl methacrylate copolymer, styrene/trimethyl methacrylate [5.2.1.0 2 , 6 ]decane-8-yl ester / 1-ethylcyclopentanyl methacrylate Ester/glycidyl methacrylate copolymer, styrene/N-cyclohexylmaleimide/1-ethylcyclopentyl methacrylate/glycidyl methacrylate copolymer, styrene/N -Phenylmaleimide/1-ethylcyclopentyl methacrylate/glycidyl methacrylate copolymer, styrene/trimethyl methacrylate [5.2.1.0 2 , 6 ] decane- 8-Base Ester/1-Methylcyclohexyl Methacrylate/Glycidyl Methacrylate Copolymer, Styrene/N-Cyclohexylmaleimide/1-Methylcyclohexane Glycol/glycidyl methacrylate copolymer, styrene/N-phenylmaleimide/1-methylcyclohexane methacrylate/glycidyl methacrylate Copolymer, styrene / methacrylic acid tricyclo [5.2.1.0 2, 6] decan-8-yl methacrylate / tetrahydro -2H- pyran-2-yl acrylate / glycidyl methacrylate copolymers, styrene Ethylene/N-cyclohexylmaleimide/tetrahydro-2H-pyran-2-yl ester/glycidyl methacrylate copolymer, styrene/N-phenylmaleimide/tetrahydro- 2H-pyran-2-yl ester/glycidyl methacrylate copolymer and the like.
(A)共聚物通過凝膠滲透色譜法(溶出溶劑為四氫呋喃)測定的聚苯乙烯換算重均分子量(以下,稱為“Mw”)較佳為1000-100000,更佳為2000-50000,特佳為3000-40000。此時,若Mw不足1000,則會出現組成物的塗敷性不夠好,或者所形成的保護膜的耐熱性不夠好的情況,另一方面,如果Mw超過100000,則會出現平坦化性能不夠好的情況。(A) The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (the elution solvent is tetrahydrofuran) is preferably from 1,000 to 100,000, more preferably from 2,000 to 50,000. Good for 3000-40000. In this case, if the Mw is less than 1,000, the coating property of the composition may not be sufficiently good, or the heat resistance of the formed protective film may be insufficient. On the other hand, if the Mw exceeds 100,000, the flattening property may be insufficient. Good situation.
此外,(A)共聚物的分子量分佈(Mw/Mn)較佳為5.0以下,更佳為3.0以下。Further, the molecular weight distribution (Mw/Mn) of the (A) copolymer is preferably 5.0 or less, more preferably 3.0 or less.
這樣的(A)共聚物可以將上述(a1)聚合性不飽和化合物和(a2)其他聚合性不飽和化合物在適當的溶劑和適當的聚合引發劑的存在下,通過公知的方法例如自由基聚合而進行合成。Such (A) copolymer may be obtained by a known method such as radical polymerization in the presence of a (a1) polymerizable unsaturated compound and (a2) another polymerizable unsaturated compound in the presence of a suitable solvent and a suitable polymerization initiator. And synthesis.
例如,上述自由基聚合可以通過將5-95重量份甲基丙烯酸縮水甘油酯等的(a1)聚合性不飽和化合物與95-5重量份苯乙烯等的(a2)其他聚合性不飽和化合物[其中,(a1)+(a2)=100重量份]混合在100-400重量份例如乙基溶纖劑乙酸酯、丙二醇單甲醚乙酸酯等溶劑中,相對於100重量份單體成分的合計量,添加0.5-15重量份作為聚合引發劑的偶氮二異丁腈(AIBN)、2,2’-偶氮(2,4-二甲基戊腈)等自由基聚合引發劑,在70-100℃下,聚合3-10小時而製得。For example, the above-mentioned radical polymerization may be carried out by using (a1) a polymerizable unsaturated compound such as 5-95 parts by weight of glycidyl methacrylate and 95 to 5 parts by weight of (a2) other polymerizable unsaturated compound of styrene [ Wherein (a1)+(a2)=100 parts by weight] is mixed in 100-400 parts by weight of a solvent such as ethyl cellosolve acetate or propylene glycol monomethyl ether acetate, relative to 100 parts by weight of the monomer component a total amount of 0.5 to 15 parts by weight of a radical polymerization initiator such as azobisisobutyronitrile (AIBN) or 2,2'-azo (2,4-dimethylvaleronitrile) as a polymerization initiator. It is obtained by polymerization at 70-100 ° C for 3-10 hours.
本發明中使用的(B)磷酸類酯具有上述式(1)表示的結構。The (B) phosphate ester used in the present invention has a structure represented by the above formula (1).
在(B)成分中,上述式(1)中的R1 較佳是碳原子數為1-18的烷基、芳基、苄基或者烷基未端或側鏈上具有碳原子數為1-4的烷氧基的碳原子數為1-8的烷基,或者是乙酸酯基,R2 較佳是碳原子數為1-18的烷基或者芳基或苄基等。In the component (B), R 1 in the above formula (1) is preferably an alkyl group having 1 to 18 carbon atoms, an aryl group, a benzyl group or an alkyl group having a carbon atom number of 1 or a side chain. The alkoxy group of -4 has an alkyl group having 1 to 8 carbon atoms or an acetate group, and R 2 is preferably an alkyl group having 1 to 18 carbon atoms or an aryl group or a benzyl group.
當(B)成分為三甲基磷酸酯和/或三乙基磷酸酯時,從膜表面的平滑性、間歇時間等方面考慮是較佳的。When the component (B) is trimethyl phosphate and/or triethyl phosphate, it is preferable from the viewpoints of smoothness of the surface of the film, intermittent time, and the like.
作為這些(B)磷酸類酯,在上述式(1)中,當X=0時,可以列舉三(十八烷基)磷酸酯、二(十八烷基)磷酸酯、單十八烷基磷酸酯、三(異)丁基磷酸酯、二(異)丁基磷酸酯、單(異)丁基磷酸酯、三(異)丙基磷酸酯、二(異)丙基磷酸酯、單(異)丙基磷酸酯、三乙基磷酸酯、二乙基磷酸酯、單乙基磷酸酯、三甲基磷酸酯、二甲基磷酸酯、單甲基磷酸酯、三苯基磷酸酯、二苯基磷酸酯、單苯基磷酸酯、三苄基磷酸酯、二苄基磷酸酯、單苄基磷酸酯等。As the (B) phosphate ester, in the above formula (1), when X = 0, tris(octadecyl) phosphate, dioctadecyl phosphate, and monooctadecyl group are exemplified. Phosphate ester, tri(iso)butyl phosphate, di(iso)butyl phosphate, mono(iso)butyl phosphate, tris(isopropyl) phosphate, di(iso)propyl phosphate, single ( Isopropyl phosphate, triethyl phosphate, diethyl phosphate, monoethyl phosphate, trimethyl phosphate, dimethyl phosphate, monomethyl phosphate, triphenyl phosphate, two Phenyl phosphate, monophenyl phosphate, tribenzyl phosphate, dibenzyl phosphate, monobenzyl phosphate, and the like.
另外,在上述式(1)中,當X=1,R1 為氫原子時,作為(B)磷酸類酯的具體例子,可以列舉膦酸二(十八烷基酯)、膦酸單十八烷基酯、膦酸二(異)丁基酯、膦酸單(異)丁基酯、膦酸二(異)丙基酯、膦酸單(異)丙基酯、膦酸二乙酯、膦酸單乙酯、膦酸二甲酯、膦酸單甲酯、膦酸二苯基酯、膦酸單苯基酯、膦酸二苄基酯、膦酸單苄基酯等。Further, in the above formula (1), when X = 1 and R 1 is a hydrogen atom, specific examples of the (B) phosphoric acid ester include dioctadecyl phosphonate and phosphonic acid mono Octaalkyl ester, di(iso)butyl phosphonate, mono(iso)butyl phosphonate, di(iso)propyl phosphonate, mono (iso)propyl phosphonate, diethyl phosphonate And monoethyl phosphonate, dimethyl phosphonate, monomethyl phosphonate, diphenyl phosphonate, monophenyl phosphonate, dibenzyl phosphonate, monobenzyl phosphonate, and the like.
並且,在上述式(1)中,當X=1,R1 的與磷原子相鄰的原子為碳原子時,作為(B)磷酸類酯的具體例子,可以列舉磷酸乙酸三甲酯、二乙基鄰苯二甲醯亞胺甲基磷酸酯、三丙烯醯氧基乙基磷酸酯、二丙烯醯氧基乙基磷酸酯、單丙烯醯氧基乙基磷酸酯等。Further, in the above formula (1), when X=1, and the atom adjacent to the phosphorus atom of R 1 is a carbon atom, specific examples of the (B) phosphate ester include trimethyl phosphate and two. Ethyl phthalic acid imine methyl phosphate, tripropylene methoxyethyl phosphate, dipropylene methoxyethyl phosphate, mono propylene oxyethyl phosphate, and the like.
(B)成分的添加量,相對於100重量份(A)成分,為0.01-50重量份,較佳為0.1-30重量份,更佳為0.5-10重量份。當不足0.01重量份時,則不能獲得足夠的硬度,另一方面,若超過50重量份,則間歇時間延長。The amount of the component (B) to be added is 0.01 to 50 parts by weight, preferably 0.1 to 30 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the component (A). When it is less than 0.01 part by weight, sufficient hardness cannot be obtained, and on the other hand, if it exceeds 50 parts by weight, the intermittent time is prolonged.
本發明的樹脂組成物必須有上述(A)~(B)成分,並且,還可以含有(C)路易士酸催化劑。(C)路易士酸催化劑在本發明的樹脂組成物中發揮促進硬化的作用。The resin composition of the present invention must have the above components (A) to (B), and may further contain (C) a Lewis acid catalyst. (C) The Lewis acid catalyst exerts a function of promoting hardening in the resin composition of the present invention.
作為本發明中所使用的(C)路易士酸催化劑,可以列舉二乙基鋅、二苯基鋅、氯化鋅、二異丁基苯基鋁、二乙基鋁乙硫化物、二乙基苯基鋁、二甲基鋁甲氧化合物、三苯基鋁、三苄基鋁、三第三丁基鋁、N-亞硝基苯基羥基胺鋁鹽、二乙基二氯矽烷、1,1-二甲基-1-矽雜環戊烷、四乙基矽烷、四甲基矽烷、三苯基氯矽烷、三甲基氯矽烷、氯三苄基鋯、氯化鋯、三乙醯氧基環戊二烯基鋯、二氯二(環戊二烯基)鋯、二丁基錫二月桂酸鹽、二丁基錫二辛酸鹽、三甲基氯錫烷、三甲基甲氧基錫烷、氯三苄基鈦、氯化鈦、氯代二(環戊二烯基)鈦、二茂鈦、三氯甲基鈦、氯三(三苯基膦)鎳、四(三苯基膦)鎳、二茂鎳、二乙基氯硼烷、二異丙基氯硼烷、二苯基氯硼烷、二丁基氯硼烷等。As the (C) Lewis acid catalyst used in the present invention, diethyl zinc, diphenyl zinc, zinc chloride, diisobutylphenyl aluminum, diethyl aluminum ethane sulfide, diethyl ether can be cited. Phenyl aluminum, dimethyl aluminum methoxy compound, triphenyl aluminum, tribenzyl aluminum, tri-tert-butyl aluminum, N-nitrosophenyl hydroxylamine aluminum salt, diethyl dichlorodecane, 1, 1-Dimethyl-1-indole heterocyclopentane, tetraethyl decane, tetramethyl decane, triphenylchlorodecane, trimethylchlorodecane, chlorotribenzyl zirconium, zirconium chloride, triethylene oxychloride Base cyclopentadienyl zirconium, dichlorobis(cyclopentadienyl)zirconium, dibutyltin dilaurate, dibutyltin dioctanoate, trimethylchlorostannane, trimethylmethoxystannane, chlorine Tribenzyl titanium, titanium chloride, chlorobis(cyclopentadienyl)titanium, titanocene, trichloromethyltitanium, chlorotris(triphenylphosphine)nickel, tetrakis(triphenylphosphine)nickel, Nickel nickel, diethyl chloroborane, diisopropyl chloroborane, diphenyl chloroborane, dibutyl chloroborane, and the like.
(C)路易士酸催化劑的添加量,相對於100重量份(A)成分,為0.0001-20重量份,較佳為0.001-10重量份,更佳為0.005-5重量份。當不足0.0001重量份時,則不能得到足夠的促進效果,另一方面,如果超過20重量份,則會出現析出而使膜表面發生皸裂的情況。The amount of the (C) Lewis acid catalyst added is 0.0001 to 20 parts by weight, preferably 0.001 to 10 parts by weight, more preferably 0.005 to 5 parts by weight per 100 parts by weight of the component (A). When the amount is less than 0.0001 part by weight, a sufficient promoting effect cannot be obtained. On the other hand, if it exceeds 20 parts by weight, precipitation may occur to cause cracking of the surface of the film.
(D)陽離子聚合性化合物(D) cationically polymerizable compound
本發明的樹脂組成物必須有上述(A)~(B)成分,並且,還可以含有(D)陽離子聚合性化合物[其中,上述(A)成分除外]。(D)陽離子聚合性化合物在本發明的樹脂組成物中發揮提高膜硬度的作用。The resin composition of the present invention must have the above components (A) to (B), and may further contain (D) a cationically polymerizable compound (wherein the above component (A) is excluded). (D) The cationically polymerizable compound functions to increase the film hardness in the resin composition of the present invention.
本發明中所使用的(D)陽離子聚合性化合物是分子內具有2個以上環氧乙烷基或環氧丙烷基的化合物(其中,上述(A)成分除外)。作為上述分子內具有2個以上環氧乙烷基或環氧丙烷基的化合物,可以列舉例如分子內具有2個以上環氧基的化合物或具有3,4-環氧環己基的化合物。The (D) cationically polymerizable compound used in the present invention is a compound having two or more oxirane groups or propylene oxide groups in the molecule (excluding the above component (A)). The compound having two or more oxirane groups or propylene oxide groups in the molecule may, for example, be a compound having two or more epoxy groups in the molecule or a compound having a 3,4-epoxycyclohexyl group.
其中,作為上述分子內具有2個以上環氧基的化合物,例如,可以列舉雙酚A二縮水甘油醚、雙酚F二縮水甘油醚、雙酚S二縮水甘油醚、氫化雙酚A二縮水甘油醚、氫化雙酚F二縮水甘油醚、氫化雙酚AD二縮水甘油醚、溴代雙酚A二縮水甘油醚、溴代雙酚F二縮水甘油醚、溴代雙酚S二縮水甘油醚等雙酚化合物的二縮水甘油醚類;1,4-丁二醇二縮水甘油醚、1,6-己二醇二縮水甘油醚、甘油三縮水甘油醚、三羥甲基丙烷三縮水甘油醚、聚乙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚等多元醇的多縮水甘油醚類;在乙二醇、丙二醇、甘油等脂肪族多元醇上加成1種或者2種以上環氧烷所得的聚醚多羥基化合物的多縮水甘油醚類;苯酚酚醛型環氧樹脂;甲酚酚醛型環氧樹脂;多酚型環氧樹脂;脂肪族長鏈二元酸的二縮水甘油酯類;高級脂肪酸的縮水甘油酯類;環氧化大豆油、環氧化亞麻子油等。In addition, examples of the compound having two or more epoxy groups in the molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, and hydrogenated bisphenol A condensed water. Glycerol ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, bromobisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether Diglycidyl ethers of bisphenol compounds; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether a polyglycidyl ether of a polyhydric alcohol such as polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether; or one or more epoxy resins added to an aliphatic polyol such as ethylene glycol, propylene glycol or glycerin; a polyglycidyl ether of a polyether polyol obtained by an alkane; a phenol novolak type epoxy resin; a cresol novolac type epoxy resin; a polyphenol type epoxy resin; a diglycidyl ester of an aliphatic long-chain dibasic acid; Glycidyl esters of higher fatty acids; large epoxidation Soybean oil, epoxidized linseed oil, etc.
作為上述分子內具有2個以上環氧基的化合物的市售品,例如,作為雙酚A型環氧樹脂可以列舉EPIKOTE1001、EPIKOTE1002、EPIKOTE1003、EPIKOTE1004、EPIKOTE1007、EPIKOTE1009、EPIKOTE1010、EPIKOTE828(以上由Japan Epoxy Resins(株)生產)等;作為雙酚F型環氧樹脂,可以列舉EPIKOTE807(由Japan Epoxy Resins(株)生產)等;作為苯酚酚醛型環氧樹脂,可以列舉EPIKOTE152、EPIKOTE154、EPIKOTE157S65(以上由Japan Epoxy Resins(株)生產)、EPPN 201、EPPN 202(以上由日本化藥(株)生產)等;作為甲酚酚醛型環氧樹脂,可以列舉EOCN 102、EOCN 103S、EOCN 104S、1020、1025、1027(以上由日本化藥(株)生產)、EPIKOTE180S75(由Japan Epoxy Resins(株)生產)等;作為多酚型環氧樹脂,可以列舉EPIKOTE1032H60、EPIKOTEXY-4000(以上由Japan Epoxy Resins(株)生產)等;作為環狀脂肪族環氧樹脂,可以列舉CY-175、CY-177、CY-179、Araldit CY-182、Araldit CY-192、184(以上由Ciba Specialty Chemicals(株)生產)、ERL-4234、4299、4221、4206(以上由U.C.C公司生產)、Shodain 509(由昭和電工(株)生產)、EPICRONE 200、EPICRONE 400(以上由大日本油墨(株)生產)、EPIKOTE871、EPIKOTE872(以上由Japan Epoxy Resins(株)生產)、ED-5661、ED-5662(以上由Celanese(株)生產)等;作為脂肪族多縮水甘油醚,可以列舉Epolaid 100MF(共榮社化學(株)生產)、Epiol TMP(日本油脂(株)生產)等。As a commercial item of the compound having two or more epoxy groups in the above-mentioned molecule, for example, EPIKOTE 1001, EPIKOTE 1002, EPIKOTE 1003, EPIKOTE 1004, EPIKOTE 1007, EPIKOTE 1009, EPIKOTE 1010, EPIKOTE 828 (above by Japan Epoxy) may be mentioned. Examples of the bisphenol F-type epoxy resin include EPIKOTE 807 (produced by Japan Epoxy Resins Co., Ltd.); and examples of the phenol novolak type epoxy resin include EPIKOTE 152, EPIKOTE 154, and EPIKOTE 157 S65 (above Japan Epoxy Resins Co., Ltd., EPPN 201, EPPN 202 (manufactured by Nippon Kayaku Co., Ltd.), etc.; as cresol novolac type epoxy resin, EOCN 102, EOCN 103S, EOCN 104S, 1020, 1025 1027 (the above is produced by Nippon Kayaku Co., Ltd.), EPIKOTE 180S75 (produced by Japan Epoxy Resins Co., Ltd.), etc., and as the polyphenol type epoxy resin, EPIKOTE 1032H60 and EPIKOTEXY-4000 (above by Japan Epoxy Resins) ))); as a cyclic aliphatic epoxy resin, CY-175, CY-177, CY-179, Araldit CY-182, Araldit CY-192, 184 (above) Ciba Specialty Chemicals Co., Ltd., ERL-4234, 4299, 4221, 4206 (manufactured by UCC Corporation), Shodain 509 (produced by Showa Denko Co., Ltd.), EPICRONE 200, EPICRONE 400 (above by Dainippon Ink ( (Production), EPIKOTE871, EPIKOTE872 (above produced by Japan Epoxy Resins Co., Ltd.), ED-5661, ED-5662 (produced by Celanese Co., Ltd.), etc.; as an aliphatic polyglycidyl ether, Epolaid 100MF can be cited. (produced by Kyoeisha Chemical Co., Ltd.), Epiol TMP (produced by Nippon Oil & Fat Co., Ltd.), and the like.
作為上述分子內具有2個以上3,4-環氧環己基的化合物,可以列舉例如3,4-環氧環己基甲基-3’,4’-環氧環己烷羧酸酯、2-(3,4-環氧環己基-5,5-螺-3,4-環氧)環己烷-間-二氧六環、二(3,4-環氧環己基甲基)己二酸酯、二(3,4-環氧-6-甲基環己基甲基)己二酸酯、3,4-環氧-6-甲基環己基-3’,4’-環氧-6’-甲基環己烷羧酸酯、亞甲基二(3,4-環氧環己烷)、二環戊二烯二環氧化物、乙二醇的二(3,4-環氧環己基甲基)醚、亞甲基二(3,4-環氧環己烷羧酸酯)、內酯改性的3,4-環氧環己基甲基-3’,4’-環氧環己烷羧酸酯等。Examples of the compound having two or more 3,4-epoxycyclohexyl groups in the molecule include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, and 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl)adipate Ester, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3',4'-epoxy-6' -Methylcyclohexanecarboxylate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol bis(3,4-epoxycyclohexyl Methyl)ether, methylene bis(3,4-epoxycyclohexanecarboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxy ring Alkyl carboxylate and the like.
這種(D)陽離子聚合性化合物中,較佳苯酚酚醛型環氧樹脂和多酚型環氧樹脂。Among such (D) cationically polymerizable compounds, a phenol novolak type epoxy resin and a polyphenol type epoxy resin are preferable.
本發明樹脂組成物中(D)陽離子聚合性化合物的用量,每100重量份(A)成分,較佳為3-200重量份,更佳為5-100重量份,特佳為10-50重量份。如果(D)陽離子聚合性化合物的用量比200重量份還多,則會產生組成物塗敷性出現問題的情況,另一方面,若不足3重量份,則會出現所得保護膜的硬度不夠的情況。The amount of the (D) cationically polymerizable compound in the resin composition of the present invention is preferably from 3 to 200 parts by weight, more preferably from 5 to 100 parts by weight, particularly preferably from 10 to 50 parts by weight per 100 parts by weight of the component (A). Share. When the amount of the (D) cationically polymerizable compound is more than 200 parts by weight, there is a problem that the coating property of the composition is problematic. On the other hand, if the amount is less than 3 parts by weight, the hardness of the obtained protective film may be insufficient. Happening.
為了提高所形成的保護膜與基板的密合性,可以在本發明的樹脂組成物中添加(E)黏結助劑。In order to improve the adhesion between the formed protective film and the substrate, (E) a bonding aid may be added to the resin composition of the present invention.
作為這種(E)黏結助劑,例如,可以使用具有反應性取代基的官能性矽烷偶合劑。作為上述反應性取代基,例如,可以列舉羧酸基、甲基丙烯醯基、異氰酸酯基、環氧基等。As such (E) bonding assistant, for example, a functional decane coupling agent having a reactive substituent can be used. Examples of the reactive substituent include a carboxylic acid group, a methacryl fluorenyl group, an isocyanate group, and an epoxy group.
作為(E)黏結助劑的具體例子,例如,可以列舉三甲氧基矽烷基安息香酸、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-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷等。Specific examples of the (E) adhesion aid include, for example, trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, and vinyl trimethyl. Oxydecane, γ-isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl triethoxy decane, β-(3, 4 - Epoxycyclohexyl)ethyltrimethoxydecane, and the like.
這種(E)黏結助劑,每100重量份(A)共聚物,較佳使用30重量份以下,更佳25重量份以下,特佳5-20重量份的量。若(E)黏結助劑的量超過30重量份,則會出現所得保護膜的耐熱性不夠好的情況。The (E) adhesion aid is preferably used in an amount of 30 parts by weight or less, more preferably 25 parts by weight or less, particularly preferably 5 to 20 parts by weight per 100 parts by weight of the (A) copolymer. If the amount of the (E) adhesion aid exceeds 30 parts by weight, the heat resistance of the obtained protective film may be insufficient.
為了改善本發明樹脂組成物的塗敷性能,可以在本發明的樹脂組成物中添加(F)界面活性劑。In order to improve the coating property of the resin composition of the present invention, (F) a surfactant may be added to the resin composition of the present invention.
作為這種(F)界面活性劑,例如,可以列舉氟類界面活性劑、聚矽氧烷類界面活性劑、非離子類界面活性劑、其他的界面活性劑。Examples of such a (F) surfactant include a fluorine-based surfactant, a polyoxyalkylene surfactant, a nonionic surfactant, and other surfactants.
作為上述氟類表面活性劑,例如,可以列舉BM CHIMIE社生產的商品名為BM-1000、BM-1100、大日本油墨化學工業株式會社生產的商品名為MEGAFAC F142D、MEGAFAC F172、MEGAFAC F173、MEGAFAC F183、住友3M(株)生產的商品名為FLUORAD FC-135、FLUORAD FC-170C、FLUORAD FC-430、FLUORAD FC-431、(株)NEOS生產的商品名為Ftergent 250、Ftergent 251、Ftergent 222F、FTX-218、旭硝子(株)生產的商品名為SARFRON S-112、SARFRON S-113、SARFRON S-131、SARFRON S-141、SARFRON S-145、SARFRON S-382、SARFRON SC-101、SARFRON SC-102、SARFRON SC-103、SARFRON SC-104、SARFRON SC-105、SARFRON SC-106等市售品。Examples of the fluorine-based surfactant include BM-1000, BM-1100, manufactured by BM CHIMIE Co., Ltd., and MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, and MEGAFAC, manufactured by Dainippon Ink and Chemicals, Inc. F183, Sumitomo 3M Co., Ltd. produced under the trade names FLUORAD FC-135, FLUORAD FC-170C, FLUORAD FC-430, FLUORAD FC-431, NEOS, and the trade names Ftergent 250, Ftergent 251, Ftergent 222F, FTX-218 and Asahi Glass Co., Ltd. are sold under the trade names SARFRON S-112, SARFRON S-113, SARFRON S-131, SARFRON S-141, SARFRON S-145, SARFRON S-382, SARFRON SC-101, SARFRON SC. -102, SARFRON SC-103, SARFRON SC-104, SARFRON SC-105, SARFRON SC-106 and other commercial products.
作為上述聚矽氧烷類表面活性劑,例如,可以列舉由Toray Dowcorning Silicone(株)生產的商品名為SH-28PA、SH-190、SH-193、SZ-6032、SF-8428、DC-57、DC-190、由信越化學工業(株)社生產的商品名為KP341、由新秋田化成(株)社生產的商品名為EFTOP EF301、EFTOP EF303、EFTOP EF352等市售品。Examples of the polysiloxane surfactants include, for example, those produced by Toray Dow Corning Silicone Co., Ltd. under the trade names of SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, and DC-57. DC-190, a trade name of KP341 produced by Shin-Etsu Chemical Co., Ltd., and a commercial item such as EFTOP EF301, EFTOP EF303, and EFTOP EF352, which are produced by New Akita Chemicals Co., Ltd.
作為上述非離子類界面活性劑,例如,可以列舉聚環氧乙烷烷基醚類、聚環氧乙烷芳基醚類、聚環氧乙烷二烷基酯類等。Examples of the nonionic surfactant include polyethylene oxide alkyl ethers, polyethylene oxide aryl ethers, and polyethylene oxide dialkyl esters.
作為上述聚環氧乙烷烷基醚類,可以列舉例如聚氧乙烯十二烷基醚、聚氧乙烯十八烷基醚、聚氧乙烯油基醚等,作為聚環氧乙烷芳基醚類,可以列舉例如聚氧乙烯辛基苯基醚、聚氧乙烯壬基苯基醚等,作為聚環氧乙烷二烷基酯類,可以列舉例如聚氧乙烯二月桂酸酯、聚氧乙烯二硬脂酸酯等。Examples of the polyoxirane alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and the like, and polyethylene oxide aryl ether. Examples thereof include polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether. Examples of the polyethylene oxide dialkyl esters include polyoxyethylene dilaurate and polyoxyethylene. Distearate and the like.
作為上述其他表面活性劑,可以列舉由共榮社化學(株)社生產的商品名為(甲基)丙烯酸類共聚物Polyfro No.57、Polyfro No.90等。For the other surfactants, the product name (meth)acrylic copolymer Polyfro No. 57, Polyfro No. 90, etc., which are produced by Kyoei Kogyo Co., Ltd., may be mentioned.
這些(F)界面活性劑的添加量,每100重量份(A)成分,較佳使用5重量份以下,更佳2重量份以下,特佳0.001-1.0重量份的範圍。當(F)界面活性劑的量超過5重量份時,則會出現在塗敷步驟中容易產生塗膜膜皸裂的情況。The amount of the (F) surfactant to be added is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, particularly preferably 0.001 to 1.0 part by weight per 100 parts by weight of the component (A). When the amount of the (F) surfactant is more than 5 parts by weight, there is a case where the coating film is easily cleaved in the coating step.
為了提高膜強度,可以在本發明的樹脂組成物中添加熱敏性酸發生劑。作為(G)熱敏性酸發生劑,可以列舉鋶鹽類、苯並噻唑鎓鹽類、銨鹽類、鏻鹽類等,其中較佳使用鋶鹽類、苯並噻唑鎓鹽類。In order to increase the film strength, a heat-sensitive acid generator may be added to the resin composition of the present invention. Examples of the (G) heat-sensitive acid generator include an onium salt, a benzothiazolium salt, an ammonium salt, and an onium salt. Among them, an onium salt or a benzothiazole salt is preferably used.
作為上述鋶鹽類的具體例子,可以列舉4-乙醯苯基二甲基鋶六氟銻酸鹽、4-乙醯氧基苯基二甲基鋶六氟砷酸鹽、二甲基-4-(苄氧羰氧基)苯基鋶六氟銻酸鹽、二甲基-4-(苯甲醯氧基)苯基鋶六氟銻酸鹽、二甲基-4-(苯甲醯氧基)苯基鋶六氟砷酸鹽、二甲基-3-氯-4-乙醯氧基苯基鋶苯基鋶六氟銻酸鹽等烷基鋶鹽;苄基-4-羥基苯基甲基鋶六氟銻酸鹽、苄基-4-羥基苯基甲基鋶六氟磷酸鹽、4-乙醯氧基苯基苄基甲基鋶六氟銻酸鹽、苄基-4-甲氧苯基甲基鋶六氟銻酸鹽、苄基-2-甲基-4-羥基苯基甲基鋶六氟銻酸鹽、苄基-3-氯-4-羥基苯基甲基鋶六氟砷酸鹽、4-甲氧基苄基-4-羥基苯基甲基鋶六氟磷酸鹽等苄基鋶鹽;二苄基-4-羥基苯基鋶六氟銻酸鹽、二苄基-4-羥基苯基鋶六氟磷酸鹽、4-乙醯氧基苯基二苄基鋶六氟銻酸鹽、二苄基-4-甲氧基苯基鋶六氟銻酸鹽、二苄基-3-氯-4-羥基苯基鋶六氟砷酸鹽、二苄基-3-甲基-4-羥基-5-第三丁基苯基鋶六氟銻酸鹽、苄基-4-甲氧基苄基-4-羥基苯基鋶六氟磷酸鹽等二苄基鋶鹽;p-氯苄基-4-羥基苯基甲基鋶六氟銻酸鹽、p-硝基苄基-4-羥基苯基甲基鋶六氟銻酸鹽、p-氯苄基-4-羥基苯基甲基鋶六氟磷酸鹽、p-硝基苄基-3-甲基-4-羥基苯基甲基鋶六氟銻酸鹽、3,5-二氯苄基-4-羥基苯基甲基鋶六氟銻酸鹽、o-氯苄基-3-氯-4-羥基苯基甲基鋶六氟銻酸鹽等取代苄基鋶鹽等。Specific examples of the above sulfonium salt include 4-ethyl phenyl phenyl hexafluoroantimonate, 4-ethyl methoxy phenyl dimethyl hexafluoro arsenate, and dimethyl-4. -(Benzyloxycarbonyloxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzylideneoxy)phenylphosphonium hexafluoroantimonate, dimethyl-4-(benzonitrile) An alkyl sulfonium salt such as phenyl hydrazine hexafluoroarsenate or dimethyl-3-chloro-4-ethoxy phenyl phenyl hexafluoroantimonate; benzyl-4-hydroxyphenyl Methyl hydrazine hexafluoroantimonate, benzyl-4-hydroxyphenylmethyl sulfonium hexafluorophosphate, 4-acetoxyphenylbenzyl methyl hexafluoroantimonate, benzyl-4-methyl Oxyphenylmethyl hydrazine hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethyl hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethyl fluorene a benzyl sulfonium salt such as fluoroarsenate or 4-methoxybenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate; dibenzyl-4-hydroxyphenylphosphonium hexafluoroantimonate, dibenzyl 4-hydroxyphenylphosphonium hexafluorophosphate, 4-ethyloxyphenyl dibenzyl hexafluoroantimonate, dibenzyl-4 Methoxyphenylphosphonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylphosphonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-third Dibenzyl sulfonium salt such as phenyl hydrazine hexafluoroantimonate or benzyl-4-methoxybenzyl-4-hydroxyphenyl sulfonium hexafluorophosphate; p-chlorobenzyl-4-hydroxyphenyl Hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, p-chlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluorophosphate, p- Nitrobenzyl-3-methyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylphosphonium hexafluoroantimonate, o-chloro A substituted benzyl sulfonium salt or the like such as benzyl-3-chloro-4-hydroxyphenylmethylphosphonium hexafluoroantimonate.
其中,較佳使用4-乙醯氧基苯基二甲基鋶六氟砷酸鹽、苄基-4-羥基苯基甲基鋶六氟銻酸鹽、4-乙醯氧基苯基苄基甲基鋶六氟銻酸鹽、二苄基-4-羥基苯基鋶六氟銻酸鹽、4-乙醯氧基苯基苄基鋶六氟銻酸鹽等。Among them, 4-ethenyloxy phenyl dimethyl hexafluoroarsenate, benzyl-4-hydroxyphenylmethyl hexafluoroantimonate, 4-ethenyloxyphenyl benzyl is preferably used. Methyl hydrazine hexafluoroantimonate, dibenzyl-4-hydroxyphenyl hexafluoroantimonate, 4-ethenyloxyphenylbenzyl hexafluoroantimonate, and the like.
作為上述苯並噻唑鎓鹽類,可以列舉3-苄基苯並噻唑鎓六氟銻酸鹽、3-苄基苯並噻唑鎓六氟磷酸鹽、3-苄基苯並噻唑鎓四氟硼酸鹽、3-(p-甲氧基苄基)苯並噻唑鎓六氟銻酸鹽、3-苄基-2-甲硫基苯並噻唑鎓六氟銻酸鹽、3-苄基-5-氯苯並噻唑鎓六氟銻酸鹽等苄基苯並噻唑鎓鹽。Examples of the above benzothiazolium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, and 3-benzylbenzothiazolium tetrafluoroborate. , 3-(p-methoxybenzyl)benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-chloro Benzylbenzothiazolium salt such as benzothiazolium hexafluoroantimonate.
其中,較佳使用3-苄基苯並噻唑鎓六氟銻酸鹽等。Among them, 3-benzylbenzothiazolium hexafluoroantimonate or the like is preferably used.
作為適合用作(G)熱敏性酸發生劑的市售品,烷基鋶鹽可以列舉旭電化工業(株)生產的商品名:ADEKA OPTON CP-66、CP-77。As a commercially available product which is suitable for use as the (G) heat-sensitive acid generator, the alkyl sulfonium salt can be exemplified by the trade names of ADEKA OPTON CP-66 and CP-77 manufactured by Asahi Kasei Kogyo Co., Ltd.
此外,作為苄基鋶,可以列舉三新化學工業(株)生產的商品名:SI-60、SI-80、SI-100、SI-110、SI-145、SI-150、SI-80L、SI-100L、SI-110L。In addition, as the benzyl hydrazine, trade names of SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, and SI can be cited. -100L, SI-110L.
其中,從所得保護膜具有高表面硬度的方面考慮,較佳為SI-80、SI-100、SI-110。Among them, from the viewpoint that the obtained protective film has high surface hardness, it is preferably SI-80, SI-100, and SI-110.
(G)熱敏性酸發生劑的用量,相對於100重量份(A)成分,較佳為20重量份以下,更佳為10重量份以下,特佳為0.1-5重量份。如果超過20重量份,則會出現析出並使膜表面發生皸裂的情況。The amount of the heat-sensitive acid generator (G) is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, even more preferably 0.1 to 5 parts by weight per 100 parts by weight of the component (A). If it exceeds 20 parts by weight, precipitation may occur and the film surface may be cleaved.
本發明的樹脂組成物可以通過將上述各成分較佳均一地溶解或者分散於適當的溶劑中而調製。作為所使用的溶劑,較佳使用能夠溶解或分散組成物的各成分,並不會與各成分反應的溶劑。The resin composition of the present invention can be prepared by preferably dissolving or dispersing the above components in a suitable solvent. As the solvent to be used, a solvent which can dissolve or disperse each component of the composition and does not react with each component is preferably used.
作為這種溶劑,可以列舉醇類、醚類、乙二醇醚類、乙二醇烷基醚乙酸酯類、二甘醇單烷基醚類、二甘醇二烷基醚類、丙二醇單烷基醚類、丙二醇烷基醚乙酸酯類、丙二醇烷基醚丙酸酯類、芳香族烴類、酮類、酯類等。Examples of such a solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, and propylene glycol monoalkanes. Alkyl ethers, propylene glycol alkyl ether acetates, propylene glycol alkyl ether propionates, aromatic hydrocarbons, ketones, esters, and the like.
作為它們的具體例子,例如,醇類可以列舉甲醇、乙醇、苄基醇等;醚類可以列舉四氫呋喃等;乙二醇醚類可以列舉乙二醇單甲醚、乙二醇單***等;乙二醇烷基醚乙酸酯類可以列舉甲基溶纖劑乙酸酯、乙基溶纖劑乙酸酯、乙二醇單丁基醚乙酸酯、二甘醇單***乙酸酯等;二甘醇單烷基醚類可以列舉二甘醇單甲醚、二甘醇單***等;二甘醇二烷基醚類可以列舉二甘醇二甲基醚、二甘醇二乙基醚、二甘醇乙基甲基醚等;丙二醇單烷基醚類可以列舉丙二醇甲醚、丙二醇***、丙二醇丙醚、丙二醇丁醚等;丙二醇烷基醚乙酸酯類可以列舉丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯、丙二醇丙基醚乙酸酯、丙二醇丁基醚乙酸酯等;丙二醇烷基醚丙酸酯類可以列舉丙二醇甲醚丙酸酯、丙二醇***乙酸酯、丙二醇丙醚乙酸酯、丙二醇丁醚乙酸酯等;作為芳香族烴類,可以列舉甲苯、二甲苯等;作為酮類,可以列舉甲基乙基酮、環己酮、4-羥基-4-甲基-2-戊酮、甲基異戊酮等;作為酯類,可以列舉乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、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、羥基乙酸甲酯、羥基乙酸乙酯、羥基乙酸丁酯、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、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、乙氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、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、3-丁氧基丙酸丁酯等。Specific examples of the alcohols include methanol, ethanol, and benzyl alcohol; examples of the ethers include tetrahydrofuran; and examples of the glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Examples of the diol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and the like; Examples of the glycol monoalkyl ethers include diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; and diethylene glycol dialkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and Examples of the propylene glycol monomethyl ethers include propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, and propylene glycol butyl ether; and propylene glycol alkyl ether acetates include propylene glycol methyl ether acetate. Propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc.; propylene glycol alkyl ether propionate can be exemplified by propylene glycol methyl ether propionate, propylene glycol diethyl ether acetate, propylene glycol Ether acetate, propylene glycol butyl ether acetate, etc.; as aromatic Examples thereof include toluene and xylene; and examples of the ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and methyl isoamyl ketone; and esters. Examples thereof include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and 2-hydroxy-2-methylpropionic acid. Ethyl ester, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, Propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, C Propyl oxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2- Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-B Ethyl oxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butyl Propyl oxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methyl Butyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-propane Methyl oxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butyl Ethyl oxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like.
其中,較佳為醇類、二甘醇類、丙二醇烷基乙酸酯類、乙二醇烷基醚乙酸酯類、二甘醇二烷基醚類,特佳為苄基醇、二甘醇乙基甲基醚、丙二醇甲醚乙酸酯、丙二醇***乙酸酯、二甘醇二甲醚、乙二醇單丁醚乙酸酯、二甘醇單***乙酸酯、二甘醇二***。Among them, preferred are alcohols, diethylene glycols, propylene glycol alkyl acetates, ethylene glycol alkyl ether acetates, diethylene glycol dialkyl ethers, particularly preferably benzyl alcohol, diethylene glycol Methyl ether, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate, diglyme, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether.
溶劑的用量為使本發明組成物的全部固體成分(從含溶劑的組成物的總量中除去溶劑的量而得到的量)的含量較佳為1-50重量%,更佳為5-40重量%的範圍。The amount of the solvent used is preferably from 1 to 50% by weight, more preferably from 5 to 40%, based on the total solid content of the composition of the present invention (the amount obtained by removing the solvent from the total amount of the solvent-containing composition). The range of % by weight.
另外,還可以與上述溶劑同時聯用高沸點溶劑。作為可在此聯用的高沸點溶劑,可以列舉例如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-甲基吡咯烷酮、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、安息香酸乙酯、草酸二乙酯、馬來酸二乙酯、γ-丁內酯、碳酸乙烯酯、碳酸丙烯酯、苯基溶纖劑乙酸酯等。Further, a high boiling point solvent may be used in combination with the above solvent. As the high boiling point solvent which can be used in combination here, for example, N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N can be mentioned. , N-dimethylacetamide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.
聯用高沸點溶劑時的使用量,相對於全部溶劑的量較佳為90重量%以下,更佳為80重量%以下。The amount of use in combination with a high boiling point solvent is preferably 90% by weight or less, and more preferably 80% by weight or less based on the total amount of the solvent.
如上調製的組成物還可以在用孔徑為0.2-3.0μm,較佳孔徑為0.2-0.5μm左右的微孔濾器等過濾後供給使用。The composition prepared as above may be used after being filtered by a micropore filter having a pore diameter of 0.2 to 3.0 μm, preferably a pore diameter of about 0.2 to 0.5 μm.
接著,對用本發明樹脂組成物形成彩色濾光片保護膜的方法進行說明。Next, a method of forming a color filter protective film using the resin composition of the present invention will be described.
即,將本發明的樹脂組成物溶液塗敷於基板表面,通過預烘焙除去溶劑形成塗膜後,進行加熱處理,可形成目標彩色濾光片保護膜。That is, the resin composition solution of the present invention is applied onto the surface of the substrate, and the solvent is removed by prebaking to form a coating film, followed by heat treatment to form a target color filter protective film.
作為可作為上述基板使用的,可以使用例如玻璃、石英、矽、樹脂等基板。作為樹脂,可以列舉例如聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚醚碸、聚碳酸酯、聚醯亞胺以及環狀烯烴的開環聚合物及其氫化產物等樹脂。As the substrate which can be used as the above substrate, for example, a substrate such as glass, quartz, rhodium or resin can be used. Examples of the resin include a ring-opening polymer of polyethylene terephthalate, polybutylene terephthalate, polyether fluorene, polycarbonate, polyimine, and cyclic olefin, and hydrogenated products thereof. Resin.
作為塗敷方法,可以採用噴塗法、輥塗法、旋塗法、棒塗法、噴墨法等適當的方法,特別適合採用旋塗機、非旋轉塗敷機、縫模塗敷機進行塗敷。As the coating method, a suitable method such as a spray coating method, a roll coating method, a spin coating method, a bar coating method, or an inkjet method can be employed, and it is particularly suitable for coating by a spin coater, a non-rotating coater, or a slit die coater. apply.
作為上述預烘焙的條件,根據各成分的種類和配合比率等而不同,通常,可以採用在70-90℃下1-15分鐘左右的條件。作為塗膜的厚度,較佳可為0.15-8.5μm,更佳為0.15-6.5μm,進一步較佳為0.15-4.5μm。另外,這裏所述的塗膜厚度,應當理解為除去溶劑後的厚度。The conditions for the prebaking described above vary depending on the type of each component, the blending ratio, and the like, and usually, a condition of about 1 to 15 minutes at 70 to 90 ° C can be employed. The thickness of the coating film is preferably from 0.15 to 8.5 μm, more preferably from 0.15 to 6.5 μm, still more preferably from 0.15 to 4.5 μm. Further, the thickness of the coating film described herein is understood to be the thickness after removal of the solvent.
塗膜形成後的加熱處理可以在加熱板或者潔淨烤箱等適當的加熱裝置中進行。處理溫度較佳為150-250℃左右,加熱時間,當使用加熱板時,可以採用5-30分鐘的處理時間,當使用烤箱時,可以採用30-90分鐘。The heat treatment after the formation of the coating film can be carried out in a suitable heating device such as a hot plate or a clean oven. The treatment temperature is preferably about 150-250 ° C, the heating time, when using the heating plate, the treatment time can be 5-30 minutes, and when the oven is used, 30-90 minutes can be used.
此外,當樹脂組成物中使用射線敏感性酸發生劑時,可以在將該射線敏感性樹脂組成物塗敷於基板上,通過預烘焙除去溶劑形成塗膜之後,進行射線照射處理(曝光處理),再通過進行加熱處理,形成目標保護膜。Further, when a radiation-sensitive acid generator is used in the resin composition, the radiation-sensitive resin composition may be applied onto a substrate, and the solvent may be removed by prebaking to form a coating film, followed by irradiation treatment (exposure treatment). Then, heat treatment is performed to form a target protective film.
本發明中所用的通過照射射線產生酸的射線敏感性酸發生劑,可以通過由曝光產生的酸的作用來促進反應。作為這樣的酸發生劑,可以列舉(1)鎓鹽、(2)含鹵素化合物、(3)重氮酮化合物、(4)碸化合物、(5)磺酸化合物等。作為這些酸發生劑的例子,可以列舉以下的物質。The radiation-sensitive acid generator which generates an acid by irradiation with radiation used in the present invention can promote the reaction by the action of an acid generated by exposure. Examples of such an acid generator include (1) a phosphonium salt, (2) a halogen-containing compound, (3) a diazoketone compound, (4) an anthracene compound, and (5) a sulfonic acid compound. Examples of such acid generators include the following.
(1)作為鎓鹽,例如,可以列舉碘鎓鹽、鋶鹽、鏻鹽、重氮鎓鹽、吡啶鎓鹽等。作為較佳的鎓鹽的具體例子,可以列舉二苯基碘鎓三氟甲磺酸鹽、二苯基碘鎓芘磺酸鹽、二苯基碘鎓十二烷基苯磺酸鹽、二(4-第三丁基苯基)碘鎓三氟甲磺酸鹽、二(4-第三丁基苯基)碘鎓十二烷基苯磺酸鹽、二(4-第三丁基苯基)碘鎓萘磺酸鹽、二(4-第三丁基苯基)碘鎓六氟銻酸鹽、三苯基鋶三氟甲磺酸鹽、三苯基鋶六氟銻酸鹽、三苯基鋶萘磺酸鹽、(羥基苯基)苯甲基鋶甲苯磺酸鹽、1-(萘基乙醯甲基)噻吩鎓三氟甲磺酸鹽、環己基甲基(2-氧代環己基)鋶三氟甲磺酸鹽、二環己基(2-氧代環己基)鋶三氟甲磺酸鹽、二甲基(2-氧代環己基)鋶三氟甲磺酸鹽、二甲基(4-羥基萘基)鋶三氟甲磺酸鹽、二甲基(4-羥基萘基)鋶甲苯磺酸鹽、二甲基(4-羥基萘基)鋶十二烷基苯磺酸鹽、二甲基(4-羥基萘基)鋶萘磺酸鹽、二苯基碘鎓六氟銻酸鹽、三苯基鋶樟腦磺酸鹽、(4-羥基苯基)苄基甲基鋶甲苯磺酸鹽等。(1) Examples of the onium salt include an iodonium salt, a phosphonium salt, a phosphonium salt, a diazonium salt, a pyridinium salt, and the like. Specific examples of the preferred phosphonium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodoniumsulfonate, diphenyliodonium dodecylbenzenesulfonate, and 4-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium dodecylbenzenesulfonate, bis(4-tert-butylphenyl) Iodine naphthalenesulfonate, bis(4-t-butylphenyl)iodonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenyl Base naphthalene sulfonate, (hydroxyphenyl)benzyl indolyl sulfonate, 1-(naphthylethylidenemethyl)thiophene trifluoromethanesulfonate, cyclohexylmethyl (2-oxo ring) Hexyl)trifluoromethanesulfonate, dicyclohexyl(2-oxocyclohexyl)phosphonium triflate, dimethyl(2-oxocyclohexyl)phosphonium triflate, dimethyl (4-hydroxynaphthyl) anthracene trifluoromethanesulfonate, dimethyl (4-hydroxynaphthyl) anthracene tosylate, dimethyl (4-hydroxynaphthyl) anthracene dodecylbenzenesulfonic acid Salt, dimethyl (4-hydroxynaphthyl) anthracene naphthalene sulfonate, diphenyl iodonium hexafluoroantimonate, triphenyl camphorsulfonate, (4- Hydroxyphenyl)benzylmethylindole tosylate or the like.
(2)作為含鹵素的化合物,例如,可以列舉含鹵代烷基的烴化合物、含鹵代烷基雜環化合物等。作為較佳的含鹵素的化合物的具體例子,可以列舉苯基-二(三氟甲基)-s-三、甲氧基苯基-二(三氟甲基)-s-三、萘基-二(三氟甲基)-s-三等(三氟甲基)-s-三衍生物,或者1,1-二(4-氯苯基)-2,2,2-三氟乙烷等。(2) The halogen-containing compound may, for example, be a halogenated alkyl group-containing hydrocarbon compound or a halogenated alkyl group-containing heterocyclic compound. Specific examples of preferred halogen-containing compounds include phenyl-bis(trifluoromethyl)-s-three. Methoxyphenyl-bis(trifluoromethyl)-s-three Naphthyl-bis(trifluoromethyl)-s-three Equivalent (trifluoromethyl)-s-three a derivative, or 1,1-bis(4-chlorophenyl)-2,2,2-trifluoroethane or the like.
(3)作為重氮酮化合物,例如,可以列舉1,3-二酮-2-重氮化合物、重氮苯醌化合物、重氮萘醌化合物等。作為較佳的重氮酮化合物的具體例子,可以列舉1,2-萘醌重氮基-4-磺醯氯、1,2-萘醌重氮基-5-磺醯氯、2,3,4,4’-四氫二苯酮的1,2-萘醌重氮基-4-磺酸酯或1,2-萘醌重氮基-5-磺酸酯、1,1,1-三(4-羥基苯基)乙烷的1,2-萘醌重氮基-4-磺酸酯或1,2-萘醌重氮基-5-磺酸酯等。(3) Examples of the diazoketone compound include a 1,3-diketone-2-diazo compound, a diazonium quinone compound, and a diazonaphthoquinone compound. Specific examples of the preferred diazoketone compound include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazo-5-sulfonyl chloride, 2,3. 1,2-naphthoquinonediazo-4-sulfonate of 4,4'-tetrahydrobenzophenone or 1,2-naphthoquinonediazo-5-sulfonate, 1,1,1-three 1,2-naphthoquinonediazo-4-sulfonate or 1,2-naphthoquinonediazo-5-sulfonate of (4-hydroxyphenyl)ethane.
(4)作為碸化合物,例如,可以列舉β-酮碸、β-磺醯基碸,或者這些化合物的α-重氮化合物等。作為較佳的碸化合物的具體例子,可以列舉4-三(苯甲醯甲基)碸、基苯甲醯甲基碸、二(苯基磺醯基)甲烷等。(4) Examples of the ruthenium compound include β-ketooxime, β-sulfonylhydrazine, or an α-diazonium compound of these compounds. Specific examples of the preferred ruthenium compound include 4-tris(benzhydrylmethyl)fluorene. Benzobenzidine methyl hydrazine, bis(phenylsulfonyl) methane, and the like.
(5)作為磺酸化合物,例如,可以列舉烷基磺酸酯、烷基磺醯亞胺、鹵代烷基磺酸酯、芳基磺酸酯、亞胺磺酸酯等。作為較佳的磺酸化合物的具體例子,可以列舉苯偶姻甲苯磺酸酯、焦沒食子酸的三(三氟甲磺酸酯)、硝基苄基-9,10-二乙氧基蒽-2-磺酸酯、三氟甲磺醯雙環[2.2.1]庚烷-5-烯-2,3-二碳化二亞胺、N-羥基琥珀醯亞胺三氟甲磺酸酯、1,8-萘二羧醯亞胺三氟甲磺酸酯等。(5) Examples of the sulfonic acid compound include an alkylsulfonate, an alkylsulfonimide, a halogenated alkylsulfonate, an arylsulfonate, and an imidesulfonate. Specific examples of preferred sulfonic acid compounds include benzoin tosylate, tris(trifluoromethanesulfonate) of pyroic acid, and nitrobenzyl-9,10-diethoxy. Indole-2-sulfonate, trifluoromethanesulfonium bicyclo[2.2.1]heptane-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide triflate, 1,8-naphthalene dicarboxy quinone imine trifluoromethanesulfonate or the like.
這些酸發生劑中,特佳為二苯基碘鎓三氟甲磺酸鹽、二(4-第三丁基苯基)碘鎓三氟甲磺酸鹽、三苯基鋶三氟甲磺酸鹽、環己基甲基(2-氧代環己基)鋶三氟甲磺酸鹽、二環己基(2-氧代環己基)鋶三氟甲磺酸鹽、二甲基(2-氧代環己基)鋶三氟甲磺酸鹽、1-(萘基乙醯甲基)噻吩鎓三氟甲磺酸鹽、4-羥基萘基二甲基鋶三氟甲磺酸鹽、二甲基(4-羥基萘基)鋶三氟甲磺酸鹽、三氟甲磺醯雙環[2.2.1]庚烷-5-烯-2,3-二碳化二亞胺、N-羥基琥珀醯亞胺三氟甲磺酸酯、1,8-萘二羧醯亞胺三氟甲磺酸酯等。Among these acid generators, particularly preferred are diphenyliodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, and triphenylsulfonium trifluoromethanesulfonic acid. Salt, cyclohexylmethyl (2-oxocyclohexyl)phosphonium triflate, dicyclohexyl (2-oxocyclohexyl)phosphonium triflate, dimethyl (2-oxo ring) Hexyl)trifluoromethanesulfonate, 1-(naphthylethylidenemethyl)thiophene trifluoromethanesulfonate, 4-hydroxynaphthyldimethylsulfonium trifluoromethanesulfonate, dimethyl (4 -hydroxynaphthyl)indole trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo[2.2.1]heptane-5-ene-2,3-dicarbodiimide, N-hydroxysuccinimide trifluoride Methanesulfonate, 1,8-naphthalenedicarboxyimine triflate, and the like.
在本發明中,酸發生劑可以單獨或者2種以上混合使用。In the present invention, the acid generators may be used singly or in combination of two or more kinds.
酸發生劑的用量,相對於100重量份(A)共聚物,通常為0.1-10重量份,較佳為0.5-7重量份。這時,當酸發生劑的用量不足0.1重量份時,則不能獲得充分的反應促進效果,另一方面,如果超過10重量份,則會出現透明性下降的情況。The amount of the acid generator is usually 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight, per 100 parts by weight of the (A) copolymer. In this case, when the amount of the acid generator is less than 0.1 part by weight, a sufficient reaction promoting effect cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the transparency may be lowered.
作為上述射線照射處理中所用的射線,可以列舉可見光線、紫外線、遠紫外線、電子束、X射線等,較佳含190-450nm波長的光的紫外線。Examples of the radiation used in the radiation irradiation treatment include visible light rays, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays, and ultraviolet rays having a wavelength of 190 to 450 nm are preferable.
作為曝光量,通常為100-20,000 J/m2 ,較佳為150-10,000 J/m2 。The exposure amount is usually from 100 to 20,000 J/m 2 , preferably from 150 to 10,000 J/m 2 .
照射射線後,進一步進行加熱處理。這時的加熱溫度較佳為150-250℃左右,作為加熱裝置,可以使用加熱板、潔淨烤箱等適當的裝置。加熱時間,當使用加熱板時可以採用5-30分鐘的處理時間,當使用烤箱時,可以採用15-90分鐘。After the irradiation of the radiation, further heat treatment is performed. The heating temperature at this time is preferably about 150 to 250 ° C, and as the heating means, a suitable device such as a hot plate or a clean oven can be used. Heating time, 5-30 minutes of processing time can be used when using the hot plate, and 15-90 minutes can be used when using the oven.
如此形成的保護膜,其膜厚較佳為0.1-8μm,更佳為0.1-6μm,進一步較佳為0.1-4μm。另外,本發明的保護膜形成於具有彩色濾光片梯層的基板上時,上述膜厚應當理解為自彩色濾光片最上部的厚度。The protective film thus formed preferably has a film thickness of from 0.1 to 8 μm, more preferably from 0.1 to 6 μm, still more preferably from 0.1 to 4 μm. Further, when the protective film of the present invention is formed on a substrate having a color filter step layer, the above film thickness is understood to be the thickness from the uppermost portion of the color filter.
從下述實施例可以看出,本發明的保護膜適合用作為滿足密合性、表面硬度、透明性、耐熱性、耐光性、耐溶劑性等的同時,即使在受熱狀態下載荷也不會凹陷,並且對襯底基板上形成的彩色濾光片的梯層的平坦化性能優良的裝置用保護膜。As can be seen from the following examples, the protective film of the present invention is suitably used for satisfying adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, etc., and does not load even under heat. A protective film for a device which is recessed and which has excellent planarization performance for a ladder layer of a color filter formed on a base substrate.
特別地,由於會遇到在面板製造步驟中遭受超過250℃的加熱的情況,本發明的保護膜具有在這種情況下也能充分耐受的耐熱性,因而在270℃下也能保證具有足夠的尺寸穩定性。In particular, since it is encountered in the case where heating of more than 250 ° C is encountered in the panel manufacturing step, the protective film of the present invention has heat resistance which is sufficiently tolerated in this case, and thus is ensured at 270 ° C as well. Sufficient dimensional stability.
本發明的樹脂組成物,通過在基膜、較佳在可透性基膜上層壓本發明的上述熱敏性樹脂組成物的感熱層,可以製得熱敏性幹膜。In the resin composition of the present invention, a heat-sensitive dry film can be obtained by laminating the heat-sensitive layer of the heat-sensitive resin composition of the present invention on a base film, preferably on a permeable base film.
熱敏性幹膜可以通過將熱敏性樹脂組成物較佳以液態組成物的形式塗敷於基膜上後進行乾燥以層壓感熱層而形成。The heat-sensitive dry film can be formed by applying a heat-sensitive resin composition to a base film as a liquid composition, followed by drying to laminate a heat-sensitive layer.
作為熱敏性幹膜的基膜,例如,可以使用聚對苯二甲酸乙二酯(PET)膜、聚乙烯、聚丙烯、聚碳酸酯、聚氯乙烯等合成樹脂膜。As the base film of the heat-sensitive dry film, for example, a polyethylene terephthalate (PET) film, a synthetic resin film such as polyethylene, polypropylene, polycarbonate, or polyvinyl chloride can be used.
基膜的厚度為15-125μm較合適。The thickness of the base film is preferably from 15 to 125 μm.
作為在基膜上層壓感熱層時的塗敷方法,對其沒有特別的限製,例如,可以採用敷料器塗敷法、棒塗法、輥塗法、簾式淋塗法等適當的方法。The coating method for laminating the heat-sensitive layer on the base film is not particularly limited, and for example, an appropriate method such as an applicator coating method, a bar coating method, a roll coating method, or a curtain coating method can be employed.
所得感熱層的厚度較佳為1-30μm左右。The thickness of the obtained heat sensitive layer is preferably about 1 to 30 μm.
此外,熱敏性幹膜在未使用時可以在其感熱層上進一步層壓覆膜而進行保存。Further, the heat-sensitive dry film can be further deposited by laminating a film on the heat-sensitive layer when it is not used.
該覆膜是為了在未使用時能夠穩定地保護感熱層,在使用時則被除去。因此,覆膜必須具備適度的脫模性,使其在未使用時不會剝落,而在使用時則能夠容易地被剝離。作為滿足這種條件的覆膜,例如,可以使用在PET膜、聚丙烯膜、聚乙烯膜、聚氯乙烯等合成樹脂膜的表面上塗敷或燒結聚矽氧烷類脫模劑的薄膜。The film is intended to stably protect the heat sensitive layer when not in use, and is removed during use. Therefore, the film must have a moderate mold release property so that it does not peel off when not in use, and can be easily peeled off during use. As the film which satisfies such a condition, for example, a film in which a polysiloxane-based release agent is applied or sintered on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film or a polyvinyl chloride can be used.
覆膜的厚度通常為25μm左右即足夠。It is sufficient that the thickness of the film is usually about 25 μm.
當使用幹膜法時,在層壓了覆膜的情況下,將其剝離後,使其感熱層對著基板一側,通過常壓熱輥壓著法、真空熱輥壓著法、真空熱壓機壓著法等適當的壓著方法,在施加適當的熱和壓力下,將熱敏性幹膜壓著在基板上,將感熱層轉印到基板表面,從而在基板上形成熱敏性樹脂組成物的覆膜。When the dry film method is used, when the film is laminated, the film is peeled off, and the heat sensitive layer is placed on the substrate side by a normal pressure hot roll pressing method, a vacuum hot roll pressing method, and a vacuum heat. a heat-sensitive dry film is pressed against the substrate under appropriate pressure and pressure by a suitable pressing method, and the heat-sensitive layer is transferred onto the surface of the substrate to form a heat-sensitive resin composition on the substrate. Laminating.
這樣得到的熱敏性幹膜,可應用於彩色濾光片用保護膜等光學器件用保護膜的用途。The heat-sensitive dry film thus obtained can be applied to a protective film for an optical device such as a protective film for a color filter.
以下例示合成例、實施例對本發明進行更具體的說明,但是本發明不局限於以下的實施例。The present invention will be more specifically described below by way of Synthesis Examples and Examples, but the present invention is not limited to the following examples.
在裝有冷卻管、攪拌機的燒瓶中,加入5重量份2,2’-偶氮二異丁腈、200重量份丙二醇單甲醚乙酸酯。接著加入50重量份甲基丙烯酸縮水甘油酯、50重量份苯乙烯,用氮氣置換後,開始緩慢攪拌。使溶液的溫度上升至70℃,保持該溫度5小時,得到含共聚物(A-1)的聚合物溶液。所得聚合物溶液的固體含量濃度為32.9重量%。In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Next, 50 parts by weight of glycidyl methacrylate and 50 parts by weight of styrene were added, and after replacing with nitrogen, stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). The solid content concentration of the obtained polymer solution was 32.9% by weight.
在裝有冷卻管、攪拌機的燒瓶中,加入5重量份2,2’-偶氮二異丁腈、200重量份丙二醇單甲醚乙酸酯。接着加入50重量份(3-乙基-3-氧乙基)甲基甲基丙烯酸脂、50重量份苯乙烯,用氮气置换后,始缓慢搅拌。使溶液的溫度上升至70℃,保持該溫度5小時,得到含共聚物(A-2)的聚合物溶液。所得聚合物溶液的固體含量濃度為33.2重量%。In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Next, 50 parts by weight of (3-ethyl-3-oxoethyl)methyl methacrylate and 50 parts by weight of styrene were added, and after replacing with nitrogen, Start stirring slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-2). The solid content concentration of the obtained polymer solution was 33.2% by weight.
在裝有冷卻管、攪拌機的燒瓶中,加入5重量份2,2’-偶氮二(2,4-二甲基戊腈)、200重量份丙二醇單甲醚乙酸酯。接著加入40重量份甲基丙烯酸縮水甘油酯、40重量份甲基丙烯酸、10重量份苯乙烯、以及10重量份甲基丙烯酸三環[5.2.1.02 , 6 ]癸烷-8-基酯,用氮氣置換後,開始緩慢攪拌。使溶液的溫度上升至70℃,保持該溫度5小時,得到含共聚物(A-3)的聚合物溶液。所得聚合物溶液的固體含量濃度為33.2重量%。In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Next, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of methacrylic acid, 10 parts by weight of styrene, and 10 parts by weight of tricyclo[5.2.1.0 2 , 6 ]decane-8-yl methacrylate were added. After replacing with nitrogen, slow stirring was started. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-3). The solid content concentration of the obtained polymer solution was 33.2% by weight.
在裝有冷卻管、攪拌機的燒瓶中,加入5重量份2,2’-偶氮二(2,4-二甲基戊腈)、200重量份丙二醇單甲醚乙酸酯。接著加入40重量份甲基丙烯酸縮水甘油酯、40重量份甲基丙烯酸1-乙基環己烷基酯、10重量份苯乙烯、以及10重量份N-環己基馬來醯亞胺,用氮氣置換後,開始緩慢攪拌。使溶液的溫度上升至70℃,保持該溫度5小時,得到含共聚物(A-4)的聚合物溶液。所得聚合物溶液的固體含量濃度為33.2重量%。In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Next, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of 1-ethylcyclohexyl methacrylate, 10 parts by weight of styrene, and 10 parts by weight of N-cyclohexylmaleimide, with nitrogen, were added. After the replacement, slow stirring was started. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-4). The solid content concentration of the obtained polymer solution was 33.2% by weight.
在裝有冷卻管、攪拌機的燒瓶中,加入5重量份2,2’-偶氮二(2,4-二甲基戊腈)、200重量份丙二醇單甲醚乙酸酯。接著加入40重量份甲基丙烯酸縮水甘油酯、20重量份苯乙烯、以及20重量份N-環己基馬來醯亞胺、20重量份2-甲基-2-丙酸四氫-2H-吡喃-2-基-酯,用氮氣置換後,開始緩慢攪拌。使溶液的溫度上升至70℃,保持該溫度5小時,得到含共聚物(A-5)的聚合物溶液。所得聚合物溶液的固體含量濃度為29.9重量%。In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were added. Next, 40 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, and 20 parts by weight of N-cyclohexylmaleimide, 20 parts by weight of 2-methyl-2-propionic acid tetrahydro-2H-pyrene were added. The butan-2-yl-ester was slowly stirred after replacement with nitrogen. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-5). The resulting polymer solution had a solid content concentration of 29.9% by weight.
加入含有上述合成例1中得到的共聚物(A-1)的溶液(相當於含100重量份共聚物(A-1)(固體成分)的量)、5.0重量份(B)三正十八烷基磷酸酯和0.1重量份(C)N-亞硝基苯基羥基胺Al鹽、10.0重量份(D)雙酚A酚醛型環氧樹脂、5.0重量份(E)γ-環氧丙氧基丙基三甲氧基矽烷、0.1重量份(F)表面活性劑SH-28PA(由Toray Dowcorning Silicone(株)生產),再加入丙二醇單甲醚乙酸酯,使固體含量濃度為20重量%,然後用孔徑為0.5μm的微孔濾器過濾,調製成樹脂組合物。A solution containing the copolymer (A-1) obtained in the above Synthesis Example 1 (corresponding to an amount containing 100 parts by weight of the copolymer (A-1) (solid content)), 5.0 parts by weight (B) of three positive 18 Alkyl phosphate and 0.1 parts by weight of (C) N-nitrosophenylhydroxylamine Al salt, 10.0 parts by weight of (D) bisphenol A phenolic epoxy resin, 5.0 parts by weight of (E) gamma-glycidoxy Propyl trimethoxy decane, 0.1 part by weight of (F) surfactant SH-28PA (manufactured by Toray Dow Corning Silicone Co., Ltd.), and then propylene glycol monomethyl ether acetate to have a solid content concentration of 20% by weight. Then, it was filtered with a micropore filter having a pore size of 0.5 μm to prepare a resin composition.
用旋塗機將上述組成物塗敷於SiO2 浸漬玻璃基板上後,在加熱板上於80℃預烘焙5分鐘,形成塗膜,進一步在烤箱中於230℃下加熱處理60分鐘,得到膜厚為2.0μm的保護膜。The composition was applied onto a SiO 2 -impregnated glass substrate by a spin coater, and then prebaked on a hot plate at 80 ° C for 5 minutes to form a coating film, which was further heat-treated in an oven at 230 ° C for 60 minutes to obtain a film. A protective film having a thickness of 2.0 μm.
(1)透明性的評價採用分光光度計(150-20型雙光束(日立製作所(株)製造)),對具有如上形成的保護膜的基板測定400-800nm的透過率。400-800nm的透過率的最小值列於表1。當該值為95%以上時,可稱之為保護膜的透明性良好。(1) Evaluation of Transparency A substrate having a protective film formed as above was measured for a transmittance of 400 to 800 nm by using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)). The minimum values of transmittance at 400-800 nm are listed in Table 1. When the value is 95% or more, the transparency of the protective film can be referred to as good.
(2)耐熱尺寸穩定性的評價將具有如上形成的保護膜的基板在烘箱中於250℃下加熱1小時,測定加熱前後的膜厚。按下述公式算出的耐熱尺寸穩定性列於表1。當該值為95%以上時,可稱之為耐熱尺寸穩定性良好。(2) Evaluation of heat-resistant dimensional stability The substrate having the protective film formed as above was heated in an oven at 250 ° C for 1 hour, and the film thickness before and after heating was measured. The heat-resistant dimensional stability calculated according to the following formula is shown in Table 1. When the value is 95% or more, it can be said that the heat resistance dimensional stability is good.
耐熱尺寸穩定性=[(加熱後的膜厚)/(加熱前的膜厚)]×100(%)Heat resistant dimensional stability = [(film thickness after heating) / (film thickness before heating)] × 100 (%)
(3)耐熱變色性評價將具有如上形成的保護膜的基板在烘箱中於250℃下加熱1小時,與上述(1)同樣地測定加熱前後的透明性。按下述公式算出的耐熱變色性列於表1。當該值為5%以下時,表示耐熱變色性良好。(3) Evaluation of heat-resistant discoloration The substrate having the protective film formed as described above was heated in an oven at 250 ° C for 1 hour, and the transparency before and after heating was measured in the same manner as in the above (1). The heat discoloration property calculated by the following formula is shown in Table 1. When the value is 5% or less, it means that the heat discoloration resistance is good.
耐熱變色性=加熱前的透光率-加熱後的透光率(%)Heat-resistant discoloration = light transmittance before heating - light transmittance after heating (%)
(4)表面硬度的測定將具有如上形成的保護膜的基板通過JIS K-5400-1990的8.4.1鉛筆劃痕硬度試驗測定保護膜的表面硬度。該值列於表1。當該值為4H或更硬時,表示表面硬度良好。(4) Measurement of surface hardness The surface of the protective film was measured by the 8.4.1 pencil scratch hardness test of JIS K-5400-1990 on the substrate having the protective film formed as above. This value is listed in Table 1. When the value is 4H or harder, it means that the surface hardness is good.
(5)動態微小硬度的測定對具有如上形成的保護膜的基板採用島津動態微小硬度計DUH-201((株)島津製作所製造),通過棱角為115°的三角壓頭(Herocobitch型)的壓入試驗,在載荷:0.1gf、速度:0.0145 gf/sec、保持時間:5sec、溫度為23℃以及140℃的測定條件下測定保護膜的動態微小硬度。結果列於表1。(5) Determination of dynamic micro hardness Shimadzu Dynamic microhardness meter DUH-201 ((Shimadzu Corporation)) manufactured on a substrate having the protective film formed as described above by edges of 115 ° triangular indenter (Herocobitch type) pressure Into the test, the dynamic microhardness of the protective film was measured under the measurement conditions of a load: 0.1 gf, a speed: 0.0145 gf/sec, a holding time: 5 sec, a temperature of 23 ° C, and 140 ° C. The results are shown in Table 1.
(6)密合性評價對具有如上形成的保護膜的基板進行高壓鍋試驗(120℃,濕度100%,4小時)後,通過JIS K-5400-1990的8.5.3黏著性方格帶法評價保護膜的密合性(對SiO2 的密合性)。在100方格中,殘留方格的數目列於表1。(6) Adhesion evaluation After the pressure cooker test (120 ° C, humidity 100%, 4 hours) on the substrate having the protective film formed as above, it was evaluated by the 8.5.3 adhesive square method of JIS K-5400-1990. Adhesion of the protective film (adhesion to SiO 2 ). In the 100 squares, the number of residual squares is listed in Table 1.
並且,作為對Cr的密合性的評價,用Cr基板替換SiO2 浸漬玻璃基板,其他與上述同樣地操作,形成膜厚為2.0μm的保護膜,通過上述方格帶法同樣地進行評價。結果列於表1。In addition, the SiO 2 -impregnated glass substrate was replaced with a Cr substrate, and a protective film having a film thickness of 2.0 μm was formed in the same manner as described above, and evaluated by the above-described checker tape method. The results are shown in Table 1.
(7)平坦化性的評價用旋塗機在SiO2 浸漬玻璃基板上塗敷顏料系彩色光阻劑(商品名“JCR RED 689”、“JCR GREEN 706”、“CR 8200B”,以上由JSR(株)生產),在加熱板上於90℃下預烘焙150秒鐘,形成塗膜。然後,通過規定圖案的掩模,採用曝光機Canon PLA 501F(Canon(株)製造),應用ghi線(波長436nm、405nm、365nm的強度比=2.7:2.5:4.8)以由i線換算的2,000 J/m2 的曝光量進行照射,再用0.05%氫氧化鉀溶液進行顯影,在超純水中沖洗60秒鐘後,再在烤箱中於230℃下加熱處理30分鐘,形成紅、綠、和藍3色的條帶狀彩色濾光片(帶寬為100μm)。(7) Evaluation of flattening property A pigment-based color resist (trade name "JCR RED 689", "JCR GREEN 706", "CR 8200B") was coated on a SiO 2 -impregnated glass substrate by a spin coater, and the above was performed by JSR ( (produced), prebaked on a hot plate at 90 ° C for 150 seconds to form a coating film. Then, using a mask of a predetermined pattern, an exposure machine Canon PLA 501F (manufactured by Canon Co., Ltd.) was used, and a ghi line (intensity ratio of wavelength 436 nm, 405 nm, 365 nm = 2.7:2.5:4.8) was applied to 2,000 in terms of i-line conversion. The exposure amount of J/m 2 was irradiated, and then developed with a 0.05% potassium hydroxide solution, rinsed in ultrapure water for 60 seconds, and then heat treated in an oven at 230 ° C for 30 minutes to form red, green, and Striped color filter with blue and blue colors (bandwidth is 100μm).
用表面糙度計“α-Step”(商品名,Tencor社製造)測定該形成了濾色器的基板表面的凹凸,結果為1.0μm。其中,以測定長度為2,000μm、測定範圍為2,000μm見方,測定點數n=5的條件進行測定。即,測定方向為紅、綠、藍方向條帶線的短軸方向和紅.紅、綠.綠、藍.藍同一色條帶線的長軸方向這2個方向,各個方向上以n=5進行測定(合計n數為10)。The unevenness of the surface of the substrate on which the color filter was formed was measured by a surface roughness meter "α-Step" (trade name, manufactured by Tencor), and it was 1.0 μm. In addition, the measurement was performed under the condition that the measurement length was 2,000 μm, the measurement range was 2,000 μm square, and the number of measurement points was n=5. That is, the measurement direction is the short-axis direction and red of the strip line in the red, green, and blue directions. Red, green. Green blue. The two directions of the long axis direction of the blue color strip line are measured in n=5 in each direction (the total number of n is 10).
接著,用旋塗機塗敷上述保護膜形成用組成物後,在加熱板上於90℃預烘焙5分鐘,形成塗膜,再在烤箱中於230℃加熱處理60分鐘,形成從彩色濾光片上面的膜厚為2.0μm的保護膜。其中,這裏所述的膜厚,是指自基板上形成的彩色濾光片最上面的厚度。Next, the composition for forming a protective film was applied by a spin coater, and then prebaked on a hot plate at 90 ° C for 5 minutes to form a coating film, which was further heat-treated in an oven at 230 ° C for 60 minutes to form a color filter. A protective film having a film thickness of 2.0 μm on the sheet. Here, the film thickness as referred to herein means the thickness of the uppermost layer of the color filter formed on the substrate.
對如上形成的在濾色器上具有保護膜的基板,採用接觸式膜厚測定裝置“α-Step”(Tencor Japan(株)製造)測定保護膜的表面凹凸。其中,以測定長度為2,000μm、測定範圍為2,000μm見方,測定點數n=5的條件進行測定。即,測定方向為紅、綠、藍方向條帶線的短軸方向和紅.紅、綠.綠、藍.藍同一色條帶線的長軸方向這2個方向,各個方向上以n=5進行測定(合計n數為10)。各測定的最高部與最低部的高低差(nm)的10次平均值列於表1。當該值為300nm以下時,能稱之為平坦化性良好。The surface unevenness of the protective film was measured by the contact type film thickness measuring device "α-Step" (manufactured by Tencor Japan Co., Ltd.) on the substrate having the protective film formed on the color filter. In addition, the measurement was performed under the condition that the measurement length was 2,000 μm, the measurement range was 2,000 μm square, and the number of measurement points was n=5. That is, the measurement direction is the short-axis direction and red of the strip line in the red, green, and blue directions. Red, green. Green blue. The two directions of the long axis direction of the blue color strip line are measured in n=5 in each direction (the total number of n is 10). The ten average values of the height difference (nm) of the highest part and the lowest part of each measurement are shown in Table 1. When the value is 300 nm or less, it can be said that the planarization property is good.
(8)保存穩定性的評價採用東京計器(株)製造的ELD型黏度計測定實施例1中調製的保護膜形成用樹脂組成物的黏度。然後,將該組成物在25℃下靜置,同時每日測定25℃下的溶液黏度。以剛調製後的黏度為基準,求出增黏5%所需的天數,該天數列於表1。當該天數為20天以上時,能稱之為保存穩定性良好。(8) Evaluation of storage stability The viscosity of the resin composition for forming a protective film prepared in Example 1 was measured by an ELD-type viscometer manufactured by Tokyo Keiki Co., Ltd. Then, the composition was allowed to stand at 25 ° C while measuring the solution viscosity at 25 ° C daily. The number of days required to increase the viscosity by 5% was determined based on the viscosity immediately after the preparation, and the number of days is shown in Table 1. When the number of days is 20 days or more, it can be said that the storage stability is good.
組成物各成分的種類和用量如表1-表2所示,除了使用表1-表2所列的溶劑配成表1-表2所示的固體含量濃度以外,與實施例1同樣地調製樹脂組成物。The types and amounts of the components of the composition are as shown in Tables 1 to 2, and were prepared in the same manner as in Example 1 except that the solid content concentrations shown in Tables 1 to 2 were used in the solvents listed in Tables 1 to 2. Resin composition.
使用如上調製的保護膜形成用樹脂組成物,與實施例1同樣地形成保護膜,並進行評價。結果列於表1-表2。Using the resin composition for forming a protective film prepared as described above, a protective film was formed in the same manner as in Example 1 and evaluated. The results are shown in Tables 1 to 2.
組成物各成分的種類和用量如表2所示,除了使用表2所列的溶劑配成表2所示的固體含量濃度以外,與實施例1同樣地調製樹脂組成物。The type and amount of each component of the composition are as shown in Table 2. The resin composition was prepared in the same manner as in Example 1 except that the solid content concentration shown in Table 2 was prepared using the solvents listed in Table 2.
除了用縫模塗敷機代替旋塗機進行塗敷以外,與實施例1同樣地調製樹脂組成物,形成保護膜,並進行評價。結果列於表2。The resin composition was prepared in the same manner as in Example 1 except that the coating was applied by a slot coater instead of the spin coater to form a protective film. The results are shown in Table 2.
其中,在表1-表2中,(A)成分、(C)成分路易士酸金屬催化劑、(D)成分陽離子聚合性化合物、(E)黏結助劑、(F)界面活性劑和(S)溶劑的簡稱分別代表以下物質:(A)成分:ST=苯乙烯GMA=甲基丙烯酸缩水甘油酯O-MA=(3-乙基-3-氧乙基)甲基甲基丙烯酸脂CHMI=N-環己基馬來醯亞胺MA=甲基丙烯酸M-THP=甲基丙烯酸1-乙基環己烷基酯ECPMA=2-甲基-2-丙酸四氫-2H-吡喃-2-基酯C-1:氯化鋅C-2:N-亞硝基苯基羥基胺Al鹽D-1:雙酚A酚醛型環氧樹脂Japan Epoxy Resins(株)生產,商品名:EPIKOTE157S65)E-1:γ-環氧丙氧基丙基三甲氧基矽烷F-1:聚矽氧烷類表面活性劑Toray Dowcorning Silicone Dowcorning(株)生產,商品名:SH-28PA)S-1:丙二醇單甲醚乙酸酯In Tables 1 to 2, (A) component, (C) component Lewis acid metal catalyst, (D) component cationically polymerizable compound, (E) adhesion aid, (F) surfactant, and (S) The abbreviations of the solvents represent the following materials: (A) Component: ST = styrene GMA = glycidyl methacrylate O-MA = (3-ethyl-3-oxyethyl) methyl methacrylate CHMI = N-cyclohexylmaleimide MA=methacrylic acid M-THP=1-ethylcyclohexane methacrylate ECPMA=2-methyl-2-propionic acid tetrahydro-2H-pyran-2 -Base ester C-1: Zinc chloride C-2: N-nitrosophenylhydroxylamine Al salt D-1: Bisphenol A phenolic epoxy resin manufactured by Japan Epoxy Resins Co., Ltd., trade name: EPIKOTE 157S65 E-1: γ-glycidoxypropyltrimethoxydecane F-1: Polyoxane type surfactant Toray Dowcorning Silicone Dowcorning Co., Ltd., trade name: SH-28PA) S-1: propylene glycol Monomethyl ether acetate
本發明的樹脂組成物即使是表面平坦性低的基體,其也能夠在該基體上形成平坦性高的固化膜,而且,適合用作為透明性和表面硬度高、耐熱耐壓性、耐酸性、耐鹼性、耐濺射性等各種耐受性優良的液晶顯示元件(LCD)用彩色濾光片或電荷偶合元件(CCD)用彩色濾光片等光學器件用保護膜。The resin composition of the present invention can form a cured film having high flatness on the substrate even in a substrate having low surface flatness, and is suitable for use as transparency, high surface hardness, heat resistance and pressure resistance, and acid resistance. A protective film for an optical device such as a color filter for a liquid crystal display element (LCD) or a color filter for a charge coupled device (CCD), which is excellent in various resistances such as alkali resistance and sputter resistance.
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JP2005234158A JP4735818B2 (en) | 2005-08-12 | 2005-08-12 | Resin composition, method for forming color filter protective film, and color filter protective film |
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KR (1) | KR101274936B1 (en) |
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JP5083540B2 (en) * | 2007-03-20 | 2012-11-28 | Jsr株式会社 | Radiation-sensitive protective film forming resin composition, method for forming protective film from the composition, liquid crystal display element, and solid-state imaging element |
JP5354207B2 (en) * | 2007-03-26 | 2013-11-27 | Jsr株式会社 | Curable resin composition, protective film and method for forming protective film |
JP5120715B2 (en) * | 2008-09-10 | 2013-01-16 | 住友化学株式会社 | Polarizing plate, method for manufacturing the same, optical member, and liquid crystal display device |
JP5196078B2 (en) | 2010-08-03 | 2013-05-15 | Jsr株式会社 | Near-infrared cut filter and imaging apparatus including the same |
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TW357176B (en) * | 1995-03-07 | 1999-05-01 | Asahi Chemical Ind | Non-inflammable resin component |
EP0990679A2 (en) * | 1998-09-29 | 2000-04-05 | Idemitsu Petrochemical Co., Ltd. | Thermoplastic resin compositons and their injection moldings |
TW200504138A (en) * | 2003-06-23 | 2005-02-01 | Jsr Corp | Curable resin composition, protective film, and the method of formation |
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JPS6131425A (en) * | 1984-07-23 | 1986-02-13 | Suriibondo:Kk | Resin composition |
JP2682256B2 (en) * | 1990-04-10 | 1997-11-26 | 日本油脂株式会社 | Thermosetting composition |
JP3384800B2 (en) * | 1990-10-12 | 2003-03-10 | ナトコ株式会社 | Coating composition |
JPH0794587B2 (en) * | 1990-11-14 | 1995-10-11 | 日本ペイント株式会社 | Novel room temperature curable resin composition and coating composition |
JP2001064357A (en) * | 1999-08-25 | 2001-03-13 | Hitachi Chem Co Ltd | Curable composition, insutating film using the same, color filter protective film, color filter, and liquid crystal display element |
JP4409683B2 (en) * | 1999-11-12 | 2010-02-03 | ダイセル化学工業株式会社 | Optical molding resin composition, method for producing the same, and optical molding |
JP3843995B2 (en) * | 2002-05-27 | 2006-11-08 | 日本ゼオン株式会社 | Radiation sensitive resin composition, method for producing substrate having patterned resin film, and use of the resin composition |
JP2004256754A (en) * | 2003-02-27 | 2004-09-16 | Jsr Corp | Resin composition, protecting film, and method for forming the same |
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TW357176B (en) * | 1995-03-07 | 1999-05-01 | Asahi Chemical Ind | Non-inflammable resin component |
EP0990679A2 (en) * | 1998-09-29 | 2000-04-05 | Idemitsu Petrochemical Co., Ltd. | Thermoplastic resin compositons and their injection moldings |
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TW200710162A (en) | 2007-03-16 |
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KR101274936B1 (en) | 2013-06-14 |
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