JP6657914B2 - Thermosetting resin composition for color filter protective film, and color filter having the cured film - Google Patents
Thermosetting resin composition for color filter protective film, and color filter having the cured film Download PDFInfo
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- JP6657914B2 JP6657914B2 JP2015245964A JP2015245964A JP6657914B2 JP 6657914 B2 JP6657914 B2 JP 6657914B2 JP 2015245964 A JP2015245964 A JP 2015245964A JP 2015245964 A JP2015245964 A JP 2015245964A JP 6657914 B2 JP6657914 B2 JP 6657914B2
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- Prior art keywords
- color filter
- protective film
- component
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- same
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- 230000001681 protective effect Effects 0.000 title claims description 40
- 239000011342 resin composition Substances 0.000 title claims description 20
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- 125000003700 epoxy group Chemical group 0.000 claims description 12
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 8
- 125000003566 oxetanyl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
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- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
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- 238000000034 method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
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- RVKJZAJQESNAQG-UHFFFAOYSA-N tris(1-propoxyethyl) cyclohexane-1,2,4-tricarboxylate Chemical compound CCCOC(C)OC(=O)C1CCC(C(=O)OC(C)OCCC)C(C(=O)OC(C)OCCC)C1 RVKJZAJQESNAQG-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Optical Filters (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、液晶表示装置などに用いられるカラーフィルター保護膜用として好適な熱硬化性樹脂組成物と、その組成物を硬化してなる保護膜を有するカラーフィルターに関する。 The present invention relates to a thermosetting resin composition suitable for a color filter protective film used in a liquid crystal display device and the like, and a color filter having a protective film obtained by curing the composition.
近年、液晶表示装置が急速に普及したことに伴い、液晶表示装置に用いられる高品質なカラーフィルターの需要も高まっている。カラーフィルターの基本的な構造は、透明基板上に、所定パターンに形成されたブラックマトリックス層、赤色、緑色、青色が所定順序に配列された着色層、及び保護膜を重ねた構造となっている。そのうえでカラーフィルターは、着色層の通過光を赤、緑、青の3つの基本色(RGB画素)とし、それらの光を加法混合することにより、中間色や白色を含む映像の色を作り出している。ここでの保護膜は、液晶表示装置の製造時又は使用時において、カラーフィルターを物理的及び化学的に保護する役割を担っている。そこで、例えばカラーフィルターによる発色の再現性を向上するため、保護膜の透明性あるいは平滑性を改善すると共に、外的衝撃から液晶部を保護するために硬度を高めることが従来から行われてきた(特許文献1)。 In recent years, with the rapid spread of liquid crystal display devices, demand for high quality color filters used in liquid crystal display devices has been increasing. The basic structure of a color filter has a structure in which a black matrix layer formed in a predetermined pattern, a colored layer in which red, green, and blue are arranged in a predetermined order, and a protective film are stacked on a transparent substrate. . In addition, the color filter creates three basic colors of red, green, and blue (RGB pixels) that pass through the colored layer, and creates an image color including an intermediate color and a white color by additively mixing those lights. Here, the protective film plays a role of physically and chemically protecting the color filter when manufacturing or using the liquid crystal display device. Therefore, for example, it has been conventionally performed to improve the transparency or smoothness of the protective film in order to improve the reproducibility of coloring by a color filter, and to increase the hardness in order to protect the liquid crystal portion from external impact. (Patent Document 1).
また、カラーフィルターは、酸・アルカリ溶液への浸漬処理等の過酷な工程を経て製造される。そのため、このような製造過程においてカラーフィルターが劣化したり損傷したりすることによる、性能低下や作動不良を防止する必要がある。そこで、硬化性、密着性、耐ITO(錫ドープ酸化インジウム層)形成プロセス性など、保護膜の様々な性能向上が図られてきた(特許文献2)。 Further, the color filter is manufactured through a severe process such as immersion treatment in an acid / alkali solution. Therefore, it is necessary to prevent performance deterioration and malfunction due to deterioration or damage of the color filter in such a manufacturing process. Therefore, various performance improvements of the protective film such as curability, adhesion, and processability of forming an ITO (tin-doped indium oxide layer) have been attempted (Patent Document 2).
ところで、最近の液晶ディスプレイは、スマートフォンやタブレットなどの携帯端末の波及に伴い、従来以上に高い性能(高画質、高精細等)が要望されている。それに伴い、コントラストの向上が求められ、ブラックマトリックスのOD値(光学濃度)の向上が必須となっている。OD値を向上する手法としては、大別すると、ブラックマトリックスの樹脂中の顔料濃度を上げる手法と、ブラックマトリックスの膜厚を厚くする手法とが挙げられる。前者の手法は、その他物性の低下が懸念されるため、後者の手法が主に適用されている。 By the way, recently, with the spread of mobile terminals such as smartphones and tablets, higher performance (higher image quality, higher definition, etc.) has been demanded for liquid crystal displays. Accordingly, an improvement in contrast is required, and an improvement in the OD value (optical density) of the black matrix is essential. The methods of improving the OD value are roughly classified into a method of increasing the pigment concentration in the resin of the black matrix and a method of increasing the thickness of the black matrix. The former method is mainly applied because there is a concern that other physical properties may be deteriorated.
しかしながら、ブラックマトリックスの膜厚が厚くなると、その上に形成される着色層(RGB画素)の段差が従来よりも大きくなってしまう。そのため、カラーフィルター保護膜の平坦性がより高いことが求められている。カラーフィルター保護膜の平坦性が低いと、液晶配向が乱れることにより液晶表示性能が劣ってしまうからである。 However, when the thickness of the black matrix increases, the level difference of the coloring layer (RGB pixel) formed thereon becomes larger than before. Therefore, higher flatness of the color filter protective film is required. If the flatness of the color filter protective film is low, the liquid crystal display performance is deteriorated due to the disorder of the liquid crystal alignment.
更に近年では、高輝度化、低消費電力化を目的として、「ホワイトマジック」と称される新たな技術を採用したカラーフィルターも登場してきている。「ホワイトマジック」は、従来のRGB画素にW(ホワイト)を加えたRGBW画素となっている。W画素は、大別するとW画素形成時に透明レジストを利用して穴を予め埋める手法と、保護膜のみでW画素を穴埋めする手法とがある。工程数を考慮すると後者が望ましいとされているが、W画素の段差がRGB画素より格段に高くなるため、より一層保護膜に高い平坦性が求められている。 Furthermore, in recent years, a color filter using a new technology called “white magic” has also appeared for the purpose of increasing luminance and reducing power consumption. “White magic” is an RGBW pixel obtained by adding W (white) to a conventional RGB pixel. The W pixels are roughly classified into a method of filling the holes in advance using a transparent resist when forming the W pixels, and a method of filling the W pixels with only the protective film. The latter is considered desirable in consideration of the number of steps. However, since the level difference of the W pixel is much higher than that of the RGB pixel, higher flatness is required for the protective film.
このように、液晶表示装置の性能向上に伴い、カラーフィルター保護膜にもより高い平坦性が求められているが、この要求を実現するためには、従来のカラーフィルター保護膜では十分ではなく、更なる改善が必要であった。 As described above, with the improvement in the performance of the liquid crystal display device, higher flatness is also required for the color filter protective film, but in order to realize this requirement, the conventional color filter protective film is not sufficient, Further improvement was needed.
そこで、本発明の目的とするところは、従来から要求されている平滑性等の基本的物性を維持したまま、平坦性に優れるカラーフィルター保護膜を形成可能な熱硬化性樹脂組成物と、これを硬化させてなる保護膜を備えるカラーフィルターを提供することにある。 Accordingly, an object of the present invention is to provide a thermosetting resin composition capable of forming a color filter protective film having excellent flatness while maintaining basic properties such as smoothness conventionally required. It is to provide a color filter provided with a protective film obtained by curing a color filter.
そのための手段として本発明は、下記の成分(A)〜(C)を含むカラーフィルター保護膜用熱硬化性樹脂組成物であって、成分(A)を5〜50重量部、成分(B)を5〜40重量部、及び成分(C)を25〜80重量部含有し、成分(A)〜(C)の合計は100重量部である。
成分(A):(a1)炭素−炭素不飽和結合とエポキシ基又はオキセタニル基を有するモノマーと、(a2)下記式(1)で表されるモノマーと、(a3)(a1)及び(a2)以外の炭素−炭素不飽和結合を有するモノマーとからなり、(a1)を10〜65質量%、(a2)を10〜60質量%、(a3)を15〜55質量%含み、(a1)、(a2)及び(a3)の合計量が100質量%となる、テトラヒドロフルフリル基含有重合体
(R1は水素またはメチル基。)
成分(B):多価カルボン酸無水物又は多価ブロックカルボン酸
成分(C):一分子中にエポキシ基を2個以上有する多官能エポキシ樹脂
As means for that purpose, the present invention provides a thermosetting resin composition for a color filter protective film containing the following components (A) to (C), wherein component (A) is 5 to 50 parts by weight, component (B) Is contained in an amount of 5 to 40 parts by weight, and the component (C) is contained in an amount of 25 to 80 parts by weight.
Component (A): (a1) a monomer having a carbon-carbon unsaturated bond and an epoxy group or an oxetanyl group; (a2) a monomer represented by the following formula (1); (a3) (a1) and (a2) (A1) is 10 to 65% by mass, (a2) is 10 to 60% by mass, (a3) is 15 to 55% by mass, and (a1) Tetrahydrofurfuryl group-containing polymer in which the total amount of (a2) and (a3) is 100% by mass
(R 1 is hydrogen or a methyl group.)
Component (B): polycarboxylic acid anhydride or polyvalent block carboxylic acid Component (C): polyfunctional epoxy resin having two or more epoxy groups in one molecule
また、本発明によれば、上記カラーフィルター保護膜用熱硬化性樹脂組成物を硬化させてなる保護膜を有する、カラーフィルターも提供することができる。 Further, according to the present invention, it is possible to provide a color filter having a protective film obtained by curing the thermosetting resin composition for a color filter protective film.
なお、本発明において数値範囲を示す「○○〜××」とは、特に明示しない限り「○○以上××以下」を意味する。 In the present invention, “XX to XX” indicating a numerical range means “XX or more and XX or less” unless otherwise specified.
本発明のカラーフィルター保護膜用熱硬化性樹脂組成物によれば、平滑性、透明性、膜硬度等の基本的物性を維持したまま、平坦性に優れるカラーフィルター保護膜を形成することができる。特に、成分(A)として、特定構造の成分(a2)を所定量含有する重合体を用いることで、平坦性が高い。 According to the thermosetting resin composition for a color filter protective film of the present invention, a color filter protective film having excellent flatness can be formed while maintaining basic properties such as smoothness, transparency, and film hardness. . Particularly, by using a polymer containing a predetermined amount of the component (a2) having a specific structure as the component (A), the flatness is high.
≪カラーフィルター保護膜用熱硬化性樹脂組成物≫
本発明の熱硬化性樹脂組成物は、カラーフィルターの保護膜として好適に使用できるものである。基本的組成を構成する必須成分として、(A)テトラヒドロフルフリル基含有重合体、(B)多価カルボン酸無水物又は多価ブロックカルボン酸化合物、及び(C)一分子中にエポキシ基を2個以上有する多官能エポキシ樹脂を含む。
熱 Thermosetting resin composition for color filter protective film≫
The thermosetting resin composition of the present invention can be suitably used as a protective film for a color filter. The essential components constituting the basic composition are (A) a polymer containing a tetrahydrofurfuryl group, (B) a polycarboxylic acid anhydride or a polyvalent block carboxylic acid compound, and (C) an epoxy group in one molecule. Includes multi-functional epoxy resin with more than one.
<(A)テトラヒドロフルフリル基含有重合体>
成分(A)は、(a1)炭素−炭素不飽和結合とエポキシ基又はオキセタニル基とを有するモノマー、(a2)所定構造のモノマー(詳細は後述する)、及び(a3)(a1)及び(a2)以外の炭素−炭素不飽和結合を有するモノマーを共重合した共重合体である。
<(A) Tetrahydrofurfuryl group-containing polymer>
Component (A) includes (a1) a monomer having a carbon-carbon unsaturated bond and an epoxy group or an oxetanyl group, (a2) a monomer having a predetermined structure (details will be described later), and (a3) (a1) and (a2). ) Is a copolymer obtained by copolymerizing a monomer having a carbon-carbon unsaturated bond other than the above.
(a1)炭素−炭素不飽和結合とエポキシ基又はオキセタニル基を有するモノマーは、炭素−炭素不飽和結合と、エポキシ基又はオキセタニル基とを有していれば良く、このような用途に周知のいかなるモノマーも利用することができる。 (A1) The monomer having a carbon-carbon unsaturated bond and an epoxy group or an oxetanyl group only needs to have a carbon-carbon unsaturated bond and an epoxy group or an oxetanyl group. Monomers can also be utilized.
エポキシ基を有するモノマーとしては、例えば下記の式(2)〜(4)で表されるモノマーが好ましい例として挙げられる。
(式中、R2は水素原子またはメチル基、kは1〜5の整数を示す。)
(式中、R3は水素原子またはメチル基、R4は−CH2O−基または−CH2−基、R5は水素原子または炭素数1〜2のアルキル基、mは1〜7の整数を示す。)
(式中、R6は水素原子またはメチル基、nは1〜8の整数を示す。)
Preferred examples of the monomer having an epoxy group include monomers represented by the following formulas (2) to (4).
(In the formula, R 2 represents a hydrogen atom or a methyl group, and k represents an integer of 1 to 5.)
(Wherein, R 3 is a hydrogen atom or a methyl group, R 4 is a —CH 2 O— group or a —CH 2 — group, R 5 is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and m is a 1 to 7 Indicates an integer.)
(In the formula, R 6 represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 8.)
また、オキセタニル基を有するモノマーとしては、例えば下記の式(5)で表されるモノマーが好ましい例として挙げられる。
(式中、R7、R8、R9は水素原子またはメチル基、jは1〜8の整数を示す。)
As a monomer having an oxetanyl group, for example, a monomer represented by the following formula (5) is a preferred example.
(In the formula, R 7 , R 8 , and R 9 represent a hydrogen atom or a methyl group, and j represents an integer of 1 to 8.)
(a2)としては、下記の式(1)で表されるモノマーを使用する。
(R1は水素またはメチル基。)
As (a2), a monomer represented by the following formula (1) is used.
(R 1 is hydrogen or a methyl group.)
(a3)(a1)及び(a2)以外の炭素−炭素不飽和結合を有するモノマーは、炭素−炭素不飽和結合を有し、(a1)及び(a2)に該当しない化合物であれば良く、このような用途に周知のいかなるモノマーも利用することができる。例えば、下記の式(6)〜(9)で表されるモノマーが挙げられる。
(式中、R10は水素原子またはメチル基、R11は炭素数1〜12のアルキル基、アリール基、アリールオキシ基、ヒドロキシアルキル基、またはポリアルキレングリコール残基、もしくは主環構成炭素数3〜12の脂環式炭素水素基を示す。)
(式中、R12は水素原子または炭素数1〜5のアルキル基、R13は炭素数1〜12のアルキル基、アルコキシ基、ヒドロキシアルキル基、ヒドロキシル基、シロキシアルキル基、または芳香族炭化水素基を示す。)
(式中、R14は水素原子または炭素数1〜12のアルキル基、シクロアルキル基、または芳香族炭化水素基を示す。)
(式中、R15は水素原子またはメチル基、pは1〜5の整数、R16、R17、R18は、それぞれ独立にメチル基またはエチル基を示す。)
(A3) The monomer having a carbon-carbon unsaturated bond other than (a1) and (a2) may be any compound having a carbon-carbon unsaturated bond and not falling under (a1) and (a2). Any monomer known for such an application can be utilized. For example, monomers represented by the following formulas (6) to (9) are exemplified.
(In the formula, R 10 is a hydrogen atom or a methyl group, R 11 is an alkyl group having 1 to 12 carbon atoms, an aryl group, an aryloxy group, a hydroxyalkyl group, a polyalkylene glycol residue, or a main ring carbon number 3 ~ 12 alicyclic hydrocarbon groups.)
(Wherein, R 12 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R 13 is an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a hydroxyalkyl group, a hydroxyl group, a siloxyalkyl group, or an aromatic hydrocarbon. Represents a group.)
(In the formula, R 14 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or an aromatic hydrocarbon group.)
(In the formula, R 15 is a hydrogen atom or a methyl group, p is an integer of 1 to 5, and R 16 , R 17 , and R 18 each independently represent a methyl group or an ethyl group.)
(A)テトラヒドロフルフリル基含有重合体は、(a1)〜(a3)を重合することによって得ることができる。その際、成分(A)中における(a1)の含有量が10〜65質量%、(a2)の含有量が10〜60質量%、(a3)の含有量が15〜55質量%であって、(a1)、(a2)及び(a3)の合計量が100質量%であれば、最終的に得られる保護膜において優れた平坦性を得ることができる。成分(A)の重合態様としては、直鎖状であっても分岐していても良い。なお、(a1)〜(a3)は、それぞれ単独でも2種以上を併用しても良い。分岐している重合態様とは、例えば、成長が終了している重合体のメチレン水素が、重合開始剤由来のラジカルに引き抜かれると炭素上にラジカルが発生し、そのラジカルが成長過程の重合体と再結合する場合である。 (A) The tetrahydrofurfuryl group-containing polymer can be obtained by polymerizing (a1) to (a3). At that time, the content of (a1) in the component (A) is 10 to 65% by mass, the content of (a2) is 10 to 60% by mass, and the content of (a3) is 15 to 55% by mass. If the total amount of (a1), (a2) and (a3) is 100% by mass, excellent flatness can be obtained in the finally obtained protective film. The polymerization mode of the component (A) may be linear or branched. (A1) to (a3) may be used alone or in combination of two or more. The branched polymerization mode is, for example, a radical is generated on carbon when methylene hydrogen of a polymer whose growth is terminated is extracted by a radical derived from a polymerization initiator, and the radical is a polymer in the growth process. This is the case when recombining.
(a1)〜(a3)の重合方法は特に限定されず、ラジカル重合、イオン重合等の重合法を用いることができる。より具体的には、重合開始剤の存在下において、塊状重合法、溶液重合法、懸濁重合法、乳化重合法などの重合法を用いることができる。また、必要に応じて触媒や溶媒などの添加物を重合反応系に添加しても良い。(A)テトラヒドロフルフリル基含有重合体の重量平均分子量(Mw)は、3,000〜100,000を目安とすればよい。 The polymerization methods (a1) to (a3) are not particularly limited, and polymerization methods such as radical polymerization and ionic polymerization can be used. More specifically, polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used in the presence of a polymerization initiator. If necessary, additives such as a catalyst and a solvent may be added to the polymerization reaction system. (A) The weight average molecular weight (Mw) of the tetrahydrofurfuryl group-containing polymer may be about 3,000 to 100,000.
<(B)多価カルボン酸無水物又は多価ブロックカルボン酸>
成分(B)としては、多価カルボン酸無水物又は多価ブロックカルボン酸を使用することができる。平坦性を良くしたい場合は、多価カルボン酸無水物の方が好ましい。多価カルボン酸無水物としては、炭素数4〜20で2〜8価のカルボン酸の無水物であることが好ましい。好ましい例としては、直鎖または分岐を有する脂肪族多価カルボン酸、脂環式多価カルボン酸、芳香族多価カルボン酸等の無水物が挙げられる。脂肪族多価カルボン酸としては、例えばイタコン酸、マレイン酸、コハク酸、シトラコン酸等が挙げられる。脂環式多価カルボン酸としては、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メチルテトラヒドロフタル酸、シクロヘキサンジカルボン酸、シクロペンタンテトラカルボン酸、シクロヘキサントリカルボン酸等が挙げられる。芳香族多価カルボン酸としては、フタル酸、テレフタル酸、イソフタル酸、メリット酸、トリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸等が挙げられる。
<(B) polyvalent carboxylic anhydride or polyvalent block carboxylic acid>
As the component (B), a polyvalent carboxylic anhydride or a polyvalent block carboxylic acid can be used. In order to improve the flatness, polycarboxylic anhydrides are more preferable. The polycarboxylic anhydride is preferably an anhydride of a dicarboxylic acid having 2 to 8 carbon atoms and 4 to 20 carbon atoms. Preferred examples include anhydrides such as linear or branched aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, and aromatic polycarboxylic acids. Examples of the aliphatic polycarboxylic acid include itaconic acid, maleic acid, succinic acid, and citraconic acid. Examples of the alicyclic polycarboxylic acid include tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, cyclohexanedicarboxylic acid, cyclopentanetetracarboxylic acid, and cyclohexanetricarboxylic acid. Examples of the aromatic polycarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, melitic acid, trimellitic acid, pyromellitic acid, and benzophenonetetracarboxylic acid.
多価ブロックカルボン酸としては、例えば、上記多価カルボン酸のカルボキシル基をビニルエーテル化合物によりヘミアセタールエステルとして潜在化、すなわちブロック化したビニルエーテルブロック多価カルボン酸化合物を挙げることができる。 Examples of the polyvalent block carboxylic acid include a vinyl ether block polyvalent carboxylic acid compound in which the carboxyl group of the above polyvalent carboxylic acid is latentized as a hemiacetal ester by a vinyl ether compound, that is, the carboxylic acid is blocked.
ビニルエーテル化合物としては、例えばメチルビニルエーテル、エチルビニルエーテル、i−プロピルビニルエーテル、n−プロピルビニルエーテル、n−ブチルビニルエーテル、i−ブチルビニルエーテル、t−ブチルビニルエーテル、2−エチルヘキシルビニルエーテル、シクロヘキシルビニルエーテル等の脂肪族ビニルエーテル化合物が挙げられる。これらの中でも、入手性および硬化温度が保護膜のプロセスに適合する点から、n−プロピルビニルエーテルおよびi−プロピルビニルエーテルが好ましく挙げられる。なお、ビニルエーテル化合物は、単独で、または2種以上を組み合わせて用いることができる。 Examples of the vinyl ether compound include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, i-propyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, and cyclohexyl vinyl ether. Is mentioned. Among these, n-propyl vinyl ether and i-propyl vinyl ether are preferred from the viewpoint that the availability and the curing temperature are compatible with the process of the protective film. In addition, a vinyl ether compound can be used individually or in combination of 2 or more types.
多価ブロックカルボン酸化合物は、多価カルボン酸とビニルエーテル化合物とを室温ないし150℃の範囲の温度で反応させることによって得ることができる。ブロック化反応は平衡反応であるため、多価カルボン酸に対してビニルエーテル化合物を若干多くすると反応が促進され、収率を向上させることができる。なお、多価カルボン酸とビニルエーテル化合物との反応には、目的に応じて触媒や溶媒を添加することもできる。 The polyvalent block carboxylic acid compound can be obtained by reacting a polyvalent carboxylic acid with a vinyl ether compound at a temperature in the range of room temperature to 150 ° C. Since the blocking reaction is an equilibrium reaction, if the amount of the vinyl ether compound is slightly increased with respect to the polyvalent carboxylic acid, the reaction is accelerated and the yield can be improved. In the reaction between the polyvalent carboxylic acid and the vinyl ether compound, a catalyst or a solvent may be added according to the purpose.
触媒としては、3級アミン類、イミダゾール類、有機リン系化合物、4級ホスホニウム塩類、ジアザビシクロアルケン類、有機金属化合物類、4級アンモニウム塩類、ホウ素化合物、金属ハロゲン化物等が挙げられる。 Examples of the catalyst include tertiary amines, imidazoles, organic phosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, organometallic compounds, quaternary ammonium salts, boron compounds, metal halides, and the like.
溶媒としては、芳香族炭化水素、エーテル類、エステルおよびエーテルエステル類、ケトン類、リン酸エステル類、ニトリル類、非プロトン性極性溶媒、プロピレングリコールアルキルエーテルアセテート類等が挙げられる。 Examples of the solvent include aromatic hydrocarbons, ethers, esters and ether esters, ketones, phosphates, nitriles, aprotic polar solvents, propylene glycol alkyl ether acetates, and the like.
<(C)多官能エポキシ樹脂>
成分(C)としては、一分子中にエポキシ基を2個以上有する多官能エポキシ樹脂を使用する。例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、臭素化ビスフェノールA型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ樹脂、3官能型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、ジシクロペンタジエンフェノール型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビスフェノールA含核ポリオール型エポキシ樹脂、ポリプロピレングリコール型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリオキザール型エポキシ樹脂、脂環式型エポキシ樹脂、複素環型エポキシ樹脂などが挙げられる。なお、(C)多官能エポキシ樹脂は、単独で用いても2種以上を組み合わせて用いても良い。
<(C) polyfunctional epoxy resin>
As the component (C), a polyfunctional epoxy resin having two or more epoxy groups in one molecule is used. For example, bisphenol A epoxy resin, bisphenol F epoxy resin, brominated bisphenol A epoxy resin, bisphenol S epoxy resin, diphenyl ether epoxy resin, hydroquinone epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, fluorene epoxy resin Epoxy resin, phenol novolak type epoxy resin, orthocresol novolak type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, hydrogenated bisphenol A Epoxy resin, bisphenol A nucleated polyol epoxy resin, polypropylene glycol epoxy resin, glycidyl ester epoxy Fat, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. The polyfunctional epoxy resin (C) may be used alone or in combination of two or more.
<添加剤>
本発明の熱硬化性樹脂組成物には、必要に応じてレベリング剤、シランカップリング剤、触媒、安定剤、溶剤等を添加することができる。また、本発明の硬化を損なわない範囲において、炭酸ガス発生防止剤、可撓性付与剤、酸化防止剤、可塑剤、滑剤、表面処理剤、難燃剤、帯電防止剤、着色剤、イオントラップ剤、摺動性改良剤、耐衝撃性改良剤、揺変性付与剤、界面活性剤、表面張力低下剤、消泡剤、沈降防止剤、光拡散剤、紫外線吸収剤、抗酸化剤、離型剤、蛍光剤等も添加することができる。
<Additives>
If necessary, a leveling agent, a silane coupling agent, a catalyst, a stabilizer, a solvent, and the like can be added to the thermosetting resin composition of the present invention. In addition, as long as the curing of the present invention is not impaired, a carbon dioxide generation inhibitor, a flexibility imparting agent, an antioxidant, a plasticizer, a lubricant, a surface treatment agent, a flame retardant, an antistatic agent, a coloring agent, and an ion trapping agent , Sliding property improver, impact resistance improver, thixotropic agent, surfactant, surface tension lowering agent, defoamer, anti-settling agent, light diffusing agent, ultraviolet absorber, antioxidant, release agent , A fluorescent agent and the like can also be added.
レベリング剤は、得られる保護膜の外観を向上させる目的で配合されるものであって、シリコン系、フッ素系、アクリル系等を特に制限無く使用することができる。レベリング剤の市販品としては、例えばメガファックF−410(DIC(株))、同F−430(同)、同F−444(同)、同F−472SF(同)、同F−477(同)、同F−552(同)、同F−553(同)、同F−554(同)、同F−555(同)、同F−556(同)、同F−558(同)、同F−559(同)、同F−561(同)、同R−94(同)、同RS−72−K(同)、同RS−75(同)、ノベックFC−4430(住友スリーエム(株))、FC−4432(同)、サーフロンS−611(AGCセイミケミカル(株))、同S−651(同)、S−386(同)、フタージェント208G(ネオス(株))、同209F(同)、同212P(同)、同220P(同)、同222F(同)、同228P(同)、同240G(同)、同602A(同)、同650A(同)、同710FL(同)、同710FM(同)、FTX−218(同)、BYK―302(ビックケミー・ジャパン(株))、BYK−307(同)、BYK−315(同)、BYK−320(同)、BYK−322(同)、BYK−323(同)、BYK−325(同)、BYK−330(同)、BYK−331(同)、BYK−337(同)、BYK−347(同)、BYK−370(同)、BYK−UV3500(同)、BYK−UV3510(同)、BYK−350(同)、BYK−354(同)、BYK−392(同)、ポリフローKL−400HF(共栄社化学(株))、同KL−401(同)、同KL−402(同)、同KL−403(同)、同KL−404(同)、同KL−100(同)、同KL−600(同)、同KL−700(同)、同WS−30(同)、同No.75(同)、同No.77(同)、同No.90(同)、同No.95(同)、同LE−604(同)等を使用できる。これらレベリング剤は、単独でも2種以上を併用しても良い。 The leveling agent is compounded for the purpose of improving the appearance of the obtained protective film, and a silicon-based, fluorine-based, acrylic-based or the like can be used without any particular limitation. Commercially available leveling agents include, for example, Megafac F-410 (DIC), F-430 (f), F-444 (f), F-472SF (f), and F-577 (f). F-552 (same), F-553 (same), F-554 (same), F-555 (same), F-556 (same), F-558 (same) F-559 (same), F-561 (same), R-94 (same), RS-72-K (same), RS-75 (same), Novec FC-4430 (Sumitomo 3M) Co., Ltd.), FC-4432 (same), Surflon S-611 (AGC Seimi Chemical Co., Ltd.), S-651 (same), S-386 (same), Futergent 208G (Neos Co., Ltd.), 209F (same), 212P (same), 220P (same), 222F (same), 228P (same) 240G (same), 602A (same), 650A (same), 710FL (same), 710FM (same), FTX-218 (same), BYK-302 (Big Chemie Japan KK), BYK-307 (same), BYK-315 (same), BYK-320 (same), BYK-322 (same), BYK-323 (same), BYK-325 (same), BYK-330 (same), BYK -331 (same), BYK-337 (same), BYK-347 (same), BYK-370 (same), BYK-UV3500 (same), BYK-UV3510 (same), BYK-350 (same), BYK- 354 (same), BYK-392 (same), Polyflow KL-400HF (Kyoeisha Chemical Co., Ltd.), KL-401 (same), KL-402 (same), KL-403 (same), KL −404 (same), KL-100 (same), KL-600 (same), KL-700 (same), WS-30 (same), the same No. No. 75 (same), No. 75 No. 77 (same as above); 90 (the same), No. 95 (same), LE-604 (same) and the like can be used. These leveling agents may be used alone or in combination of two or more.
シランカップリング剤は、シランを利用して有機材料と無機材料とを結合する連結剤である。有機材料と反応結合する官能基として、一般にビニル基、エポキシ基、アミノ基などを有する。これらシランカップリング剤は、単独でも2種以上を併用しても良い。 The silane coupling agent is a linking agent that binds an organic material and an inorganic material using silane. As a functional group that reacts with an organic material, it generally has a vinyl group, an epoxy group, an amino group, and the like. These silane coupling agents may be used alone or in combination of two or more.
触媒としては、3級アミン類、イミダゾール類、有機リン系化合物、4級ホスホニウム塩類、ジアザビシクロアルケン類、及び有機金属化合物類などが挙げられる。これら触媒は、単独でも2種以上を併用しても良い。 Examples of the catalyst include tertiary amines, imidazoles, organic phosphorus compounds, quaternary phosphonium salts, diazabicycloalkenes, and organometallic compounds. These catalysts may be used alone or in combination of two or more.
溶剤は、熱硬化性樹脂組成物の使用に際して粘度等を調整する目的で添加される。具体的には、芳香族炭化水素、エーテル類、エステル及びエーテルエステル類、ケトン類、リン酸エステル類、非プロトン性極性溶剤、グリコール誘導体等が挙げられる。これら溶剤は、単独でも2種以上を併用しても良い。 The solvent is added for the purpose of adjusting the viscosity and the like when the thermosetting resin composition is used. Specific examples include aromatic hydrocarbons, ethers, esters and ether esters, ketones, phosphates, aprotic polar solvents, glycol derivatives and the like. These solvents may be used alone or in combination of two or more.
炭酸ガス発生防止剤としては、例えばエチレングリコール、プロピレングリコール等の脂肪族ポリオール、脂肪族または芳香族カルボン酸化合物、フェノール化合物等を挙げることができる。可撓性付与剤としては、例えばポリアルキレングリコール等を挙げることができる。耐衝撃性改良剤としては、例えば各種ゴム、有機ポリマービーズ、ガラスビーズ、グラスファイバー等の無機充填材を挙げることができる。 Examples of the carbon dioxide gas generation inhibitor include aliphatic polyols such as ethylene glycol and propylene glycol, aliphatic or aromatic carboxylic acid compounds, and phenol compounds. Examples of the flexibility imparting agent include polyalkylene glycol and the like. Examples of the impact resistance improver include inorganic fillers such as various rubbers, organic polymer beads, glass beads, and glass fibers.
(カラーフィルター保護膜用熱硬化性樹脂組成物の製造)
カラーフィルター保護膜用熱硬化性樹脂組成物は、成分(A)〜(C)の合計100重量部中に、成分(A)を5〜50重量部、成分(B)を5〜40重量部、及び成分(C)を25〜80重量部含有する。各成分の含有量がこの範囲を外れると、得られる保護膜の平滑性、平坦性、透明性、膜硬度のいずれかにおいて求める物性が得られなくなるおそれがある。
(Production of thermosetting resin composition for color filter protective film)
The thermosetting resin composition for a color filter protective film comprises 5 to 50 parts by weight of the component (A) and 5 to 40 parts by weight of the component (B) in a total of 100 parts by weight of the components (A) to (C). , And 25 to 80 parts by weight of the component (C). If the content of each component is out of this range, physical properties required in any of smoothness, flatness, transparency, and film hardness of the obtained protective film may not be obtained.
(カラーフィルター保護膜の形成)
カラーフィルターは、上記熱硬化性樹脂組成物を硬化させてなる硬化物の層を、保護膜として備える。熱硬化性樹脂組成物は、基板上に配置された着色層やブラックマトリックス層を覆うように塗布される。その塗布方法は特に限定されることは無く、グラビアコート法、スピンコート法、ダイコート法等の従来公知の塗工方法を採用することができる。
(Formation of color filter protective film)
The color filter includes, as a protective film, a layer of a cured product obtained by curing the thermosetting resin composition. The thermosetting resin composition is applied so as to cover the colored layer and the black matrix layer disposed on the substrate. The coating method is not particularly limited, and a conventionally known coating method such as a gravure coating method, a spin coating method, and a die coating method can be employed.
得られた塗膜を乾燥し、さらに必要に応じて予備加熱(プリベーク)を行った後、本硬化加熱(ポストベーク)を経て樹脂硬化物の層を形成する。プリベーク条件は、40〜140℃、0〜1時間とすればよい。ポストベーク条件は、150〜280℃、0.2〜2時間とすればよい。加熱手法は特に限定されるものではなく、例えば密閉式硬化炉や連続硬化が可能なトンネル炉等の硬化装置を採用することができる。加熱源は特に制約されることなく、熱風循環、赤外線加熱、高周波加熱等の方法で行うことができる。 The obtained coating film is dried and, if necessary, preheated (prebaked), followed by full curing heating (postbaked) to form a layer of a cured resin. The pre-bake conditions may be 40 to 140 ° C. and 0 to 1 hour. Post-bake conditions may be 150 to 280 ° C. and 0.2 to 2 hours. The heating method is not particularly limited, and for example, a curing device such as a closed curing furnace or a tunnel furnace capable of continuous curing can be employed. The heating source is not particularly limited, and the heating can be performed by a method such as hot air circulation, infrared heating, or high-frequency heating.
以下に、実施例及び比較例を挙げて本発明を具体的に説明するが、本発明はこれらに限られるものではない。
<重合例−1:テトラヒドロフルフリル基含有重合体(A−1)の合成>
温度計、還流冷却器、攪拌機、滴下ロートを備えた容量300mLの4つ口フラスコに、溶剤としてプロピレングリコールモノメチルエーテルアセテート(PGMEA)を76.0重量部仕込み、攪拌しながら加熱して90℃に昇温した。次いで、90℃の温度で、単量体成分(a1)として(3-エチルオキセタン-3-イル)メチルメタクリレート(OXE−30)22.5重量部、単量体成分(a2)としてテトラヒドロフルフリルメタクリレート(THFMA)36.5重量部、単量体成分(a3)としてブチルアクリレート(BA)41.0重量部、過酸化物系重合開始剤(日油(株)製「パーヘキシルO」)6.0重量部、及びPGMEA18.0重量部を予め均一混合したもの(滴下成分)を、2時間かけて滴下ロートより等速滴下した。その後、90℃の温度を5時間維持し、重量平均分子量(Mw)20,000の、エポキシ基を有する重合体(A−1)の50%PGMEA溶液を得た。
Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
<Polymerization Example 1: Synthesis of tetrahydrofurfuryl group-containing polymer (A-1)>
In a 300 mL four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 76.0 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was charged as a solvent, and heated to 90 ° C. while stirring. The temperature rose. Then, at a temperature of 90 ° C., 22.5 parts by weight of (3-ethyloxetane-3-yl) methyl methacrylate (OXE-30) as the monomer component (a1) and tetrahydrofurfuryl as the monomer component (a2) 5. methacrylate (THFMA) 36.5 parts by weight, butyl acrylate (BA) 41.0 parts by weight as a monomer component (a3), peroxide-based polymerization initiator (“Perhexyl O” manufactured by NOF Corporation) A mixture obtained by uniformly mixing 0 parts by weight and 18.0 parts by weight of PGMEA (dropping components) was dropped at a constant speed from the dropping funnel over 2 hours. Thereafter, the temperature of 90 ° C. was maintained for 5 hours to obtain a 50% PGMEA solution of the polymer (A-1) having an epoxy group and having a weight average molecular weight (Mw) of 20,000.
<重合例−2〜10:テトラヒドロフルフリル基含有重合体(A−2〜A−10)の合成>
表1に示す原料を表1に示す条件で混合し、重合例−1と同様の方法でA−2〜A−10の重合体溶液を得た。なお、表1において組成(各成分の含有量)を示す数値は重量部である。また、表1中の略号は次の通りである。
GMA:グリシジルメタクリレート
4HBAGE:4−ヒドロキシブチルアクリレートグリシジルエーテル
OXE−30:(3-エチルオキセタン-3-イル)メチルメタクリレート
OXE−10:(3-エチルオキセタン-3-イル)メチルアクリレート
THFMA:テトラヒドロフルフリルメタクリレート
BA:ブチルアクリレート
BMA:ブチルメタクリレート
St:スチレン
CHMA:シクロヘキシルメタクリレート
CHMI:シクロヘキシルマレイミド
パーヘキシルO:日油(株)製の過酸化物系重合開始剤
PGMEA:プロピレングリコールモノメチルエーテルアセテート
<Polymerization Examples-2 to 10: Synthesis of Tetrahydrofurfuryl Group-Containing Polymers (A-2 to A-10)>
The raw materials shown in Table 1 were mixed under the conditions shown in Table 1, and polymer solutions A-2 to A-10 were obtained in the same manner as in Polymerization Example-1. In Table 1, numerical values indicating the composition (content of each component) are parts by weight. Abbreviations in Table 1 are as follows.
GMA: glycidyl methacrylate 4HBAGE: 4-hydroxybutyl acrylate glycidyl ether OXE-30: (3-ethyloxetane-3-yl) methyl methacrylate OXE-10: (3-ethyloxetane-3-yl) methyl acrylate THFMA: tetrahydrofurfuryl Methacrylate BA: Butyl acrylate BMA: Butyl methacrylate St: Styrene CHMA: Cyclohexyl methacrylate CHMI: Cyclohexyl maleimide Perhexyl O: Peroxide polymerization initiator manufactured by NOF Corporation PGMEA: Propylene glycol monomethyl ether acetate
なお、重量平均分子量(Mw)は、東ソー(株)製ゲルパーミエーションクロマトグラフィー装置HLC−8220GPCを用いて、カラムとして東ソー(株)製「TSKgel HZM−M」を用い、THFを溶離液とし、RI検出器により測定してポリスチレン換算により求めた。 The weight average molecular weight (Mw) was measured using a gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh Corporation, using TSKgel HZM-M manufactured by Tosoh Corporation as a column, and using THF as an eluent. It was measured with an RI detector and determined in terms of polystyrene.
<比較重合例−1〜6:比較重合体(A′−1〜A′−6)の合成>
表2に示す原料を表2に示す条件で混合し、重合例−1と同様の方法でA′−1〜A′−6の比較重合体溶液を得た。なお、表2において組成(各成分の含有量)を示す数値は重量部である。また、表1には記載されていない表2中の略号は次の通りである。
MSMA:メチルセロソルブメタクリレート
MPEGA:メトキシポリエチレングリコールアクリレート
PhMA:フェノキシメタクリレート
<Comparative Polymerization Examples -1 to 6: Synthesis of Comparative Polymers (A'-1 to A'-6)>
The raw materials shown in Table 2 were mixed under the conditions shown in Table 2, and comparative polymer solutions of A'-1 to A'-6 were obtained in the same manner as in Polymerization Example-1. In Table 2, the numerical values indicating the composition (content of each component) are parts by weight. Abbreviations in Table 2 not described in Table 1 are as follows.
MSMA: Methyl cellosolve methacrylate MPEGA: Methoxy polyethylene glycol acrylate PhMA: Phenoxy methacrylate
<実施例1〜10、比較例1〜10>
表3及び表4に示す各成分を表3及び表4に示す配合量で溶解混合し、実施例1〜10及び比較例1〜10用のカラーフィルター保護膜用樹脂組成物の塗工液を調整した。なお、表3及び表4において、各成分の含有量を示す数値は重量部である。また、表3及び表4中の略号は次の通りである。
<Examples 1 to 10, Comparative Examples 1 to 10>
The components shown in Tables 3 and 4 were dissolved and mixed in the amounts shown in Tables 3 and 4, and the coating liquids of the color filter protective film resin compositions for Examples 1 to 10 and Comparative Examples 1 to 10 were prepared. It was adjusted. In Tables 3 and 4, numerical values indicating the content of each component are parts by weight. Abbreviations in Tables 3 and 4 are as follows.
<多価カルボン酸無水物(B)>
CHTA−an:シクロヘキサン−1,2,4−トリカルボン酸−1,2−無水物
TMA−an:トリメリット酸無水物
<多価ブロックカルボン酸(B)>
TMA−NPVE(トリメリット酸をノルマルプロピルビニルエーテルでブロックした化合物):1,2,4−ベンゼントリカルボン酸−1,2,4−トリス(1−プロポキシエチル)エステル
CHTA−NPVE(シクロヘキサントリカルボン酸をノルマルプロピルビニルエーテルでブロックした化合物):1,2,4−シクロヘキサントリカルボン酸−1,2,4−トリス(1−プロポキシエチル)エステル
CHTA−IPVE(シクロヘキサントリカルボン酸をイソプロピルビニルエーテルでブロックした化合物):1,2,4−シクロヘキサントリカルボン酸−1,2,4−トリス[1−(1−メチルエトキシ)エチル]エステル
TMA−IPVE(トリメリット酸をイソプロピルビニルエーテルでブロックした化合物):1,2,4−ベンゼントリカルボン酸−1,2,4−トリス[1−(1−メチルエトキシ)エチル]エステル
<Polycarboxylic anhydride (B)>
CHTA-an: cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride TMA-an: trimellitic anhydride <polyvalent block carboxylic acid (B)>
TMA-NPVE (a compound in which trimellitic acid is blocked with normal propyl vinyl ether): 1,2,4-benzenetricarboxylic acid-1,2,4-tris (1-propoxyethyl) ester CHTA-NPVE (cyclohexane tricarboxylic acid is normal) Compound blocked with propyl vinyl ether): 1,2,4-cyclohexanetricarboxylic acid-1,2,4-tris (1-propoxyethyl) ester CHTA-IPVE (compound obtained by blocking cyclohexanetricarboxylic acid with isopropyl vinyl ether): 1, 2,4-cyclohexanetricarboxylic acid-1,2,4-tris [1- (1-methylethoxy) ethyl] ester TMA-IPVE (compound obtained by blocking trimellitic acid with isopropyl vinyl ether): 1,2,2 - benzenetricarboxylic acid, 2,4-tris [1- (1-methylethoxy) ethyl] ester
<多官能エポキシ樹脂(C)>
Ep−157:ビスフェノールAノボラック型エポキシ化合物(三菱化学(株)製、商品名:「jER 157S70」、エポキシ当量210g/eq)
Cel2021P:3’,4’−エポキシシクロヘキシルメチル3,4−エポキシシクロヘキサンカルボキシレート(ダイセル化学工業(株)製、商品名:「セロキサイド2021P」、エポキシ当量130g/eq)
CG−500: ナフチル基含有フルオレン型エポキシ化合物(大阪ガスケミカル(株)製、商品名:「OGSOL CG−500」、エポキシ当量311g/eq)
VG3101L:グリシジルエーテル型エポキシ化合物((株)プリンテック製、商品名:「テクモアVG3101L」、エポキシ当量210g/eq)
<Polyfunctional epoxy resin (C)>
Ep-157: bisphenol A novolak type epoxy compound (manufactured by Mitsubishi Chemical Corporation, trade name: “jER157S70”, epoxy equivalent 210 g / eq)
Cel2021P: 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Chemical Industries, Ltd., trade name: “Celoxide 2021P”, epoxy equivalent: 130 g / eq)
CG-500: Naphthyl group-containing fluorene type epoxy compound (manufactured by Osaka Gas Chemical Co., Ltd., trade name: "OGSOL CG-500", epoxy equivalent: 311 g / eq)
VG3101L: Glycidyl ether type epoxy compound (manufactured by Printec Co., Ltd., trade name: "Techmore VG3101L", epoxy equivalent 210 g / eq)
<レベリング剤>
F−554:フッ素系レベリング剤(DIC(株)製、商品名:「メガファック F−554」)
FTX−218:フッ素系レベリング剤((株)ネオス製、商品名:「FTX−218」)
F−559:フッ素系レベリング剤(DIC(株)製、商品名:「メガファック F−559」)
602A:フッ素系レベリング剤((株)ネオス製、商品名:「フタージェント 602A」)
F−477:フッ素系レベリング剤(DIC(株)製、商品名:「メガファック F−477」)
BYK−307:シリコーン系レベリング剤(ビックケミー・ジャパン(株)製、商品名:「BYK−307」)
<Leveling agent>
F-554: Fluorine-based leveling agent (trade name: “MegaFac F-554” manufactured by DIC Corporation)
FTX-218: Fluorine-based leveling agent (manufactured by Neos Corporation, trade name: "FTX-218")
F-559: Fluorinated leveling agent (manufactured by DIC Corporation, trade name: "MegaFac F-559")
602A: Fluorine leveling agent (manufactured by Neos Co., Ltd., trade name: "Futhergent 602A")
F-177: Fluorine-based leveling agent (trade name: "Megafac F-177", manufactured by DIC Corporation)
BYK-307: silicone-based leveling agent (trade name: "BYK-307" manufactured by BYK Japan KK)
<シランカップリング剤>
OFS−6040:3−グリシドキシプロピルトリメトキシシラン(東レ・ダウコーニング(株)製、商品名:「OFS−6040」)
X−41−1059A:シラン化合物(信越化学(株)製、商品名:「X−41−1059A」)
X−41−1053:シラン化合物(信越化学(株)製、商品名:「X−41−1053」)
<Silane coupling agent>
OFS-6040: 3-glycidoxypropyltrimethoxysilane (manufactured by Dow Corning Toray Co., Ltd., trade name: “OFS-6040”)
X-41-1059A: silane compound (trade name: “X-41-1059A” manufactured by Shin-Etsu Chemical Co., Ltd.)
X-41-1053: silane compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: "X-41-1053")
<触媒>
ZrOct:2−エチルヘキシル酸ジルコニル(日本化学産業(株)製、商品名「ニッカオクチックスジルコニウム10%(K)」
<安定剤>
IPVE:i−プロピルビニルエーテル
NPVE:n−プロピルビニルエーテル
<溶剤>
PGMEA: プロピレングリコールモノメチルエーテルアセテート
MMBA: 3−メトキシ−3−メチル−1−ブチルアセテート
EDM: ジエチレングリコールメチルエチルエーテル
EEP: エチルエトキシプロピオネート
<Catalyst>
ZrOct: Zirconyl 2-ethylhexylate (manufactured by Nippon Chemical Industry Co., Ltd., trade name “Nikka Octix Zirconium 10% (K)”)
<Stabilizer>
IPVE: i-propyl vinyl ether NPVE: n-propyl vinyl ether <solvent>
PGMEA: Propylene glycol monomethyl ether acetate MMBA: 3-Methoxy-3-methyl-1-butyl acetate EDM: Diethylene glycol methyl ethyl ether EEP: Ethyl ethoxy propionate
得られた実施例1〜10及び比較例1〜10用のカラーフィルター保護膜用樹脂組成物の塗工液は、それぞれメンブレンフィルター(材質:PE、孔径:0.2μm)で濾過した後、更に中空系フィルター(材質:PP、孔径:0.02μm)で濾過した。得られたカラーフィルター保護膜用樹脂組成物の塗工液を、スピンコーター(型式1H−DX−2、ミカサ(株)製)により10cm角の石英ガラスもしくは無アルカリガラス基板上に回転塗布した。塗布後、基板を90℃のクリーンオーブン中にて2分間乾燥処理後、230℃のクリーンオーブン中にて30分間加熱することにより、膜厚1.5μmの硬化膜を得た。得られた硬化膜の平滑性(塗布性)、平坦性、透明性、及び鉛筆硬度の評価を、次のように行った。その結果も表3及び表4に示す。 The coating liquids of the obtained resin compositions for a color filter protective film for Examples 1 to 10 and Comparative Examples 1 to 10 were each filtered through a membrane filter (material: PE, pore size: 0.2 μm), and then further filtered. Filtration was performed with a hollow filter (material: PP, pore size: 0.02 μm). The coating solution of the obtained resin composition for a color filter protective film was spin-coated on a 10 cm square quartz glass or non-alkali glass substrate by a spin coater (model 1H-DX-2, manufactured by Mikasa Corporation). After the application, the substrate was dried in a 90 ° C. clean oven for 2 minutes, and then heated in a 230 ° C. clean oven for 30 minutes to obtain a cured film having a thickness of 1.5 μm. The smoothness (applicability), flatness, transparency, and pencil hardness of the obtained cured film were evaluated as follows. The results are also shown in Tables 3 and 4.
<平滑性>
無アルカリガラス基板上に膜厚1.0μm、1.5μm、2.0μm、2.5μmで形成した硬化膜を目視で観察し、ハジキが確認されなかったものを○、ハジキが確認されたものを×と評価した。
<Smoothness>
A cured film formed with a film thickness of 1.0 μm, 1.5 μm, 2.0 μm, 2.5 μm on a non-alkali glass substrate was visually observed, and when no repelling was confirmed, it was evaluated as ○, and when repelling was confirmed. Was evaluated as x.
<平坦性>
平坦性評価用のダミーカラーフィルターで、赤色画素と緑色画素中心部分の高さの差、赤色画素と青色画素中心部分の高さの差、および緑色画素と青色画素中心部分の高さの差(画素間段差)を求めた。引き続き、前述の硬化膜作成方法に従い、膜厚が1.5±0.05μmの硬化膜を形成したのちに、同一部分の赤色画素と緑色画素中心部分の高さの差、赤色画素と青色画素中心部分の高さの差、および緑色画素と青色画素中心部分の高さの差を求めた。これらの段差は触針式表面粗度計(型式EK4000AK、小坂研究所(株)製)にて測定した。保護膜塗布前の画素間段差の内、大きい値を塗布前最大画素間段差(d1)とし、保護膜塗布後の画素間段差の内、大きい値を塗布後最大画素間段差(d2)とし、これらのd1、d2から下記の計算式(1)により、保護膜用組成物の平坦化率Xを求めた。
平坦化率X(%)が、90%以上を◎、80〜90%を○、70〜80%を△、70%以下を×と評価した。
<Flatness>
A dummy color filter for evaluating flatness, the difference in height between a red pixel and a green pixel center, the difference in height between a red pixel and a blue pixel center, and the difference in height between a green pixel and a blue pixel center ( (Step between pixels). Subsequently, after forming a cured film having a thickness of 1.5 ± 0.05 μm according to the above-described method of forming a cured film, the difference in height between the center portion of the red pixel and the green pixel in the same portion, the red pixel and the blue pixel The difference in height between the center portions and the difference in height between the center portions of the green and blue pixels were determined. These steps were measured by a stylus type surface roughness meter (model EK4000AK, manufactured by Kosaka Laboratory Co., Ltd.). Of the steps between pixels before the application of the protective film, a large value is defined as a maximum inter-pixel level difference (d1) before application, and a large value of the steps between pixels after the application of the protective film is defined as a maximum inter-pixel level (d2) after application. From these d1 and d2, the flattening rate X of the composition for a protective film was determined by the following formula (1).
The flattening rate X (%) was evaluated as ◎ when 90% or more, ○ when 80 to 90%, Δ when 70 to 80%, and X when 70% or less.
<透明性>
硬化膜を形成した無アルカリガラス基板を、紫外−可視光分光光度計(型式UV−3700、(株)島津製作所製)を用いて波長300nm〜800nmまでスキャンし、光線透過率を測定した。380〜580nmの平均透過率が98.0%以上必要である。
<Transparency>
The alkali-free glass substrate on which the cured film was formed was scanned from a wavelength of 300 nm to 800 nm using an ultraviolet-visible light spectrophotometer (model UV-3700, manufactured by Shimadzu Corporation) to measure the light transmittance. The average transmittance at 380 to 580 nm needs to be 98.0% or more.
<硬度>
硬化膜を形成した無アルカリガラス基板をJISK5600−5−4:1999「塗料一般試験方法−第5部:塗膜の機械的性質−第4節:引っかき硬度(鉛筆法)」に準拠した方法で評価した。評価結果が3H以上必要である。
<Hardness>
The alkali-free glass substrate on which the cured film was formed was subjected to a method according to JIS K5600-5-4: 1999 "General paint test method-Part 5: Mechanical properties of coating film-Section 4: Scratch hardness (pencil method)". evaluated. The evaluation result must be 3H or more.
表3の結果から、実施例1〜10では、成分(A)〜(C)を適量含有し、且つ成分(A)に特定構造の成分(a2)を所定量含有する重合体を用いていることで、従来から求められていた平滑性、透明性、膜硬度を維持しながら、優れた平坦性が得られていた。 From the results in Table 3, in Examples 1 to 10, polymers containing an appropriate amount of components (A) to (C) and a predetermined amount of component (a2) having a specific structure in component (A) are used. As a result, excellent flatness has been obtained while maintaining the smoothness, transparency, and film hardness that have been conventionally required.
一方、表4の結果から、比較例1,2では(a3)を含有しない成分(A)を用いているため、透明性が悪かった。さらに、比較例2では(C)成分を含有していないため、透明性が比較例1よりも悪かった。比較例3〜6は、(a2)を含有しない成分(A)を用いているため、平坦性が悪かった。比較例7は、(a3)を過度に含有した成分(A)を用いているため、白化した。このため、平滑性と平坦性も悪化した。比較例8は、成分(B)の含有量が過多であり、且つ成分(C)を含有していないため、透明性が悪かった。比較例9は、成分(A)の含有量が過少なため、平坦性が悪かった。比較例10は、成分(A)の含有量が過多であるため、白化した。このため、平滑性と平坦性も悪化した。
On the other hand, from the results in Table 4, in Comparative Examples 1 and 2, since the component (A) containing no (a3) was used, the transparency was poor. Further, Comparative Example 2 did not contain the component (C), so that the transparency was worse than Comparative Example 1. In Comparative Examples 3 to 6, the flatness was poor because the component (A) containing no (a2) was used. Comparative Example 7 was whitened because the component (A) excessively containing (a3) was used. For this reason, the smoothness and flatness also deteriorated. In Comparative Example 8, the content of the component (B) was excessive and the component (C) was not contained, so that the transparency was poor. Comparative Example 9 was poor in flatness because the content of the component (A) was too small. Comparative Example 10 was whitened because the content of the component (A) was excessive. For this reason, the smoothness and flatness also deteriorated.
Claims (2)
成分(A)を5〜50重量部、成分(B)を5〜40重量部、及び成分(C)を25〜80重量部含有し、成分(A)〜(C)の合計が100重量部である、カラーフィルター保護膜用熱硬化性樹脂組成物。
成分(A):(a1)炭素−炭素不飽和結合とエポキシ基又はオキセタニル基を有するモノマーと、(a2)下記式(1)で表されるモノマーと、(a3)(a1)及び(a2)以外の炭素−炭素不飽和結合を有するモノマーとからなり、(a1)を10〜65質量%、(a2)を10〜60質量%、(a3)を15〜55質量%含み、(a1)、(a2)及び(a3)の合計量が100質量%となる、テトラヒドロフルフリル基含有重合体
(R1は水素またはメチル基。)
成分(B):多価カルボン酸無水物又は多価ブロックカルボン酸
成分(C):一分子中にエポキシ基を2個以上有する多官能エポキシ樹脂 A thermosetting resin composition for a color filter protective film comprising the following components (A) to (C),
It contains 5 to 50 parts by weight of the component (A), 5 to 40 parts by weight of the component (B), and 25 to 80 parts by weight of the component (C), and the total of the components (A) to (C) is 100 parts by weight. A thermosetting resin composition for a color filter protective film.
Component (A): (a1) a monomer having a carbon-carbon unsaturated bond and an epoxy group or an oxetanyl group; (a2) a monomer represented by the following formula (1); (a3) (a1) and (a2) (A1) is 10 to 65% by mass, (a2) is 10 to 60% by mass, (a3) is 15 to 55% by mass, and (a1) Tetrahydrofurfuryl group-containing polymer in which the total amount of (a2) and (a3) is 100% by mass
(R 1 is hydrogen or a methyl group.)
Component (B): polycarboxylic acid anhydride or polyvalent block carboxylic acid Component (C): polyfunctional epoxy resin having two or more epoxy groups in one molecule
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JP7027905B2 (en) * | 2018-01-18 | 2022-03-02 | 日油株式会社 | A color filter comprising a thermosetting resin composition and a cured film thereof. |
KR102259745B1 (en) | 2018-12-07 | 2021-06-02 | 주식회사 엘지화학 | Adhesive resin and adhesive composition for optical member |
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