TW201641575A - Thermosetting resin composition, cured film thereof and display device - Google Patents
Thermosetting resin composition, cured film thereof and display device Download PDFInfo
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Abstract
Description
本發明涉及一種可在低溫下硬化、且保存穩定性良好的熱硬化性樹脂組成物及其硬化膜。The present invention relates to a thermosetting resin composition which can be cured at a low temperature and which has good storage stability and a cured film thereof.
隨著信息終端、液晶顯示元件的發展,在現有使用玻璃或金屬等無機材料的部位使用有機材料的電子電路、顯示器、感測器等製品的開發急速推進。With the development of information terminals and liquid crystal display elements, development of electronic circuits, displays, sensors, and the like using organic materials in parts where inorganic materials such as glass or metal are used has been rapidly advanced.
使用有機材料的優點除了在於可利用分子設計或合成條件來容易地調整諸特性以外,還在於實現製品的輕量化或製程的改善。特別是將現有的玻璃基材替代為有機材料基材,不僅具有輕量化的優點,而且由於有機材料所具有的機械柔軟性而對可撓化的適合性高,從而可應用卷對卷(roll to roll)等印刷方式,借此可期待製程的低成本化。另一方面,因將現有的玻璃替代為有機材料來作為基材,而產生基材的耐熱性下降的問題。The advantage of using an organic material is that it is possible to easily adjust the properties by molecular design or synthesis conditions, and also to achieve weight reduction or process improvement of the article. In particular, the replacement of an existing glass substrate with an organic material substrate not only has the advantage of being lightweight, but also has high flexibility for flexibility due to mechanical softness of the organic material, so that roll-to-roll can be applied. To roll) and other printing methods, it is expected that the cost of the process can be reduced. On the other hand, the conventional glass is replaced with an organic material as a base material, and the heat resistance of the base material is lowered.
在進行以有機材料作為基材的開發的基礎上,並且在為了形成彩色濾光片保護膜、或設置於薄膜電晶體(Thin Film Transistor,TFT)與配向膜間或者TFT與透明電極間的透明絕緣膜而使用硬化性樹脂組成物的情況下,為了防止對基材的熱過載所引起的劣化,而期望低溫(較基材的玻璃化轉變溫度更低的溫度)下的硬化容易、與有機材料的適合性高的材料。另外,就減少製程能量(process energy)的觀點而言,也要求硬化性樹脂的低溫下的硬化。On the basis of the development of an organic material as a substrate, and in order to form a color filter protective film, or to be transparent between a thin film transistor (TFT) and an alignment film or between a TFT and a transparent electrode When a curable resin composition is used as the insulating film, in order to prevent deterioration due to thermal overload of the substrate, it is desirable to harden at a low temperature (a temperature lower than the glass transition temperature of the substrate) and to organically A highly suitable material for the material. Further, from the viewpoint of reducing process energy, hardening of the curable resin at low temperatures is also required.
以前,已進行了很多用來對應低溫硬化的研究,提出了使用可溶性聚合物(參照專利文獻1)、使用硬化促進劑(參照專利文獻2及專利文獻3)等。In the past, many studies have been conducted to cope with low-temperature curing, and it has been proposed to use a soluble polymer (see Patent Document 1), a curing accelerator (see Patent Document 2 and Patent Document 3), and the like.
但是,使用可溶性聚合物的體系中,聚合物合成複雜,且聚合物對溶劑的溶解性也低,因此為了去除溶劑而需要能量。另外,使用硬化促進劑的體系即便在室溫下也緩緩地進行硬化反應,因此樹脂組成物的保存穩定性劣化。因此,要求聚合物合成容易且保存穩定性優異的可低溫硬化的樹脂組成物。 [現有技術文獻] [專利文獻]However, in a system using a soluble polymer, the polymer synthesis is complicated, and the solubility of the polymer in a solvent is also low, so energy is required in order to remove the solvent. Further, the system using the curing accelerator gradually undergoes a curing reaction even at room temperature, and thus the storage stability of the resin composition is deteriorated. Therefore, a low-temperature-curable resin composition which is easy to synthesize a polymer and has excellent storage stability is required. [Prior Art Document] [Patent Literature]
[專利文獻1]日本專利特開2009-203414號公報 [專利文獻2]國際公開2009/011304 [專利文獻3]日本專利特開2002-69311號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-203414 [Patent Document 2] International Publication No. 2009/011304 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2002-69311
[發明所欲解決的問題] 本發明的目的在於提供一種保存穩定性優異、且在低溫下硬化的熱硬化性樹脂組成物。 [解決問題的技術手段][Problem to be Solved by the Invention] An object of the present invention is to provide a thermosetting resin composition which is excellent in storage stability and which is cured at a low temperature. [Technical means to solve the problem]
本發明者等發現,含有使具有三官能以上的聚合性雙鍵的化合物(a)在鏈轉移劑(b)的存在下進行自由基聚合而獲得的聚合體(c)的熱硬化性樹脂組成物的保存穩定性優異,且在低溫下成為硬化膜,並且基於該見解而完成本發明。本發明包含以下的項目。The present inventors have found that a thermosetting resin composition containing a polymer (c) obtained by radically polymerizing a compound (a) having a trifunctional or higher polymerizable double bond in the presence of a chain transfer agent (b) The object is excellent in storage stability and becomes a cured film at a low temperature, and the present invention has been completed based on this finding. The present invention encompasses the following items.
[1] 一種熱硬化性樹脂組成物,其含有聚合體(c),所述聚合體(c)是使具有三官能以上的聚合性雙鍵的化合物(a)在鏈轉移劑(b)的存在下進行自由基聚合而獲得。[1] A thermosetting resin composition containing a polymer (c) which is a compound (a) having a trifunctional or higher polymerizable double bond in a chain transfer agent (b) Obtained by performing radical polymerization in the presence.
[2] 如[1]項所述的熱硬化性樹脂組成物,其中化合物(a)為三官能以上的(甲基)丙烯酸酯。[2] The thermosetting resin composition according to [1], wherein the compound (a) is a trifunctional or higher (meth) acrylate.
[3] 如[1]項或[2]項所述的熱硬化性樹脂組成物,其中鏈轉移劑(b)為加成斷裂型鏈轉移劑。[3] The thermosetting resin composition according to [1] or [2] wherein the chain transfer agent (b) is an addition-cracking chain transfer agent.
[4] 如[1]項~[3]項中任一項所述的熱硬化性樹脂組成物,其中鏈轉移劑(b)為2,4-二苯基-4-甲基-1-戊烯。[4] The thermosetting resin composition according to any one of [1], wherein the chain transfer agent (b) is 2,4-diphenyl-4-methyl-1- Pentene.
[5] 如[1]項~[4]項中任一項所述的熱硬化性樹脂組成物,其中聚合體(c)是通過批次聚合來製造。[5] The thermosetting resin composition according to any one of [1], wherein the polymer (c) is produced by batch polymerization.
[6] 如[1]項~[5]項中任一項所述的熱硬化性樹脂組成物,其中聚合體(c)的重量平均分子量為2,000~200,000。[6] The thermosetting resin composition according to any one of [1], wherein the polymer (c) has a weight average molecular weight of 2,000 to 200,000.
[7] 一種硬化膜,其是將如[1]項~[6]項中任一項所述的熱硬化性樹脂組成物進行熱硬化而獲得。[7] A cured film obtained by thermally curing the thermosetting resin composition according to any one of [1] to [6].
[8] 一種硬化膜,其是將如[1]項~[6]項中任一項所述的熱硬化性樹脂組成物在100℃~150℃下進行熱硬化而獲得。[8] A cured film obtained by thermally curing the thermosetting resin composition according to any one of [1] to [6] at 100 ° C to 150 ° C.
[9] 一種顯示元件,其包含如[7]項或[8]項所述的硬化膜。 [發明的效果][9] A display element comprising the cured film according to [7] or [8]. [Effects of the Invention]
本發明的熱硬化性樹脂組成物具有良好的保存穩定性及低溫硬化性,可用於形成彩色濾光片保護膜、設置於TFT與配向膜間或者TFT與透明電極間的透明絕緣膜等。The thermosetting resin composition of the present invention has excellent storage stability and low-temperature curability, and can be used for forming a color filter protective film, a transparent insulating film provided between a TFT and an alignment film, or between a TFT and a transparent electrode.
本說明書中,有時為了表示丙烯酸與甲基丙烯酸的兩者而表述為“(甲基)丙烯酸”。另外,同樣地,有時為了表示丙烯酸酯與甲基丙烯酸酯的一者或兩者而表述為“(甲基)丙烯酸酯”。In the present specification, it is sometimes referred to as "(meth)acrylic acid" in order to show both of acrylic acid and methacrylic acid. In addition, similarly, it is expressed as "(meth)acrylate" in order to show one or both of an acrylate and a methacrylate.
本說明書中,所謂“烷基”是直鏈或分支鏈的烷基,例如可列舉:甲基、乙基、丙基、正丁基、第三丁基、戊基、己基等。In the present specification, the "alkyl group" is a linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a n-butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
<1. 本發明的熱硬化性樹脂組成物> 本發明的熱硬化性樹脂組成物的特徵在於含有聚合體(c),所述聚合體(c)是使具有三官能以上的聚合性雙鍵的化合物(a)在鏈轉移劑(b)的存在下進行自由基聚合而獲得。<1. The thermosetting resin composition of the present invention> The thermosetting resin composition of the present invention contains a polymer (c) which has a polymerizable double bond having a trifunctional or higher functional group. The compound (a) is obtained by radical polymerization in the presence of a chain transfer agent (b).
<1-1. 具有三官能以上的聚合性雙鍵的化合物(a)> 本發明的熱硬化性樹脂組成物中所含有的所謂“具有三官能以上的聚合性雙鍵的化合物”是指在分子內具有3個以上的聚合性雙鍵的化合物,只要具有該結構的特徵,則無特別限定。<1-1. Compound (a) having a trifunctional or higher polymerizable double bond> The "compound having a trifunctional or higher polymerizable double bond" contained in the thermosetting resin composition of the present invention means The compound having three or more polymerizable double bonds in the molecule is not particularly limited as long as it has the characteristics of the structure.
本發明的具有三官能以上的聚合性雙鍵的化合物(a)優選為選自具有三官能以上的(甲基)丙烯醯基的化合物、具有三官能以上的α-乙基丙烯醯基的化合物、具有三官能以上的苯乙烯基的化合物、以及具有三官能以上的乙烯基的化合物的群組中,更優選為選自具有三官能以上的(甲基)丙烯醯基的化合物以及具有三官能以上的α-乙基丙烯醯基的化合物的群組中。The compound (a) having a trifunctional or higher functional double bond of the present invention is preferably a compound selected from a (meth)acryl fluorenyl group having a trifunctional or higher functional group and a compound having a trifunctional or higher α-ethyl propylene fluorenyl group. In the group of the compound having a trifunctional or higher styrene group and the compound having a trifunctional or higher vinyl group, a compound selected from a (meth)acryl fluorenyl group having a trifunctional or higher group and a trifunctional group are more preferable. The above group of α-ethylacrylinyl compounds.
具有三官能以上的(甲基)丙烯醯基的化合物以及具有三官能以上的α-乙基丙烯醯基的化合物優選為使用(甲基)丙烯酸、α-乙基丙烯酸或者這些酸的酯。The compound having a trifunctional or higher (meth)acrylinyl group and the compound having a trifunctional or higher α-ethylpropenyl group are preferably (meth)acrylic acid, α-ethylacrylic acid or an ester of these acids.
(甲基)丙烯酸或者α-乙基丙烯酸的酯可列舉烷基酯、鹵代烷基酯等。Examples of the (meth)acrylic acid or the α-ethylacrylic acid ester include an alkyl ester and a halogenated alkyl ester.
所述具有三官能以上的聚合性雙鍵的化合物(a)的具體例為:三羥甲基丙烷三丙烯酸酯、環氧乙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷環氧丙烷(propylene oxide,PO)改質三丙烯酸酯、三羥甲基丙烷環氧乙烷(ethylene oxide,EO)改質三丙烯酸酯、丙三醇三(甲基)丙烯酸酯、乙氧基化甘油三(甲基)丙烯酸酯、表氯醇改質丙三醇三(甲基)丙烯酸酯、二甘油EO改質丙烯酸酯、烷基改質二季戊四醇五(甲基)丙烯酸酯、烷基改質二季戊四醇四(甲基)丙烯酸酯、烷基改質二季戊四醇三(甲基)丙烯酸酯、乙氧基化異氰脲酸基環三(甲基)丙烯酸酯、ε-己內酯改質三-(2-丙烯醯氧基乙基)異氰脲酸酯、環氧丙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、表氯醇改質三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、異氰脲酸EO改質二/三丙烯酸酯、季戊四醇三/四丙烯酸酯、二季戊四醇五/六丙烯酸酯、二甘油EO改質丙烯酸酯、乙氧基化異氰脲酸三丙烯酸酯、三[(甲基)丙烯醯氧基乙基]異氰脲酸酯、乙氧基化甘油三丙烯酸酯、以及乙氧基化季戊四醇四丙烯酸酯。Specific examples of the compound (a) having a trifunctional or higher polymerizable double bond are: trimethylolpropane triacrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, and three Hydroxymethylpropane propylene oxide (PO) modified triacrylate, trimethylolpropane ethylene oxide (EO) modified triacrylate, glycerol tri (meth) acrylate , ethoxylated glycerol tri(meth) acrylate, epichlorohydrin modified glycerol tri (meth) acrylate, diglycerin EO modified acrylate, alkyl modified dipentaerythritol penta (meth) acrylate Ester, alkyl modified dipentaerythritol tetra(meth) acrylate, alkyl modified dipentaerythritol tri(meth) acrylate, ethoxylated isocyanurate ring tri(meth) acrylate, ε- Caprolactone modified tris-(2-propenyloxyethyl) isocyanurate, propylene oxide modified trimethylolpropane tri(meth)acrylate, epichlorohydrin modified trimethylol Propane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, isocyanuric acid EO modified di/triacrylate, pentaerythritol Alcohol tri/tetraacrylate, dipentaerythritol penta/hexaacrylate, diglycerin EO modified acrylate, ethoxylated isocyanuric acid triacrylate, tris[(methyl)acryloxyethyl)isocyanate Urea, ethoxylated glycerol triacrylate, and ethoxylated pentaerythritol tetraacrylate.
所述化合物中,就聚合體的低溫硬化性的觀點而言,優選為二季戊四醇五/六丙烯酸酯、季戊四醇三/四丙烯酸酯。Among the above compounds, dipentaerythritol penta/hexaacrylate and pentaerythritol tri/tetraacrylate are preferable from the viewpoint of low-temperature curability of the polymer.
具有三官能以上的聚合性雙鍵的化合物(a)可單獨使用,也可將兩種以上混合使用。The compound (a) having a trifunctional or higher polymerizable double bond may be used singly or in combination of two or more.
<1-2. 鏈轉移劑(b)> 本發明中使用的鏈轉移劑(b)的具體例為:硫代乙醇酸(thioglycolic acid)、巰基丙酸、2,4-二苯基-4-甲基-1-戊烯、川崎化成工業股份有限公司製造的奎諾克斯塔(Quinoexter)QE-2014(商品名)、以及川崎化成工業股份有限公司製造的奎諾克斯塔(Quinoexter)QE-3214(商品名)。<1-2. Chain Transfer Agent (b)> Specific examples of the chain transfer agent (b) used in the present invention are: thioglycolic acid, mercaptopropionic acid, 2,4-diphenyl-4 -Methyl-1-pentene, Quinoxer QE-2014 (trade name) manufactured by Kawasaki Chemical Industry Co., Ltd., and Quinoexter manufactured by Kawasaki Chemical Industry Co., Ltd. QE-3214 (trade name).
鏈轉移劑(b)可單獨使用,也可將兩種以上混合使用。The chain transfer agent (b) may be used singly or in combination of two or more.
鏈轉移劑(b)中更優選為加成斷裂型鏈轉移劑,加成斷裂型鏈轉移劑中,就聚合的穩定性以及熱硬化性樹脂組成物的硬化性的觀點而言,更優選為2,4-二苯基-4-甲基-1-戊烯。In the chain transfer agent (b), an addition-cracking type chain transfer agent is more preferable, and in the addition-type chain transfer agent, it is more preferable from the viewpoint of stability of polymerization and hardenability of the thermosetting resin composition. 2,4-diphenyl-4-methyl-1-pentene.
<1-3. 聚合體(c)的聚合方法> 本發明的熱硬化性樹脂組成物中所含的聚合體(c)的聚合方法優選為溶液中的自由基聚合,其使用一種以上的具有三官能以上的聚合性雙鍵的化合物(a)。聚合溫度若為自所使用的聚合起始劑中充分產生自由基的溫度,則並無特別限定,通常為50℃~110℃的範圍,就抑制凝膠化的觀點而言,優選為90℃以下。聚合時間也無特別限定,通常為1小時~24小時的範圍,就作業性的觀點而言,優選為8小時以下。另外,該聚合可在加壓、減壓或大氣壓的任一種壓力下進行。<1-3. Polymerization method of the polymer (c)> The polymerization method of the polymer (c) contained in the thermosetting resin composition of the present invention is preferably a radical polymerization in a solution, which has one or more types. A compound (a) having a trifunctional or higher polymerizable double bond. The polymerization temperature is not particularly limited as long as the radical is sufficiently generated from the polymerization initiator to be used, and is usually in the range of 50 ° C to 110 ° C, and is preferably 90 ° C from the viewpoint of suppressing gelation. the following. The polymerization time is not particularly limited, but is usually in the range of from 1 hour to 24 hours, and from the viewpoint of workability, it is preferably 8 hours or shorter. Further, the polymerization can be carried out under any pressure of pressurization, reduced pressure or atmospheric pressure.
所述的聚合反應中使用的溶劑優選為可將所使用的具有三官能以上的聚合性雙鍵的化合物(a)、與其併用的鏈轉移劑(b)、以及所獲得的聚合體(c)溶解的溶劑。此種溶劑的具體例為:甲醇、乙醇、1-丙醇、2-丙醇、丙二醇、甲基丙二醇、丙酮、甲基異丁基酮、2-丁酮、乙酸乙酯、乙酸丙酯、乙酸丁酯、四氫呋喃、乙腈、二噁烷、甲苯、二甲苯、環己酮、環戊酮、乙二醇單***、丙二醇單甲醚、丙二醇單甲醚乙酸酯、二乙二醇二甲醚、二乙二醇乙基甲醚、二乙二醇單***、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、N,N-二甲基甲醯胺、乙酸、以及水。溶劑可為這些的一種,也可為這些的兩種以上的混合物。The solvent used in the polymerization reaction is preferably a compound (a) having a trifunctional or higher polymerizable double bond, a chain transfer agent (b) used therewith, and the obtained polymer (c). Solvent solvent. Specific examples of such a solvent are: methanol, ethanol, 1-propanol, 2-propanol, propylene glycol, methyl propylene glycol, acetone, methyl isobutyl ketone, 2-butanone, ethyl acetate, propyl acetate, Butyl acetate, tetrahydrofuran, acetonitrile, dioxane, toluene, xylene, cyclohexanone, cyclopentanone, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethicone Ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, N,N-dimethylformamide, acetic acid And water. The solvent may be one of these or a mixture of two or more of these.
製造聚合體(c)時所使用的聚合起始劑可使用通過熱而產生自由基的化合物、偶氮雙異丁腈等偶氮系起始劑、或過氧化苯甲醯等過氧化物系起始劑。As the polymerization initiator used in the production of the polymer (c), a compound which generates a radical by heat, an azo initiator such as azobisisobutyronitrile, or a peroxide system such as benzamidine peroxide can be used. Starting agent.
熱自由基產生劑可列舉:2,2'-偶氮雙(4-甲氧基-2,4-二甲基戊腈)(2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile))(和光純藥工業(股)製造的V-70(商品名))、2,2'-偶氮雙(2,4-二甲基戊腈)(2,2'-Azobis(2,4-dimethylvaleronitrile))(和光純藥工業(股)製造的V-65(商品名))、2,2'-偶氮雙(異丁腈)(2,2'-Azobis(isobutyronitrile))(和光純藥工業(股)製造的V-60(商品名))、2,2'-偶氮雙(2-甲基丁腈)(2,2'-Azobis(2-methylbutyronitrile))(和光純藥工業(股)製造的V-59(商品名))、2,2'-偶氮雙[N-(2-丙烯基)-2-甲基丙醯胺](2,2'-Azobis[N-(2-propenyl)-2-methylpropionamide])(和光純藥工業(股)製造的VF-096(商品名))、2,2'-偶氮雙(N-丁基-2-甲基丙醯胺)(2,2'-Azobis(N-butyl-2-methylpropionamide))(和光純藥工業(股)製造的VAm-110(商品名))、2,2'-偶氮雙(異丁酸)二甲酯(Dimethyl 2,2'-Azobis(isobutyrate))(和光純藥工業(股)製造的V-601(商品名))、VPE-0201、VPE-0401、VPE-0601、VPS-1001(以上均為商品名,和光純藥工業(股))等。The thermal radical generating agent is exemplified by 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (2,2'-Azobis(4-methoxy-2,4-dimethylvaleronitrile). )) (V-70 (trade name) manufactured by Wako Pure Chemical Industries Co., Ltd.), 2,2'-azobis(2,4-dimethylvaleronitrile) (2,2'-Azobis (2, 4-dimethylvaleronitrile)) (V-65 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-Azobis (isobutyronitrile) (and V-60 (trade name) manufactured by Wako Pure Chemical Industries Co., Ltd., 2,2'-Azobis(2-methylbutyronitrile) (Wako Pure Chemicals) V-59 (trade name) manufactured by Industry Co., Ltd., 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide] (2,2'-Azobis[N -(2-propenyl)-2-methylpropionamide]) (VF-096 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis(N-butyl-2-methylpropane) (2,2'-Azobis (N-butyl-2-methylpropionamide)) (VAm-110 (trade name) manufactured by Wako Pure Chemical Industries, Ltd.), 2,2'-azobis (isobutyl) Dimethyl 2,2'-Azobis (isobutyrate) V-601 (trade name) manufactured by Wako Pure Chemical Industries Co., Ltd., VPE-0201, VPE-0401, VPE-0601, and VPS-1001 (all of which are trade names, and Wako Pure Chemical Industries Co., Ltd.).
聚合體(c)的重量平均分子量優選為2,000~200,000,就成膜性的觀點而言,更優選為10,000~100,000。The weight average molecular weight of the polymer (c) is preferably 2,000 to 200,000, and more preferably 10,000 to 100,000 from the viewpoint of film formability.
本說明書中的重量平均分子量是利用凝膠滲透色譜(Gel Permeation Chromatography,GPC)法(管柱溫度:35℃,流速:1 mL/min)來求出的聚苯乙烯換算的值。標準的聚苯乙烯是使用分子量為645~285,300的聚苯乙烯(例如:安捷倫(Agilent)S-M2-10聚苯乙烯校正套組PL2010-0102(商品名,安捷倫科技(Agilent Technology)股份有限公司)),管柱是使用PLgel MIXED-D(商品名,安捷倫科技(Agilent Technology)股份有限公司),且使用四氫呋喃(tetrahydrofuran,THF)作為移動相來測定。此外,本說明書中的市售品的重量平均分子量為產品目錄登載值。The weight average molecular weight in the present specification is a value in terms of polystyrene obtained by a gel permeation chromatography (GPC) method (column temperature: 35 ° C, flow rate: 1 mL/min). Standard polystyrene is polystyrene with a molecular weight of 645 to 285,300 (for example: Agilent S-M2-10 polystyrene calibration kit PL2010-0102 (trade name, Agilent Technology, Inc.) )), the column was measured using PLgel MIXED-D (trade name, Agilent Technology, Inc.) and using tetrahydrofuran (THF) as the mobile phase. Further, the weight average molecular weight of the commercially available product in the present specification is a catalogue value.
就熱硬化性樹脂組成物的硬化性的觀點而言,通過所述方式而獲得的聚合體(c)優選為利用再沉澱法而去除未反應物。作為利用再沉澱的純化方法,對所獲得的聚合體溶液的3倍~10倍體積的無極性溶劑進行攪拌,在其中滴加聚合體溶液而使聚合體沉澱。去除上清液後,可通過再溶解於聚合溶劑中而純化。From the viewpoint of the curability of the thermosetting resin composition, the polymer (c) obtained by the above method preferably removes the unreacted material by a reprecipitation method. As a purification method by reprecipitation, a 3-fold to 10-fold volume of the nonpolar solvent of the obtained polymer solution is stirred, and a polymer solution is dropped thereto to precipitate a polymer. After the supernatant is removed, it can be purified by redissolving in a polymerization solvent.
所述再沉澱法中使用的無極性溶劑優選為己烷或庚烷。The nonpolar solvent used in the reprecipitation method is preferably hexane or heptane.
<1-4. 其他成分> 就附加進一步的特性的觀點而言,本發明的熱硬化性樹脂組成物也可視需要而含有所述以外的其他成分。所述其他成分例如可列舉溶劑或添加劑等。<1-4. Other components> The thermosetting resin composition of the present invention may contain other components than the above, as needed, from the viewpoint of adding further characteristics. Examples of the other components include a solvent, an additive, and the like.
<1-4-1. 溶劑> 本發明的熱硬化性樹脂組成物中也可添加溶劑。本發明的熱硬化性樹脂組成物中所任意添加的溶劑優選為可將聚合物及其他的添加劑溶解的溶劑。可添加的溶劑的具體例為:水、丙酮、甲基異丁基酮、甲醇、乙醇、1-丙醇、2-丙醇、丙二醇、甲基丙二醇、2-丁酮、乙酸乙酯、乙酸丙酯、乙酸丁酯、丙酸丁酯、乳酸乙酯、氧基乙酸甲酯、氧基乙酸乙酯、氧基乙酸丁酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-氧基丙酸甲酯、3-氧基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-氧基丙酸甲酯、2-氧基丙酸乙酯、2-氧基丙酸丙酯、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-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-氧基-2-甲基丙酸甲酯、2-氧基-2-甲基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、2-氧代丁酸甲酯、2-氧代丁酸乙酯、四氫呋喃、乙腈、二噁烷、乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、三丙二醇、1,4-丁二醇、乙二醇單異丙醚、乙二醇單丁醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯、乙二醇單丁醚乙酸酯、環己酮、環戊酮、二乙二醇單甲醚、二乙二醇單甲醚乙酸酯、二乙二醇單***、二乙二醇丁基甲醚、二乙二醇單***乙酸酯、二乙二醇單丁醚、二乙二醇單丁醚乙酸酯、二乙二醇二甲醚、二乙二醇二***、二乙二醇乙基甲醚、甲苯、二甲苯、γ-丁內酯、N,N-二甲基乙醯胺、以及N,N-二甲基甲醯胺。這些溶劑可單獨使用,也可將兩種以上組合使用。<1-4-1. Solvent> A solvent may be added to the thermosetting resin composition of the present invention. The solvent to be arbitrarily added to the thermosetting resin composition of the present invention is preferably a solvent which can dissolve the polymer and other additives. Specific examples of the solvent which can be added are: water, acetone, methyl isobutyl ketone, methanol, ethanol, 1-propanol, 2-propanol, propylene glycol, methyl propylene glycol, 2-butanone, ethyl acetate, acetic acid Propyl ester, butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, methoxy Butyl acetate, ethoxyacetic acid methyl ester, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methyl Ethyl oxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxypropane Acid propyl ester, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropane Ethyl acetate, methyl 2-oxy-2-methylpropanoate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropanoate, 2-B Ethyl oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, 2-oxo Methyl ester, ethyl 2-oxobutanoate, tetrahydrofuran, acetonitrile, dioxane, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol , ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether Acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol butyl methyl ether, diethylene glycol single Ethyl acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, toluene, Xylene, γ-butyrolactone, N,N-dimethylacetamide, and N,N-dimethylformamide. These solvents may be used singly or in combination of two or more.
就提高本發明的熱硬化性樹脂組成物的塗佈均勻性的觀點而言,溶劑優選為選自丙二醇、丙二醇單甲醚、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、二乙二醇單***、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯、二乙二醇二甲醚、二乙二醇乙基甲醚、乳酸乙酯及乙酸丁酯中的至少一種。進而,就提高本發明的熱硬化性樹脂組成物的塗佈均勻性的觀點以及對人體的安全性的觀點而言,更優選為選自丙二醇、丙二醇單甲醚、丙二醇單甲醚乙酸酯、3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、二乙二醇乙基甲醚、乳酸乙酯及乙酸丁酯中的至少一種。From the viewpoint of improving the coating uniformity of the thermosetting resin composition of the present invention, the solvent is preferably selected from the group consisting of propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and 3- Methyl methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol At least one of dimethyl ether, diethylene glycol ethyl methyl ether, ethyl lactate, and butyl acetate. Further, from the viewpoint of improving the uniformity of coating of the thermosetting resin composition of the present invention and safety to the human body, it is more preferably selected from the group consisting of propylene glycol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. At least one of methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol ethyl methyl ether, ethyl lactate, and butyl acetate.
本發明的熱硬化性樹脂組成物中,溶劑優選為以作為固體成分的聚合體(c)以及其他的添加劑以總量計成為5重量%~90重量%的方式來調配。In the thermosetting resin composition of the present invention, the solvent is preferably formulated so that the polymer (c) as a solid component and other additives are 5% by weight to 90% by weight based on the total amount.
<1-4-2. 添加劑> 本發明的熱硬化性樹脂組成物也可含有添加劑。本發明的熱硬化性樹脂組成物中所任意添加的添加劑是出於提高塗佈均勻性、黏接性、穩定性等本發明的熱硬化性樹脂組成物的特性的觀點而添加。添加劑中,例如可列舉:聚合抑制劑、丙烯酸系、苯乙烯系、聚乙烯亞胺系或胺基甲酸酯系的高分子分散劑,陰離子系、陽離子系、非離子系或氟系的界面活性劑,矽酮樹脂系塗佈性提高劑,矽烷偶合劑等密合性提高劑,聚丙烯酸鈉等凝聚防止劑,環氧化合物、三聚氰胺化合物或雙疊氮化合物等熱交聯劑,受阻系酚等抗氧化劑,以及咪唑系或多官能丙烯酸酯系的硬化促進劑等。<1-4-2. Additives> The thermosetting resin composition of the present invention may contain an additive. The additive which is arbitrarily added to the thermosetting resin composition of the present invention is added from the viewpoint of improving the properties of the thermosetting resin composition of the present invention such as coating uniformity, adhesion, and stability. Examples of the additive include a polymerization inhibitor, an acrylic, a styrene-based, a polyethyleneimine-based or a urethane-based polymer dispersant, and an anionic, cationic, nonionic or fluorine-based interface. An active agent, an oxime resin-based coating improver, an adhesion improver such as a decane coupling agent, a coagulant preventive agent such as sodium polyacrylate, a thermal cross-linking agent such as an epoxy compound, a melamine compound or a diazide compound, and a hindered system. An antioxidant such as phenol, or an imidazole-based or polyfunctional acrylate-based hardening accelerator.
本發明的熱硬化性樹脂組成物中也可添加界面活性劑、塗佈性提高劑。界面活性劑、塗佈性提高劑是為了提高對基底基板的潤濕性、流平性、或者塗佈性而使用。本發明的熱硬化性樹脂組成物中所任意添加的界面活性劑、塗佈性提高劑可列舉:珀利弗洛(Polyflow)No.45、珀利弗洛(Polyflow)KL-245、珀利弗洛(Polyflow)No.75、珀利弗洛(Polyflow)No.90、珀利弗洛(Polyflow)No.95(以上均為商品名,共榮社化學工業股份有限公司),畢克(BYK)-300、畢克(BYK)-306、畢克(BYK)-310、畢克(BYK)-320、畢克(BYK)-330、畢克(BYK)-342、畢克(BYK)-346(以上均為商品名,日本畢克化學(BYK-Chemie Japan)股份有限公司),KP-341、KP-358、KP-368、KF-96-50CS、KF-50-100CS(以上均為商品名,信越化學工業股份有限公司),沙福隆(Surflon)SC-101、沙福隆(Surflon)KH-40、沙福隆(Surflon)S-611(以上均為商品名,AGC清美化學(AGC Seimi Chemical)股份有限公司),福傑特(Ftergent)222F、福傑特(Ftergent)208G、福傑特(Ftergent)251、福傑特(Ftergent)710FL、福傑特(Ftergent)710FM、福傑特(Ftergent)710FS、福傑特(Ftergent)601AD、福傑特(Ftergent)602A、福傑特(Ftergent)650A、FTX-218(以上均為商品名,尼歐斯(Neos)股份有限公司),艾福拓(EFTOP)EF-351、艾福拓(EFTOP)EF-352、艾福拓(EFTOP)EF-601、艾福拓(EFTOP)EF-801、艾福拓(EFTOP)EF-802(以上均為商品名,三菱材料(Mitsubishi Material)股份有限公司),美佳法(Megafac)F-171、美佳法(Megafac)F-177、美佳法(Megafac)F-410、美佳法(Megafac)F-430、美佳法(Megafac)F-444、美佳法(Megafac)F-472SF、美佳法(Megafac)F-475、美佳法(Megafac)F-477、美佳法(Megafac)F-552、美佳法(Megafac)F-553、美佳法(Megafac)F-554、美佳法(Megafac)F-555、美佳法(Megafac)F-556、美佳法(Megafac)F-558、美佳法(Megafac)R-30、美佳法(Megafac)R-94、美佳法(Megafac)RS-75、美佳法(Megafac)RS-72-K、美佳法(Megafac)RS-76-NS(以上均為商品名,迪愛生(DIC)股份有限公司),迪高特溫(TEGO Twin)4000、迪高特溫(TEGO Twin)4100、迪高弗洛(TEGO Flow)370、迪高格萊德(TEGO Glide)420、迪高格萊德(TEGO Glide)440、迪高格萊德(TEGO Glide)450、迪高拉德(TEGO Rad)2200N、迪高拉德(TEGO Rad)2250N(以上均為商品名,日本贏創德固賽(Evonik Degussa Japan)股份有限公司),氟烷基苯磺酸鹽、氟烷基羧酸鹽、氟烷基聚氧乙烯醚、碘化氟烷基銨、氟烷基甜菜鹼、氟烷基磺酸鹽、二甘油四(氟烷基聚氧乙烯醚)、氟烷基三甲基銨鹽、氟烷基胺基磺酸鹽、聚氧乙烯壬基苯基醚、聚氧乙烯辛基苯基醚、聚氧乙烯烷基醚、聚氧乙烯月桂基醚、聚氧乙烯油烯基醚、聚氧乙烯十三烷基醚、聚氧乙烯鯨蠟基醚、聚氧乙烯硬脂基醚、聚氧乙烯月桂酸酯、聚氧乙烯油酸酯、聚氧乙烯硬脂酸酯、聚氧乙烯月桂基胺、脫水山梨糖醇月桂酸酯、脫水山梨糖醇棕櫚酸酯、脫水山梨糖醇硬脂酸酯、脫水山梨糖醇油酸酯、脫水山梨糖醇脂肪酸酯、聚氧乙烯脫水山梨糖醇月桂酸酯、聚氧乙烯脫水山梨糖醇棕櫚酸酯、聚氧乙烯脫水山梨糖醇硬脂酸酯、聚氧乙烯脫水山梨糖醇油酸酯、聚氧乙烯萘基醚、烷基苯磺酸鹽、或者烷基二苯基醚二磺酸鹽等。優選為將選自這些中的至少一種用於添加劑。A surfactant and a coatability improver may be added to the thermosetting resin composition of the present invention. The surfactant and the coatability improver are used to improve wettability, leveling property, or coatability to the base substrate. The surfactant and the coating property improver which are arbitrarily added to the thermosetting resin composition of the present invention include Polyflow No. 45, Polyflow KL-245, and Poli Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (all of which are trade names, Kyoei Chemical Industry Co., Ltd.), BYK ( BYK)-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK -346 (all of the above are trade names, BYK-Chemie Japan Co., Ltd.), KP-341, KP-358, KP-368, KF-96-50CS, KF-50-100CS (all of the above) For the trade name, Shin-Etsu Chemical Co., Ltd.), Surflon SC-101, Surflon KH-40, Surflon S-611 (all of which are trade names, AGC Qingmei) AGC Seimi Chemical Co., Ltd., Ftergent 222F, Ftergent 208G, Ftergent 251, Ftergent 710FL, Ftergent 710FM, Ftergent 710FS, Ftergent 601AD, Ftergent 602A, Ftergent 650A, FTX-218 (all of which are commodities) Name, Neos Co., Ltd., EFTOP EF-351, EFTOP EF-352, EFTOP EF-601, EFTOP EF -801, EFTOP EF-802 (all of which are trade names, Mitsubishi Material Co., Ltd.), Megafac F-171, Megafac F-177, Meijiafa (Megafac) F-410, Megafac F-430, Megafac F-444, Megafac F-472SF, Megafac F-475, Megafac F- 477, Megafac F-552, Megafac F-553, Megafac F-554, Megafac F-555, Megafac F-556, Meijiafa ( Megafac) F-558, Megafac R-30, Megafac R-94, Megafac RS-75, Megafac RS-72-K, Megafac RS-76-NS (all of the above are trade names, Di Ai Sheng (DIC) Co., Ltd.), TEGO Twin 4000, Tego Twin (TEGO Twin) 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450, Digord (TEGO Rad) 2200N, TEGO Rad 2250N (all of the above are trade names, Evonik Degussa Japan Co., Ltd.), fluoroalkylbenzenesulfonate, fluoroalkylcarboxylate Acid salt, fluoroalkyl polyoxyethylene ether, fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl sulfonate, diglycerol tetrakis(fluoroalkyl polyoxyethylene ether), fluoroalkyl trimethyl Ammonium salt, fluoroalkylamino sulfonate, polyoxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl Ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene Fatty acid ester, polyoxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid Ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene Naphthyl ether, alkylbenzenesulfonate or alkyldiphenyl ether disulfonate. It is preferred to use at least one selected from these for the additive.
這些界面活性劑、塗佈性提高劑中,若添加選自氟烷基苯磺酸鹽、氟烷基羧酸鹽、氟烷基聚氧乙烯醚、碘化氟烷基銨、氟烷基甜菜鹼、氟烷基磺酸鹽、二甘油四(氟烷基聚氧乙烯醚)、氟烷基三甲基銨鹽、氟烷基胺基磺酸鹽,美佳法(Megafac)R-08、美佳法(Megafac)R-30、美佳法(Megafac)F-477、美佳法(Megafac)F-556、美佳法(Megafac)F-554等氟系界面活性劑,畢克(BYK)-306、畢克(BYK)-342、畢克(BYK)344、畢克(BYK)346、KP-341、KP-358、或者KP-368等矽酮樹脂系塗佈性提高劑中的至少一種,則就提高本發明的熱硬化性樹脂組成物的塗佈均勻性的觀點而言優選。Among these surfactants and coatability improvers, if added, it is selected from a fluoroalkylbenzenesulfonate, a fluoroalkylcarboxylate, a fluoroalkylpolyoxyethylene ether, a fluoroalkylammonium iodide, or a fluoroalkyl beet. Alkali, fluoroalkyl sulfonate, diglycerol tetrakis(fluoroalkyl ethoxylate), fluoroalkyltrimethylammonium salt, fluoroalkylamine sulfonate, Megafac R-08, Meijia Method (Megafac) R-30, Megafac F-477, Megafac F-556, Megafac F-554 and other fluorine-based surfactants, BYK-306, Bi At least one of an oxime resin-based coating improver such as BYK-342, BYK 344, BYK 346, KP-341, KP-358, or KP-368 It is preferable from the viewpoint of improving the coating uniformity of the thermosetting resin composition of the present invention.
相對於組成物的總體量,本發明的熱硬化性樹脂組成物中的界面活性劑、塗佈提高劑的含量分別優選為0.001重量%~0.1重量%。The content of the surfactant and the coating enhancer in the thermosetting resin composition of the present invention is preferably 0.001% by weight to 0.1% by weight, based on the total amount of the composition.
本發明的熱硬化性樹脂組成物中也可添加硬化促進劑。所述硬化促進劑是為了促進熱硬化性樹脂組成物的硬化反應,提高硬化膜的硬度、耐熱性、耐化學品性而使用。本發明的熱硬化性樹脂組成物中所任意添加的硬化促進劑為:三羥甲基丙烷三丙烯酸酯、環氧乙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、三羥甲基丙烷PO改質三丙烯酸酯、三羥甲基丙烷EO改質三丙烯酸酯、丙三醇三(甲基)丙烯酸酯、乙氧基化甘油三(甲基)丙烯酸酯、表氯醇改質丙三醇三(甲基)丙烯酸酯、二甘油EO改質丙烯酸酯、烷基改質二季戊四醇五(甲基)丙烯酸酯、烷基改質二季戊四醇四(甲基)丙烯酸酯、烷基改質二季戊四醇三(甲基)丙烯酸酯、乙氧基化異氰脲酸基環三(甲基)丙烯酸酯、ε-己內酯改質三-(2-丙烯醯氧基乙基)異氰脲酸酯、環氧丙烷改質三羥甲基丙烷三(甲基)丙烯酸酯、表氯醇改質三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、異氰脲酸EO改質二/三丙烯酸酯、季戊四醇三/四丙烯酸酯、二季戊四醇五/六丙烯酸酯、二甘油EO改質丙烯酸酯、乙氧基化異氰脲酸三丙烯酸酯、三[(甲基)丙烯醯氧基乙基]異氰脲酸酯、乙氧基化甘油三丙烯酸酯、乙氧基化季戊四醇四丙烯酸酯、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、2,3-二氫-1H-吡咯並[1,2-a]苯并咪唑等。A hardening accelerator may be added to the thermosetting resin composition of the present invention. The hardening accelerator is used to promote the hardening reaction of the thermosetting resin composition and to improve the hardness, heat resistance, and chemical resistance of the cured film. The hardening accelerator added arbitrarily in the thermosetting resin composition of the present invention is: trimethylolpropane triacrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, trishydroxyl Propane PO modified triacrylate, trimethylolpropane EO modified triacrylate, glycerol tri(meth) acrylate, ethoxylated glycerol tri(meth) acrylate, epichlorohydrin modification Glycerol tri(meth) acrylate, diglycerin EO modified acrylate, alkyl modified dipentaerythritol penta (meth) acrylate, alkyl modified dipentaerythritol tetra (meth) acrylate, alkyl modification Dipentaerythritol tri(meth)acrylate, ethoxylated isocyanurate ring tri(meth)acrylate, ε-caprolactone modified tris-(2-propenyloxyethyl)isocyanate Urea, propylene oxide modified trimethylolpropane tri(meth) acrylate, epichlorohydrin modified trimethylolpropane tri(meth) acrylate, di-trimethylolpropane tetra (a) Acrylate, isocyanuric acid EO modified di/triacrylate, pentaerythritol tri/tetraacrylate, dipentaerythritol penta/hexaacrylate, diglycerol E O modified acrylate, ethoxylated isocyanuric acid triacrylate, tris[(meth)acryloxyethyl]isocyanurate, ethoxylated glycerol triacrylate, ethoxylated Pentaerythritol tetraacrylate, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2,3-dihydro-1H-pyrrolo[ 1,2-a]benzimidazole and the like.
硬化促進劑可單獨使用,也可將兩種以上混合使用。The hardening accelerator may be used singly or in combination of two or more.
本發明的熱硬化性樹脂組成物中也可添加密合性提高劑。密合性提高劑是為了提高熱硬化性樹脂組成物與基板的密合性而使用。本發明的熱硬化性樹脂組成物中所任意添加的密合性提高劑可適合使用偶合劑。密合性提高劑可為一種,也可為兩種以上。偶合劑中可使用矽烷系、鋁系或鈦酸酯系的化合物。此種偶合劑例如可列舉:3-縮水甘油氧基丙基二甲基乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷、乙醯烷氧基二異丙醇鋁(acetoalkoxy aluminum diisopropylate)、以及雙(二辛基亞磷酸)鈦酸四異丙酯(tetraisopropyl bis(dioctylphosphite)titanate)。這些化合物中,3-縮水甘油氧基丙基三甲氧基矽烷由於提高密合性的效果大而優選。An adhesion improver may be added to the thermosetting resin composition of the present invention. The adhesion improver is used to improve the adhesion between the thermosetting resin composition and the substrate. A coupling agent which is arbitrarily added to the thermosetting resin composition of the present invention can be suitably used. The adhesion improver may be one type or two or more types. A decane-based, aluminum-based or titanate-based compound can be used as the coupling agent. Examples of such a coupling agent include 3-glycidoxypropyldimethylethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltrimethoxy. Baseline, acetoalkoxy aluminum diisopropylate, and tetraisopropyl bis (dioctylphosphite) titanate. Among these compounds, 3-glycidoxypropyltrimethoxydecane is preferred because it has a large effect of improving adhesion.
本發明的熱硬化性樹脂組成物中也可添加凝聚防止劑。凝聚防止劑是為了與溶劑相溶以防止凝聚而使用。本發明的熱硬化性樹脂組成物中所任意添加的凝聚防止劑的具體例為:迪斯帕畢克(DISPERBYK)-145、迪斯帕畢克(DISPERBYK)-161、迪斯帕畢克(DISPERBYK)-162、迪斯帕畢克(DISPERBYK)-163、迪斯帕畢克(DISPERBYK)-164、迪斯帕畢克(DISPERBYK)-182、迪斯帕畢克(DISPERBYK)-184、迪斯帕畢克(DISPERBYK)-185、迪斯帕畢克(DISPERBYK)-2163、迪斯帕畢克(DISPERBYK)-2164、畢克(BYK)-220S、迪斯帕畢克(DISPERBYK)-191、迪斯帕畢克(DISPERBYK)-199、迪斯帕畢克(DISPERBYK)-2015(均為商品名,日本畢克化學(BYK-Chemie Japan)股份有限公司),FTX-218、福傑特(Ftergent)710FM、福傑特(Ftergent)710FS(均為商品名,尼歐斯(Neos)股份有限公司),弗洛蘭(Flowlen)G-600、弗洛蘭(Flowlen)G-700(均為商品名,共榮社化學工業股份有限公司)。A coagulation preventing agent may be added to the thermosetting resin composition of the present invention. The coagulation preventing agent is used in order to be compatible with a solvent to prevent aggregation. Specific examples of the coagulation preventing agent added arbitrarily in the thermosetting resin composition of the present invention are: DISPERBYK-145, DISPERBYK-161, and Despabike ( DISPERBYK)-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-182, DISPERBYK-184, DIS DISPERBYK-185, DISPERBYK-2163, DISPERBYK-2164, BYK-220S, DISPERBYK-191 , DISPERBYK-199, DISPERBYK-2015 (all trade names, BYK-Chemie Japan Co., Ltd.), FTX-218, Fojet (Ftergent) 710FM, Ftergent 710FS (both trade names, Neos Co., Ltd.), Flowlen G-600, Flowlen G-700 (both For the trade name, Gongrongshe Chemical Industry Co., Ltd.).
本發明的熱硬化性樹脂組成物中也可添加抗氧化劑。抗氧化劑可適合使用受阻酚系、受阻胺系、磷系、及硫系化合物。抗氧化劑可單獨使用,也可將兩種以上混合使用。就耐候性的觀點而言,抗氧化劑優選為受阻酚系化合物的抗氧化劑。An antioxidant may also be added to the thermosetting resin composition of the present invention. As the antioxidant, a hindered phenol type, a hindered amine type, a phosphorus type, and a sulfur type compound can be suitably used. The antioxidant may be used singly or in combination of two or more. From the viewpoint of weather resistance, the antioxidant is preferably an antioxidant of a hindered phenol compound.
本發明的熱硬化性樹脂組成物中所任意添加的抗氧化劑可使用受阻胺系、受阻酚系等。具體而言,可列舉:易璐佛斯(IRGAFOS)XP40、易璐佛斯(IRGAFOS)XP60、易璐諾斯(IRGANOX)1010、易璐諾斯(IRGANOX)1035、易璐諾斯(IRGANOX)1076、易璐諾斯(IRGANOX)1135、易璐諾斯(IRGANOX)1520L(均為商品名,日本巴斯夫(BASF)(股)製造),艾迪科斯塔布(ADK STAB)AO-20、艾迪科斯塔布(ADK STAB)AO-30、艾迪科斯塔布(ADK STAB)AO-50、艾迪科斯塔布(ADK STAB)AO-60、艾迪科斯塔布(ADK STAB)AO-70、艾迪科斯塔布(ADK STAB)AO-80(商品名;艾迪科(ADEKA)股份有限公司)。這些化合物中,就抑制本發明的熱硬化性樹脂組成物的變色的觀點而言,更優選為易璐諾斯(IRGANOX)1010、艾迪科斯塔布(ADK STAB)AO-60。A hindered amine-based, hindered phenol-based or the like can be used as the antioxidant to be added arbitrarily in the thermosetting resin composition of the present invention. Specifically, it can be listed as: IRGAFOS XP40, IRGAFOS XP60, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 1520L (all trade names, manufactured by BASF (Japan)), ADK STAB AO-20, Ai ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70 , ADK STAB AO-80 (trade name; ADEKA). Among these compounds, from the viewpoint of suppressing discoloration of the thermosetting resin composition of the present invention, IRGANOX 1010 and ADK STAB AO-60 are more preferable.
就提高耐熱性、耐化學品性、膜面內均勻性、可撓性、柔軟性、彈性的觀點而言,本發明的熱硬化性樹脂組成物也可任意地添加交聯劑。The thermosetting resin composition of the present invention may optionally contain a crosslinking agent from the viewpoint of improving heat resistance, chemical resistance, film in-plane uniformity, flexibility, flexibility, and elasticity.
本發明的熱硬化性樹脂組成物中所任意添加的熱交聯劑的具體例可列舉:jER807、jER815、jER825、jER827、jER828、jER190P及jER191P(均為商品名,三菱化學(股)),jER1004、jER1256、YX8000(均為商品名,三菱化學(股)),愛牢達(Araldite)CY177、愛牢達(Araldite)CY184(均為商品名,日本亨斯邁(Huntsman Japan)(股)),賽羅西德(Celloxide)2021P、EHPE-3150(均為商品名,大賽璐化學工業(Daicel Chemical industries)(股)),特克摩阿(Techmore)VG3101L(商品名,普林泰科(Printec)股份有限公司),尼卡拉克(Nikalac)MW-30HM、尼卡拉克(Nikalac)MW-100LM、尼卡拉克(Nikalac)MW-270、尼卡拉克(Nikalac)MW-280、尼卡拉克(Nikalac)MW-290、尼卡拉克(Nikalac)MW-390、尼卡拉克(Nikalac)MW-750LM(均為商品名,三和化學(股))。Specific examples of the thermal crosslinking agent arbitrarily added to the thermosetting resin composition of the present invention include jER807, jER815, jER825, jER827, jER828, jER190P, and jER191P (all are trade names, Mitsubishi Chemical Corporation). jER1004, jER1256, YX8000 (all trade names, Mitsubishi Chemical (shares)), Araldite CY177, Araldite CY184 (both trade names, Japan Huntsman Japan) ), Celloxide 2021P, EHPE-3150 (all trade names, Daicel Chemical industries (shares)), Techmore VG3101L (trade name, Principal) (Printec) Co., Ltd., Nikalac MW-30HM, Nikalac MW-100LM, Nikalac MW-270, Nikalac MW-280, Nika Nikalac MW-290, Nikalac MW-390, Nikalac MW-750LM (both trade names, Sanwa Chemical Co., Ltd.).
<1-5. 熱硬化性樹脂組成物的保存> 本發明的熱硬化性樹脂組成物若在-30℃~25℃的範圍內遮光而保存,則組成物的經時穩定性變得良好,故而優選。更優選為在-10℃~20℃下保存。<1-5. Storage of Thermosetting Resin Composition> When the thermosetting resin composition of the present invention is stored in a range of from -30 to 25 ° C, the stability of the composition is improved over time. Therefore, it is preferable. More preferably, it is stored at -10 ° C to 20 ° C.
<2. 由熱硬化性樹脂組成物獲得的硬化膜> 本發明的熱硬化性樹脂組成物可通過包含聚合體(c),且根據目標特性,進而視需要來選擇添加溶劑、偶合劑、界面活性劑、抗氧化劑及其他添加劑,並將它們均勻地混合溶解而獲得。 若將本發明的熱硬化性樹脂或者使用其的熱硬化性組成物(在無溶劑的固體狀態的情況下溶解於溶劑中後)塗佈於基材表面,例如通過加熱等而去除溶劑,則可形成塗膜。<2. Cured film obtained from a thermosetting resin composition> The thermosetting resin composition of the present invention can contain a polymer (c), and depending on the target characteristics, optionally, a solvent, a coupling agent, and an interface are added. Active agents, antioxidants, and other additives are obtained by uniformly mixing and dissolving them. When the thermosetting resin of the present invention or a thermosetting composition (after being dissolved in a solvent in a solid state without a solvent) is applied onto the surface of the substrate, for example, by heating or the like, the solvent is removed. A coating film can be formed.
本發明的熱硬化性樹脂組成物的塗佈方法可利用旋轉塗佈法、輥塗佈法、浸漬法、狹縫塗佈法、噴墨法、柔版印刷法及凹版印刷法等現有公知的方法來形成塗膜。The method for applying the thermosetting resin composition of the present invention can be any conventionally known such as a spin coating method, a roll coating method, a dipping method, a slit coating method, an inkjet method, a flexographic printing method, and a gravure printing method. The method is to form a coating film.
成膜時所使用的基材可列舉塑膠、玻璃、氟摻雜氧化錫(Fluorine-doped Tin Oxide,FTO)或氧化銦錫(Indium Tin Oxide,ITO)等帶透明電極的玻璃等基材。塑膠的具體例可列舉:聚碳酸酯、聚(甲基)丙烯酸酯、聚胺基甲酸酯、聚對苯二甲酸乙二酯、環烯烴、三乙醯基纖維素。Examples of the substrate used for film formation include substrates such as plastic, glass, Fluorine-doped Tin Oxide (FTO), or Indium Tin Oxide (ITO), and the like. Specific examples of the plastics include polycarbonate, poly(meth)acrylate, polyurethane, polyethylene terephthalate, cycloolefin, and triethylenesulfonyl cellulose.
該塗膜是利用加熱板、或者烘箱等進行加熱(預烘烤)。加熱條件根據各成分的種類及調配比例而不同,通常為60℃~100℃、1分鐘~15分鐘。然後,為了使塗膜硬化,可通過在100℃~150℃、優選為120℃~150℃下,進行5分鐘~60分鐘加熱處理(後烘烤)而獲得硬化膜。The coating film is heated (prebaked) by a hot plate or an oven. The heating conditions vary depending on the type of each component and the blending ratio, and are usually 60 to 100 ° C for 1 minute to 15 minutes. Then, in order to cure the coating film, a cured film can be obtained by heat treatment (post-baking) at 100 ° C to 150 ° C, preferably 120 ° C to 150 ° C for 5 minutes to 60 minutes.
本發明的熱硬化性樹脂組成物即便在作為使塗膜硬化的溫度的120℃~150℃的低溫下進行熱硬化,也可獲得硬化膜。因此,若對如塑膠之類的玻璃化轉變點低的基材應用本發明的熱硬化性樹脂組成物,則不會引起基材的劣化、破損,可獲得硬化膜。 [實施例]The thermosetting resin composition of the present invention can be cured by heat curing at a low temperature of 120 to 150 ° C which is a temperature at which the coating film is cured. Therefore, when the thermosetting resin composition of the present invention is applied to a substrate having a low glass transition point such as plastic, deterioration or breakage of the substrate is not caused, and a cured film can be obtained. [Examples]
以下,通過實施例來對本發明進一步進行說明,但本發明不受這些實施例的限定。以下示出本發明的熱硬化性樹脂組成物的評價方法。Hereinafter, the present invention will be further illustrated by the examples, but the present invention is not limited by these examples. The evaluation method of the thermosetting resin composition of the present invention is shown below.
[熱硬化性樹脂組成物的評價方法] 1)膜厚 在玻璃基板(康寧(Corning)(股)製造的伊格爾(Eagle)XG(商品名),40 mm×40 mm×0.7 mm)上,以既定的轉數來旋轉塗佈熱硬化性樹脂組成物10秒,在90℃的加熱板上進行2分鐘預烘烤。將該基板在既定溫度的加熱板上進行10分鐘後烘烤,並測定膜厚。膜厚是使用階差・表面粗糙度・微細形狀測定裝置(P-16+(商品名),日本科磊(KLA-Tencor Japan)股份有限公司)來測定,將三個部位的測定的平均值作為膜厚。轉數是以後烘烤後的膜厚成為3.0 μm的方式來調整。 2)塗佈性 以目視對所形成的硬化膜進行觀察,將無不均的良好的情況設為“○”,將產生不均的情況設為“△”,將產生排斥而未充分地成膜於基板上的情況設為“×”。 3)硬化性 將經膜厚測定的樹脂膜基板在保持為24℃的熱硬化性樹脂組成物所使用的溶劑中浸漬2分鐘。自溶劑中取出,通過鼓風而去除溶劑後,測定膜厚,算出殘膜率=(浸漬後膜厚/浸漬前膜厚)×100。在硬化溫度100℃、120℃、140℃及230℃下進行測定,確認殘膜率成為95%以上的後烘烤溫度。將無法製成硬化膜者設為“×”,將即便在230℃下殘膜率也未達到95%以上者設為“>230”。 4)透明性 對於所獲得的帶硬化膜的玻璃基板,利用紫外可見近紅外分光光度計(商品名:V-670,日本分光(股)製造),僅測定硬化膜的在光的波長400 nm下的透光率。若透光率為95%以上,則判斷為透明性良好。將無法充分成膜而無法測定透光率的樣品表示為“-”。 5)保存穩定性 將熱硬化性樹脂組成物的製備時的黏度設為100,將室溫保存7天、14天、30天後的黏度為110以上設為“×”,將室溫保存7天、14天、30天後的黏度為95~105設為“○”。[Method for Evaluating Thermosetting Resin Composition] 1) The film thickness was on a glass substrate (Eagle XG (trade name) manufactured by Corning Co., Ltd., 40 mm × 40 mm × 0.7 mm) The thermosetting resin composition was spin-coated at a predetermined number of revolutions for 10 seconds, and prebaked on a hot plate at 90 ° C for 2 minutes. The substrate was baked on a hot plate at a predetermined temperature for 10 minutes, and the film thickness was measured. The film thickness is measured using a step, surface roughness, and fine shape measuring device (P-16+ (product name), KLA-Tencor Japan Co., Ltd.), and the average value of the three parts is measured. As the film thickness. The number of revolutions was adjusted in such a manner that the film thickness after baking was 3.0 μm. 2) Applicability The cured film formed was observed by visual observation, and the case where the unevenness was not good was set to "○", and the case where the unevenness occurred was set to "△", and the repulsion was caused to be insufficiently formed. The case where the film was on the substrate was set to "x". 3) Sturability The resin film substrate having a film thickness measurement was immersed in a solvent used for a thermosetting resin composition maintained at 24 ° C for 2 minutes. After taking out from the solvent and removing the solvent by blowing, the film thickness was measured, and the residual film ratio = (film thickness after immersion / film thickness before immersion) × 100 was calculated. The measurement was performed at a curing temperature of 100 ° C, 120 ° C, 140 ° C, and 230 ° C, and it was confirmed that the residual film ratio became a post-baking temperature of 95% or more. The case where the cured film cannot be produced is set to "x", and the case where the residual film rate does not reach 95% or more at 230 ° C is set to ">230". 4) Transparency For the obtained glass substrate with a cured film, an ultraviolet visible near-infrared spectrophotometer (trade name: V-670, manufactured by JASCO Corporation) was used to measure only the light wavelength of the cured film at 400 nm. Light transmittance under. When the light transmittance is 95% or more, it is judged that the transparency is good. A sample in which the film could not be sufficiently formed and the light transmittance could not be measured was indicated as "-". 5) Storage stability The viscosity at the time of preparation of the thermosetting resin composition was set to 100, and the viscosity after storage at room temperature for 7 days, 14 days, and 30 days was set to "x" at 110 or more, and the room temperature was stored. The viscosity after days, 14 days, and 30 days was 95 to 105 and was set to "○".
[聚合例1] 在帶攪拌器的四口燒瓶中,一邊使氮氣起泡,一邊加入作為聚合溶劑的18.0 g的丙二醇甲醚、作為單體的4.51 g的亞羅尼斯(Aronix)M-402(商品名,東亞合成股份有限公司)、作為鏈轉移劑的0.90 g的2,4-二苯基-4-甲基-1-戊烯(α-MSD)、作為聚合起始劑的0.23 g的V-65(商品名,和光純藥工業股份有限公司),在35℃下攪拌5分鐘而確認內容物的溶解後,花15分鐘升溫至80℃。繼而,在80℃下加熱3小時而進行聚合。[Polymerization Example 1] In a four-necked flask equipped with a stirrer, 18.0 g of propylene glycol methyl ether as a polymerization solvent and 4.51 g of Aronix M-402 as a monomer were added while bubbling nitrogen gas. (trade name, East Asia Synthetic Co., Ltd.), 0.90 g of 2,4-diphenyl-4-methyl-1-pentene (α-MSD) as a chain transfer agent, and 0.23 g as a polymerization initiator V-65 (trade name, Wako Pure Chemical Industries, Ltd.) was stirred at 35 ° C for 5 minutes to confirm the dissolution of the contents, and then the temperature was raised to 80 ° C for 15 minutes. Then, polymerization was carried out by heating at 80 ° C for 3 hours.
將聚合液冷卻至室溫,獲得聚合體(c1)。對聚合液的一部分進行採樣,通過GPC分析(聚苯乙烯標準)來測定重量平均分子量。其結果為,重量平均分子量為11,800。The polymerization solution was cooled to room temperature to obtain a polymer (c1). A part of the polymerization liquid was sampled, and the weight average molecular weight was measured by GPC analysis (polystyrene standard). As a result, the weight average molecular weight was 11,800.
[聚合例2~聚合例6] 除了如表1所述,變更具有三官能以上的聚合性雙鍵的化合物(a)與聚合條件以外,利用與聚合例1相同的方法來獲得聚合體(c2)~聚合體(c6)。[Polymerization Example 2 to Polymerization Example 6] A polymer (c2) was obtained by the same method as in Polymerization Example except that the compound (a) having a trifunctional or higher polymerizable double bond was changed and the polymerization conditions were changed as described in Table 1. ) - Polymer (c6).
[比較聚合例1] 如表1所述,將具有三官能以上的聚合性雙鍵的化合物(a)變更為具有單官能的聚合性雙鍵的化合物,獲得聚合體(c7)。[Comparative Polymerization Example 1] As described in Table 1, a compound (a) having a trifunctional or higher polymerizable double bond was changed to a compound having a monofunctional polymerizable double bond, and a polymer (c7) was obtained.
[比較聚合例2] 如表1所述,以所獲得的聚合體的重量平均分子量超過200,000的方式獲得聚合體(c8)。[Comparative Polymerization Example 2] As described in Table 1, the polymer (c8) was obtained in such a manner that the weight average molecular weight of the obtained polymer exceeded 200,000.
[比較聚合例3] 如表1所述,除了不使用鏈轉移劑以外,利用與聚合例1相同的方法來進行聚合。在聚合時的升溫的階段確認到凝膠化,無法獲得聚合體溶液。[Comparative Polymerization Example 3] As described in Table 1, the polymerization was carried out by the same method as in Polymerization Example 1, except that the chain transfer agent was not used. Gelation was confirmed at the stage of temperature rise at the time of polymerization, and the polymer solution was not obtained.
表1
表中的略號分別表示以下的單體、聚合起始劑、鏈轉移劑、溶劑等。 M-402:亞羅尼斯(Aronix)M-402(商品名,東亞合成股份有限公司) M-450:亞羅尼斯(Aronix)M-450(商品名,東亞合成股份有限公司) M-520:亞羅尼斯(Aronix)M-520(商品名,東亞合成股份有限公司) BMA:甲基丙烯酸丁酯 MMA:甲基丙烯酸甲酯 V-65:偶氮聚合起始劑V-65(商品名,和光純藥工業股份有限公司) VPE-0201:高分子偶氮起始劑VPE-0201(商品名,和光純藥工業股份有限公司) α-MSD:2,4-二苯基-4-甲基-1-戊烯 PGME:甲基丙二醇(商品名,日本乳化劑股份有限公司)The abbreviations in the tables indicate the following monomers, polymerization initiators, chain transfer agents, solvents, and the like, respectively. M-402: Aronix M-402 (trade name, East Asia Synthetic Co., Ltd.) M-450: Aronix M-450 (trade name, East Asia Synthetic Co., Ltd.) M-520: Aronix M-520 (trade name, East Asia Synthetic Co., Ltd.) BMA: butyl methacrylate MMA: methyl methacrylate V-65: azo polymerization initiator V-65 (trade name, Wako Pure Chemical Industry Co., Ltd.) VPE-0201: Polymer azo initiator VPE-0201 (trade name, Wako Pure Chemical Industries Co., Ltd.) α-MSD: 2,4-diphenyl-4-methyl -1-pentene PGME: methyl propylene glycol (trade name, Japan Emulsifier Co., Ltd.)
[實施例1~實施例6] 對於10 g的聚合液(c1~c6),分別添加0.0011 g的界面活性劑畢克(BYK)-342(商品名,日本畢克化學(BYK-Chemie Japan)股份有限公司),進行所述評價,獲得表2的結果。[Examples 1 to 6] For 10 g of the polymerization liquids (c1 to c6), 0.0011 g of a surfactant, BYK-342, was added, respectively (trade name, BYK-Chemie Japan) Co., Ltd.), the evaluation was carried out, and the results of Table 2 were obtained.
[比較例1及比較例2] 以與實施例相同的方式,對於聚合液(c7)及聚合液(c8),分別添加0.0011 g的畢克(BYK)-342(商品名,日本畢克化學(BYK-Chemie Japan)股份有限公司),進行所述評價,獲得表2的結果。[Comparative Example 1 and Comparative Example 2] In the same manner as in the examples, 0.011 g of BYK-342 was added to the polymerization liquid (c7) and the polymerization liquid (c8) (trade name, Japan BYK Chemical Co., Ltd.) (BYK-Chemie Japan) Co., Ltd.), the evaluation was carried out, and the results of Table 2 were obtained.
表2
如表2的結果所明示,含有實施例1~實施例6的聚合體的熱硬化性組成物表現出低溫硬化性及保存穩定性優異。As is clear from the results of Table 2, the thermosetting composition containing the polymer of Examples 1 to 6 exhibited excellent low-temperature curability and storage stability.
比較例1在聚合體單體中使用具有單官能的聚合性雙鍵的化合物。比較例1中雖然保存穩定性良好,但未表現出如實施例1~實施例6中所示的低溫硬化性,因此顯示出,有效的是在聚合體單體中使用具有三官能以上的聚合性雙鍵的化合物(a)。Comparative Example 1 A compound having a monofunctional polymerizable double bond was used in the polymer monomer. In Comparative Example 1, although the storage stability was good, the low-temperature curability as shown in Examples 1 to 6 was not exhibited, and therefore it was found that it is effective to use a polymerization having a trifunctional or higher function in the polymer monomer. Compound (a) which is a double bond.
比較例2使聚合體的重量平均分子量增大。比較例2中,在保存穩定以及塗佈性方面,未表現出如實施例1~實施例6中所示的良好特性,顯示出聚合體的重量平均分子量重要。Comparative Example 2 increased the weight average molecular weight of the polymer. In Comparative Example 2, good properties as shown in Examples 1 to 6 were not exhibited in terms of storage stability and coatability, and it was revealed that the weight average molecular weight of the polymer was important.
比較聚合例3是不使用鏈轉移劑(b)的聚合。比較聚合例3中在聚合時產生凝膠化,表現出未獲得聚合液。因此顯示出,為了獲得如實施例1~實施例6所示的顯示出良好特性的聚合體,有效的是鏈轉移劑。 [工業上的可利用性]Comparative Polymerization Example 3 is a polymerization which does not use the chain transfer agent (b). In Comparative Polymerization Example 3, gelation occurred at the time of polymerization, and it was revealed that a polymerization liquid was not obtained. Therefore, it has been found that a chain transfer agent is effective in order to obtain a polymer exhibiting good characteristics as shown in Examples 1 to 6. [Industrial availability]
本發明中使用的熱硬化性樹脂組成物及其硬化膜可適用於在需要低溫處理的基板上的硬化膜的製造。例如,可用作保護表面的材料。The thermosetting resin composition used in the present invention and the cured film thereof can be suitably used for the production of a cured film on a substrate requiring low temperature treatment. For example, it can be used as a material to protect the surface.
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