JP2016012053A - Thermosetting resin composition for color filter protective film, and color filter provided with the cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermocurable resin composition capable of producing a color filter protective film that exhibits superior adhesion, wettability, and smoothness.SOLUTION: A color filter protective film-forming thermocurable resin composition contains A, B, and C components, where the B component content and C component content are 10-130 pts.wt. and 1.0-4.4 pts.wt., respectively, per 100 pts.wt. of the A component. A component: an epoxy group-containing polymer comprising (a) a monomer containing a carbon-carbon unsaturated bond and an epoxy group and (b) a monomer containing a carbon-carbon unsaturated bond other than the one in (b). B component: a carboxylic acid derivative compound having a predetermined structure. C component: a silane compound obtained by having alkoxysilane containing an epoxy group with a predetermined structure react with tetraalkoxysilane having a predetermined structure.

Description

  The present invention relates to a thermosetting resin composition for a color filter protective film used in a liquid crystal display device and the like, and a color filter having a protective film formed by curing the composition.

  In recent years, with the rapid spread of liquid crystal display devices, the demand for high-quality color filters used in liquid crystal display devices has also increased. The color filter is a structure in which a protective layer and a black matrix layer formed in a predetermined pattern or a colored layer in which a plurality of colors such as red, green, and blue are arranged in a predetermined order on a transparent substrate, The light passing through the colored layer has three basic colors of red, green, and blue, and these lights are additively mixed to create an image color including intermediate colors and white. The protective film plays a role of physically or chemically protecting the colored layer of the color filter during the production of the liquid crystal display device, and is required to be excellent in hardness, adhesion, solvent resistance, and heat resistance. The protective film is also required to have excellent performance such as transparency and smoothness so as not to adversely affect the color of the colored layer. Furthermore, the liquid crystal display device is non-polluting so that the liquid crystal compound is not contaminated when used, for example, the passivation property that prevents the migration of contaminants from the colored layer side to the liquid crystal compound and the protective film itself does not elute into the liquid crystal compound. Non-eluting properties are also required. Therefore, the protective film of the color filter needs to have properties such as hardness, adhesion, solvent resistance, heat resistance, transparency, smoothness, and non-contamination.

  In recent liquid crystal panels, as the screen size and size of the liquid crystal display are increased, the frame is often narrowed in order to realize a larger display area in a limited space. Narrowing the frame means narrowing the width of the frame (frame) surrounding the liquid crystal panel. The smaller the frame width of the liquid crystal panel, the larger the display area with the same liquid crystal panel size, or There is an advantage that the liquid crystal panel size can be reduced while maintaining the display area. In particular, in a portable information terminal or the like, the liquid crystal display is directly increased in size and size. Along with this narrowing of the frame, the seal width (sealing area) for bonding the TFT array substrate and the color filter substrate (CF substrate) becomes narrower. There is a concern that the color filter protective film part, and the adhesion strength between the color filter protective film and the glass part on the CF substrate side, that is, the panel strength of a so-called liquid crystal panel will be reduced. Accordingly, a color filter protective film applied to a liquid crystal panel having a narrow frame design is required to have higher adhesion even under severe conditions such as high humidity.

  Therefore, in Patent Document 1, for example, by adding an alkoxy group-containing silane-modified epoxy resin to the protective film resin composition, the adhesion of the color filter protective film made of a cured product of the composition is improved. Yes.

  However, as the liquid crystal panel is further narrowed, the seal area becomes narrower, and the conventional effect of improving the adhesion is not sufficient. Therefore, further improvement of the adhesion of the color filter protective film is required. ing.

JP 2012-21155 A

  An object of the present invention is to provide a thermosetting resin composition capable of forming a color filter protective film with further improved adhesion, and a color filter using a protective film made of the cured product.

（式中のＲ^１、Ｒ^２及びＲ^３は炭素数１〜６のアルキル基である。）

（式中のＲ^４、Ｒ^５及びＲ^６は炭素数１〜６のアルキル基である。）
Ｃ成分：下記の式（３）で表されるエポキシ基を有するアルコキシシラン及び下記の式（４）で表されるテトラアルコキシシランを反応させて得られるシラン化合物

（式中のＲ^７、Ｒ^８、及びＲ^９は炭素数１又は２のアルキル基である。）

（式中のＲ^１０、Ｒ^１１、Ｒ^１２、及びＲ^１３は炭素数１又は２のアルキル基である。） This invention is the thermosetting resin composition for color filter protective films containing the following A component-C component, Comprising: B component is 10-130 weight part with respect to 100 weight part of A component, C component Is 1.0 to 4.4 parts by weight.
Component A: (a) 10.0 to 90.0 parts by weight of a monomer having a carbon-carbon unsaturated bond and an epoxy group, and (b) a monomer having a carbon-carbon unsaturated bond other than (a) 90.0 An epoxy group-containing polymer B component having a weight average molecular weight of 3,000 to 50,000, which is 10.0 parts by weight, and the sum of (a) and (b) is 100.0 parts by weight: ) Or a carboxylic acid derivative compound represented by formula (2)

(R ¹ , R ² and R ³ in the formula are alkyl groups having 1 to 6 carbon atoms.)

(R ⁴ , R ⁵ and R ⁶ in the formula are alkyl groups having 1 to ⁶ carbon atoms.)
Component C: Silane compound obtained by reacting an alkoxysilane having an epoxy group represented by the following formula (3) and a tetraalkoxysilane represented by the following formula (4)

(Wherein R ⁷ , R ⁸ and R ⁹ are alkyl groups having 1 or 2 carbon atoms.)

(In the formula, R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are alkyl groups having 1 or 2 carbon atoms.)

  Moreover, according to this invention, the color filter which has a protective film formed by hardening | curing the said thermosetting resin composition can also be provided.

  In the present invention, “OO to XX” indicating a numerical range means that the lower limit numerical value (OO) and the upper limit numerical value (XX) are included unless otherwise specified. That is, if it is accurately described, it will be “XX or more and XX or less”.

  According to the thermosetting resin composition for a color filter protective film of the present invention, a color filter protective film having excellent adhesion can be formed.

<Thermosetting resin composition for color filter protective film>
The thermosetting resin composition for a color filter protective film of the present invention comprises (A) an epoxy group-containing polymer, (B) a carboxylic acid derivative compound, and (C) a silane compound.

Component A: Epoxy group-containing polymer Component A is composed of (a) 10.0 to 90.0 parts by weight of a monomer having a carbon-carbon unsaturated bond and an epoxy group, and (b) a carbon-carbon non-carbon other than (a). An epoxy group containing a weight average molecular weight of 3,000 to 50,000, comprising 90.0 to 10.0 parts by weight of a monomer having a saturated bond, and the sum of (a) and (b) being 100.0 parts by weight It is a polymer.

（式中、Ｒ^１３は水素原子または炭素数１〜５のアルキル基、ｍは１〜５の整数を示す。）

（式中、Ｒ^１４は水素原子または炭素数１〜５のアルキル基、ｎは１〜８の整数を示す。） (A) The monomer having a carbon-carbon unsaturated bond and an epoxy group only needs to have a carbon-carbon unsaturated bond and an epoxy group, and any monomer known for such use can be used. . For example, preferable examples include monomers represented by the following formulas (5) and (6).

(In the formula, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and m represents an integer of 1 to 5)

(In the formula, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 1 to 8)

（式中、Ｒ^１５は水素原子または炭素数１〜５のアルキル基、Ｒ^１６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、ポリアルキレングリコール残基、又は主環構成炭素数３〜１２の脂環式炭素水素基を示す。）

（式中、Ｒ^１７は水素原子または炭素数１〜５のアルキル基、Ｒ^１８は水素原子、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、Ｒ^１９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、Ｒ^２０は水素原子または炭素数１〜５のアルキル基、pは１〜５の整数、Ｒ^２１、Ｒ^２２、Ｒ^２３はそれぞれ独立にメチル基またはエチル基を示す。） (B) The monomer having a carbon-carbon unsaturated bond other than (a) may have a carbon-carbon unsaturated bond, and any monomer known for such use can be used. For example, monomers represented by the following formulas (7) to (10) are preferable examples.

(Wherein R ¹⁵ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁶ is an alkyl group having 1 to 12 carbon atoms, an aryl group, an aryloxy group, a polyalkylene glycol residue, or the number of carbon atoms constituting the main ring. 3 to 12 alicyclic carbon hydrogen groups are shown.)

Wherein R ¹⁷ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ¹⁸ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group, a hydroxyalkyl group, a hydroxyl group, a siloxyalkyl group, or an aromatic Represents a hydrocarbon group.)

(In the formula, R ¹⁹ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or an aromatic hydrocarbon group.)

(In the formula, R ²⁰ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, p is an integer of 1 to 5, and R ²¹ , R ²² and R ²³ each independently represents a methyl group or an ethyl group.)

  The epoxy group-containing polymer is produced by copolymerizing (a) 10.0 to 90.0 parts by weight and (b) 90.0 to 10.0 parts by weight with a total of 100.0 parts by weight. The polymerization mode may be linear or branched, and any of a random copolymer, a block copolymer, a graft copolymer, and the like may be used. In addition, when (a) is less than 10.0 parts by weight and (b) exceeds 90.0 parts by weight, the hardness of the protective film decreases, and (a) exceeds 90.0 parts by weight (b) Is less than 10.0 parts by weight, the adhesion of the protective film is lowered.

  The polymerization method of (a) and (b) is not particularly limited, and a polymerization method such as radical polymerization or ionic polymerization can be used. More specifically, polymerization methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be used in the presence of a polymerization initiator. Moreover, you may add additives, such as a catalyst and a solvent, to a polymerization reaction system as needed.

  The epoxy group-containing polymer is polymerized so that the weight average molecular weight is 3,000 to 50,000, and when the weight average molecular weight is less than 3,000, a decrease in the hardness of the protective film is observed, and 50,000 is obtained. Exceeding this is not preferred because the appearance after application and curing may be deteriorated.

（式中のＲ^１、Ｒ^２及びＲ^３は炭素数１〜６のアルキル基である。また、Ｒ^１、Ｒ^２及びＲ^３は互いに同一であっても良いし、異なっていても良い。）

（式中のＲ^４、Ｒ^５及びＲ^６は炭素数１〜６のアルキル基である。Ｒ^４、Ｒ^５及びＲ^６は、互いに同一であっても良いし、異なっていても良い。） Component B: Carboxylic Acid Derivative Compound The component B carboxylic acid derivative compound is a carboxylic acid derivative compound represented by the following formula (1) or (2).

(In the formula, R ¹ , R ² and R ³ are alkyl groups having 1 to 6 carbon atoms. R ¹ , R ² and R ³ may be the same as or different from each other. )

(R ⁴ , R ⁵ and R ⁶ in the formula are alkyl groups having 1 to ⁶ carbon atoms. R ⁴ , R ⁵ and R ⁶ may be the same or different from each other.)

（式中のＲ^７、Ｒ^８、及びＲ^９は炭素数１又は２のアルキル基である。Ｒ^７、Ｒ^８、及びＲ^９は、互いに同一であっても良いし、異なっていても良い。）

（式中のＲ^１０、Ｒ^１１、Ｒ^１２、及びＲ^１３は炭素数１又は２のアルキル基である。Ｒ^１０、Ｒ^１１、Ｒ^１２、及びＲ^１３は、互いに同一であっても良いし、異なっていても良い。） C component: Silane compound The C component is a silane compound obtained by reacting an alkoxysilane having an epoxy group represented by the following formula (3) and a tetraalkoxysilane represented by the following formula (4).

(In the formula, R ⁷ , R ⁸ and R ⁹ are each an alkyl group having 1 or 2 carbon atoms. R ⁷ , R ⁸ and R ⁹ may be the same or different from each other. .)

(In the formula, R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are alkyl groups having 1 or 2 carbon atoms. R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ may be the same as each other. , May be different.)

(Manufacture of thermosetting resin composition for color filter protective film)
The thermosetting resin composition for a color filter protective film of the present invention contains 10 to 130 parts by weight of the B component and 1.0 to 4.4 parts by weight of the C component with respect to 100 parts by weight of the A component. If the B component is less than 10 parts by weight, the hardness of the protective film made of a cured product of the composition will decrease, and if it exceeds 130 parts by weight, the adhesion of the protective film may be impaired. On the other hand, when the C component is less than 1.0 part by weight, the adhesion of the protective film cannot be sufficiently improved, and when it exceeds 4.4 parts by weight, the wettability of the cured film and the smoothness of the film surface are deteriorated. Further, the C component is more preferably 1.5 to 3.0 parts by weight with respect to 100 parts by weight of the A component. When the content of component C is 1.5 to 3.0 parts by weight, the adhesion, wettability, and film surface smoothness of the cured film can be further improved. In addition, the mixing method of a resin composition is not specifically limited, All components may be mixed simultaneously or each component may be mixed sequentially.

  An epoxy resin, a leveling agent, a catalyst, a solvent, and other additives can be added to the thermosetting resin composition for a color filter protective film of the present invention according to the purpose.

Component D: Epoxy Resin The thermosetting resin composition for color filter protective film of the present invention contains A as necessary within the range not impairing the effects of the present invention for the purpose of improving heat resistance, hardness, and solvent resistance. An epoxy resin other than the component and the C component may be contained. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type Epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional type epoxy resin, tetraphenylolethane type epoxy resin, dicyclopentadienephenol type epoxy resin, hydrogenated bisphenol A Type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy Fat, glycidyl amine type epoxy resin, glyoxal type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins. These epoxy resins may be used alone or in combination of two or more. When the epoxy resin is added and used, the D component is usually blended at a ratio of 0.01 to 175 parts by weight with respect to 100 parts by weight of the A component.

E component: Leveling agent The thermosetting resin composition for a color filter protective film of the present invention may contain a leveling agent as necessary within a range not inhibiting the effects of the present invention. For example, MegaFuck F-410 (DIC Corporation), F-430 (same), F-444 (same), F-472SF (same), F-477 (same), 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 Ltd.), FC- 4432 (same), Surflon S-611 (AGC Seimi Chemical Co., Ltd.), S-651 (same), S-386 (same), Footgent 208G (Neos), 209F (same), 212P (same), 220P (same), 222F (same), 228P (same), 240G (same), 6 2A (same), 650A (same), 710FL (same), 710FM (same), FTX-218 (same), BYK-302 (Bicchemy Japan Co., Ltd.), 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), same L-600 (same), the KL-700 (same), the WS-30 (same), the No. 75 (same), No. 77 (same), No. 90 (same), No. 95 (same as above) and LE-604 (same as above). Moreover, these leveling agents may be used alone or in combination of two or more. When the leveling agent is added and used, the E component is usually blended at a ratio of 0.01 to 3 parts by weight with respect to 100 parts by weight of the A component.

F component: catalyst The thermosetting resin composition for a color filter protective film of the present invention may contain a catalyst, if necessary, within a range not impairing the effects of the present invention. For example, tertiary amines such as benzyldimethylamine tris (dimethylaminomethyl) phenol and dimethylcyclohexylamine; 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2 -Imidazoles such as methylimidazole; Organophosphorus compounds such as triphenylphosphine and triphenyl phosphite; Quaternary phosphonium salts such as tetraphenylphosphonium bromide and tetra-n-butylphosphonium bromide; 1,8-diazabicyclo [5 4.0] diazabicycloalkenes such as undecene-7 and organic acid salts thereof; and catalysts such as organometallic compounds such as zinc octylate, tin octylate, zirconium octylate, and aluminum acetylacetonate complex. . When these catalysts are added and used, the F component is usually blended at a ratio of 0.01 to 3 parts by weight with respect to 100 parts by weight of the A component.

G component: Solvent The thermosetting resin composition for a color filter protective film of the present invention may contain a solvent, if necessary, as long as the effects of the present invention are not impaired. For example, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, monomethyl ether, methoxybutyl acetate, ethyl 3-ethoxypropionate, 3-methoxy- Esters and ether esters such as 3-methyl-1-butyl acetate; ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diester Butyl ether, diethylene glycol ethyl methyl ether, diethylene glycol Glycols such as isopropyl methyl ether, diethylene glycol butyl methyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol methyl ether acetate, propylene glycol diacetate, propylene glycol phenyl ether Examples include solvents such as derivatives. These solvents may be used alone or in combination of two or more. When the solvent is added and used, the G component is usually blended at a ratio of 0.01 to 4500 parts by weight with respect to 100 parts by weight of the A component.

  Furthermore, various other additives can be added to the thermosetting resin composition for a color filter protective film of the present invention in accordance with the purpose within a range not inhibiting the effects of the present invention. For example, BYK-051 (BIC Chemie Japan Co., Ltd.), BYK-052 (same), BYK-053 (same), BYK-055 (same), BYK-057 (same), BYK-1790 (same) BYK-063 (same), BYK-065 (same), BYK-066N (same), BYK-067A (same), BYK-077 (same), BYK-141 (same), BYK-354 (same), Antifoaming agents such as BYK-392 (same), IRGANOX 1010 (Ciba Japan), IRGANOX 1035 (same), IRGANOX 1076 (same), IRGANOX 1098 (same), IRGANOX 1135 (same), IRGANOX 1330 (same), IRGANOX 1726 (same) ), IRGANOX1425WL (same), IRGANOX1520L (same), IRGA OX245 (same), IRGANOX259 (same), IRGANOX3114 (same), Irganox 5057 (same), IRGANOX 565 (same) include antioxidants such as IRGANOD295 (same). When the additive is used after being added, the additive is usually blended at a ratio of 0.01 to 4 parts by weight per 100 parts by weight of component A.

(Formation of color filter protective film)
The color filter of this invention has the layer of the hardened | cured material formed by hardening | curing the said thermosetting resin composition for color filter protective films. The layer of the cured product obtained by curing the thermosetting composition for the color filter protective film is generally a layer called a protective film, but is not limited to the protective film, and is not limited to the color filter. You may be comprised as another layer.

  The said thermosetting resin composition is apply | coated so that the colored layer and black matrix arrange | positioned on a board | substrate may be covered. The coating method is not particularly limited, and conventionally known coating methods such as a gravure coating method, a spin coating method, a die coating method, and an ink jet method can be employed.

  The obtained coating film is dried, and further preheated (hereinafter referred to as prebaking) as necessary, and then subjected to main curing heating (hereinafter referred to as postbaking) to form a cured resin layer. In this case, 40 to 140 ° C. and 0 to 1 hour are preferable as prebaking conditions, and 150 to 280 ° C. and 0.2 to 2 hours are preferable as post baking conditions. In addition, the heating method in this case is not particularly limited, and for example, a curing apparatus 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 can be performed by a method such as hot air circulation, infrared heating, high frequency heating or the like.

<Synthesis Example 1-1: Synthesis of epoxy group-containing polymer (A-1)>
A 300 mL four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel was charged with 78.5 parts by weight of propylene glycol monomethyl ether acetate (hereinafter PGMEA) and heated to 80 ° C. while stirring. The temperature rose. Subsequently, at a temperature of 80 ° C., 71.1 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate (hereinafter referred to as M-100), 28.9 parts by weight of cyclohexyl methacrylate (hereinafter referred to as CHMA), and peroxide manufactured by NOF Corporation. A product obtained by uniformly mixing 3.5 parts by weight of a physical polymerization initiator “perhexyl O (hereinafter referred to as PHO)” and 25 parts by weight of PGMEA in advance (dropping component) was dropped at a constant rate from a dropping funnel over 2 hours. After completion of the dropping, the temperature was maintained at 80 ° C. for 5 hours, and then the reaction was terminated to obtain a 50% PGMEA solution of the epoxy group-containing polymer (A-1). It was 50,000 when the weight average molecular weight (Mw) of the obtained epoxy-group-containing polymer (A-1) was measured by the following method.

表１中の略号は次の通りである。
Ｍ−１００：３，４−エポキシシクロヘキシルメチルメタクリレート
ＧＭＡ：グリシジルメタクリレート
ＣＨＭＡ：シクロヘキシルメタクリレート
ＤＣＰＭＡ：ジシクロペンタニルメタクリレート
Ｓｔ：スチレン
ＣＨＭＩ：シクロヘキシルマレイミド
ＭＰＳ：メタクリロキシプロピルトリメトキシシラン
ＰＨＯ：過酸化物系重合開始剤（商品名：「パーヘキシルＯ」）
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 <Synthesis Examples 1-2 to 1-11: Synthesis of Epoxy Group-Containing Polymer (A2 to 11)>
A-2 to 11 polymers were obtained in the same manner as in Synthesis Example 1-1 except that the raw materials, preparation ratios, and dropping / reaction temperatures shown in Table 1 below were used. Table 1 shows the weight average molecular weights of the obtained epoxy group-containing polymers (A2 to 11).

Abbreviations in Table 1 are as follows.
M-100: 3,4-epoxycyclohexylmethyl methacrylate GMA: glycidyl methacrylate CHMA: cyclohexyl methacrylate DCPMA: dicyclopentanyl methacrylate St: styrene CHMI: cyclohexylmaleimide MPS: methacryloxypropyltrimethoxysilane PHO: initiation of peroxide polymerization Agent (trade name: “Perhexyl O”)
PGMEA: Propylene glycol monomethyl ether acetate

<Synthesis Example 2-1: Synthesis of carboxylic acid derivative compound (B-1)>
In a four-necked flask equipped with a thermometer, reflux condenser, and stirrer, 26.9 parts by weight of propylene glycol monomethyl ether acetate (PGMEA), 26.9 parts by weight of trimellitic acid (hereinafter referred to as TMA), n-propyl vinyl ether ( Hereinafter, 46.3 parts by weight of nPr-VE) was charged, heated with stirring, and heated to 80 ° C. Next, stirring was continued while maintaining the temperature, and the acid value of the mixture was measured by the following method at regular intervals. After confirming that the acid value of the mixture was 2.0 mgKOH / g or less, heating and mixing were terminated, and the mixture was air-cooled to obtain a 60% PGMEA solution (B-1) of a polyvalent carboxylic acid derivative compound. Obtained. When the acid value of the obtained polyvalent carboxylic acid derivative compound solution was measured, the reaction proceeded during air cooling and was 0.6 mgKOH / g.

表２中の略号は次の通りである。
ＴＭＡ：トリメリット酸
ＣＨＴＡ：１，２，４−シクロヘキサントリカルボン酸
ｎＰｒ−ＶＥ：ｎ−プロピルビニルエーテル
ｉＰｒ−ＶＥ：ｉ−プロピルビニルエーテル
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 <Synthesis Example 2-2, 2-3: Synthesis of carboxylic acid derivative compound (B-2, B-3)>
Compounds B-2 and B-3 were obtained in the same manner as in Synthesis Example 2-1, except that the raw materials and the charging ratios shown in Table 2 below were used. Table 2 shows the acid values of the obtained polyvalent carboxylic acid derivative compound solutions (B-2, B-3).

Abbreviations in Table 2 are as follows.
TMA: trimellitic acid CHTA: 1,2,4-cyclohexanetricarboxylic acid nPr-VE: n-propyl vinyl ether iPr-VE: i-propyl vinyl ether PGMEA: propylene glycol monomethyl ether acetate

<Synthesis Example 3-1: Synthesis of Silane Compound (C-1)>
In a four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 236.0 parts by weight of 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as GPTM), tetramethoxysilane (hereinafter referred to as TMOS) 152. 0 parts by weight, 320.0 parts by weight of methanol (hereinafter referred to as MeOH) and 0.06 parts by weight of potassium fluoride (hereinafter referred to as KF) were charged, and 28.8 parts by weight of H ₂ O was slowly dropped from the dropping funnel at room temperature while stirring. did. After completion of the dropwise addition, the mixture was maintained at room temperature for 3 hours and then stirred for 2 hours under methanol reflux. Thereafter, the low boiling point component was distilled off under reduced pressure and filtered to obtain a silane compound which was a colorless and transparent liquid. When the epoxy equivalent and the weight average molecular weight of the obtained silane compound were measured by the following methods, the epoxy equivalent was 319 g / mol and the weight average molecular weight (Mw) was 1,600.

表３中の略号は次の通りである。
ＧＰＴＭ：３−グリシドキシプロピルトリメトキシシラン
ＧＰＴＥ：３−グリシドキシプロピルトリエトキシシラン
ＥＣＥＴＭ：２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン
ＥＣＥＴＥ：２−（３，４−エポキシシクロヘキシル）エチルトリエトキシシラン
ＧＰＭＤＭ：３−グリシドキシプロピルメチルジメトキシシラン
ＧＰＭＤＥ：３−グリシドキシプロピルメチルジエトキシシラン
ＮＧＡ：Ｎ−グリシジルーＮ，Ｎ−ビス[３−（メチルジメトキシシリル）プロピル]アミン
ＥＯＭＴＭ：（３−エチルオキセタン−３−イル）プロピルトリエトキシシラン
ＭＰＴＭ：３−メルカプトプロピルトリメトキシシラン
ＴＭＯＳ：テトラメトキシシラン
ＴＥＯＳ：テトラエトキシシラン
ＭＴＭＳ：メチルトリメトキシシラン
ＰｈＴＭＳ：フェニルトリメトキシシラン
ＫＦ：フッ化カリウム
ＭｅＯＨ：メタノール <Synthesis Examples 3-2 to 3-5 and Comparative Synthesis Examples 3-1 to 3-9: Synthesis of Silane Compound (C-2 to C-14)>
Compounds C-2 to 14 were obtained in the same manner as in Synthesis Example 3-1, except that the raw materials and the charging ratios shown in Table 3 below were used. Table 3 shows the epoxy equivalent and the weight average molecular weight of the obtained silane compounds (C-2 to C-14).

Abbreviations in Table 3 are as follows.
GPTM: 3-glycidoxypropyltrimethoxysilane GPTE: 3-glycidoxypropyltriethoxysilane ECETM: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane ECETE: 2- (3,4-epoxycyclohexyl) Ethyltriethoxysilane GPMDM: 3-glycidoxypropylmethyldimethoxysilane GPMDE: 3-glycidoxypropylmethyldiethoxysilane NGA: N-glycidyl N, N-bis [3- (methyldimethoxysilyl) propyl] amine EOMTM: (3-Ethyloxetane-3-yl) propyltriethoxysilane MPTM: 3-mercaptopropyltrimethoxysilane TMOS: tetramethoxysilane TEOS: tetraethoxysilane MTMS: methyltrimethoxysilane HTMS: phenyltrimethoxysilane KF: potassium fluoride MeOH: methanol

表４及び表５中の略号は次の通りである。
ＴＭＡ：トリメリット酸
ＴＭＡ−Ａｎ：無水トリメリット酸
Ｘ−４１−１０５３：シラン化合物（信越化学（株）製、商品名：「Ｘ−４１−１０５３」、エポキシ当量８３０ｇ／ｅｑ）
Ｘ−４１−１０５９Ａ：シラン化合物（信越化学（株）製、商品名：「Ｘ−４１−１０５９Ａ」、エポキシ当量３５０ｇ／ｅｑ）
ＧＰＴＭ：３−グリシドキシプロピルトリメトキシシラン
ＴＭＯＳ：テトラメトキシシラン
Ｘ−４１−１０５６：シラン化合物（信越化学（株）製、商品名：「Ｘ−４１−１０５６」、エポキシ当量２８０ｇ／ｅｑ）
Ｅｐ−８２８：ビスフェノールＡ型エポキシ樹脂（三菱化学（株）製、商品名：「Ｅｐ−８２８」、エポキシ当量１８９ｇ／ｅｑ）
Ｅｐ−１５７：ビスフェノールＡノボラック型エポキシ樹脂（三菱化学（株）製、商品名：「ｊＥＲ１５７Ｓ７０」、エポキシ当量２１０ｇ／ｅｑ）
ＧＴ−４０１：ブタンテトラカルボン酸テトラ（３，４−エポキシシクロヘキシルメチル）修飾ε−カプロラクトン（（株）ダイセル製、商品名：「エポリードＧＴ−４１０」、エポキシ当量２２０ｇ／ｅｑ）
Ｃｅｌ−２０２１ｐ：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（（株）ダイセル製、商品名：「セロキサイド２０２１Ｐ」、エポキシ当量１３０ｇ／ｅｑ）
ＶＧ３１０１Ｌ：グリシジルエーテル型エポキシ樹脂（プリンテック（株）製、商品名：「テクモアＶＧ３１０１Ｌ」、エポキシ当量２１０ｇ／ｅｑ）
ＥＨＰＥ−３１５０：２，２−ビス（ヒドロキシメチル）−１−ブタノールの１，２−エポキシ−４−（２−オキシラニル）シクロヘキサン付加物（（株）ダイセル製、商品名：「ＥＨＰＥ３１５０」、エポキシ当量１８０ｇ／ｅｑ）
ＣＧ−５００：フルオレン系エポキシ樹脂（大阪ガスケミカル（株）製、商品名：「ＣＧ−５００」、エポキシ当量３１１ｇ／ｅｑ）
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」）
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」）
ＦＴＸ−２１８：フッ素系レベリング剤（（株）ネオス製、商品名：「ＦＴＸ−２１８」）
ＬＣＡＴ−１：オクチル酸亜鉛とＮ−メチルモルホリンの反応物
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
尚、Ｘ−４１−１０５３およびＸ−４１−１０５９Ａは本願のＣ成分に該当するシラン化合物である。 <Examples 1-9, Comparative Examples 1-18>
The mixture dissolved and mixed with the components and blending amounts shown in Tables 4 and 5 below was filtered through a membrane filter (material: PE, pore size: 0.2 μm), and then a hollow filter (material: PP, pore size: 0.00). 02 μm) to obtain resin compositions for color filter protective films of Examples 1 to 9 and Comparative Examples 1 to 18. Each color filter protective film resin composition was spin-coated on a 10 cm square glass substrate by a spin coater (model 1H-DX-2, manufactured by Mikasa Corporation). The glass substrate coated with the color filter protective film resin composition is dried in a clean oven at 90 ° C. for 2 minutes and then heated in a clean oven at 230 ° C. for 30 minutes to cure to a thickness of 1.5 μm. A membrane was obtained. About the obtained resin composition for color filter protective films and a cured film, adhesiveness (cross-cut test, pimple test), wettability (water contact angle after UV irradiation), smoothness (surface roughness) are as follows. And physical properties of storage stability were evaluated. Tables 4 and 5 show the blending ratio of each component and the results of physical property evaluation.

Abbreviations in Table 4 and Table 5 are as follows.
TMA: trimellitic acid TMA-An: trimellitic anhydride X-41-1053: silane compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “X-41-1053”, epoxy equivalent 830 g / eq)
X-41-1059A: Silane compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “X-41-1059A”, epoxy equivalent 350 g / eq)
GPTM: 3-glycidoxypropyltrimethoxysilane TMOS: tetramethoxysilane X-41-1056: silane compound (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: “X-41-1056”, epoxy equivalent 280 g / eq)
Ep-828: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: “Ep-828”, epoxy equivalent 189 g / eq)
Ep-157: Bisphenol A novolac type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: “jER157S70”, epoxy equivalent 210 g / eq)
GT-401: Butanetetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone (manufactured by Daicel Corporation, trade name: “Epolide GT-410”, epoxy equivalent 220 g / eq)
Cel-2021p: 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name: “Celoxide 2021P”, epoxy equivalent 130 g / eq)
VG3101L: Glycidyl ether type epoxy resin (manufactured by Printec Co., Ltd., trade name: “Techmore VG3101L”, epoxy equivalent 210 g / eq)
EHPE-3150: 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol (manufactured by Daicel Corporation, trade name: “EHPE3150”, epoxy equivalent) 180g / eq)
CG-500: Fluorene-based epoxy resin (manufactured by Osaka Gas Chemical Co., Ltd., trade name: “CG-500”, epoxy equivalent of 311 g / eq)
F-477: Fluorine-based leveling agent (manufactured by DIC Corporation, trade name: “Megafuck F-477”)
602A: Fluorine leveling agent (manufactured by Neos Co., Ltd., trade name: “Furgent 602A”)
FTX-218: Fluorine-based leveling agent (trade name: “FTX-218”, manufactured by Neos Co., Ltd.)
LCAT-1: Reaction product of zinc octylate and N-methylmorpholine PGMEA: Propylene glycol monomethyl ether acetate MMBA: 3-methoxy-3-methyl-1-butyl acetate EDM: Diethylene glycol methyl ethyl ether EEP: Ethyl ethoxypropionate , X-41-1053 and X-41-1059A are silane compounds corresponding to the C component of the present application.

[Measurement and evaluation methods]
<Weight average molecular weight>
The weight average molecular weight (Mw) was measured using a column (model SHODEX K-801, manufactured by Showa Denko KK) using a gel permeation chromatography device (model HLC-8820GPC, manufactured by Tosoh Corporation), and THF. The eluent was measured with an RI detector and determined in terms of polystyrene.

<Acid value>
The acid value was measured by hydrolysis acid value measurement according to JIS K 0070: 1992 “Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”.

<Epoxy equivalent>
After an epoxy group ring-opening reaction with an excess of 0.2N · dioxane hydrochloride solution, unreacted hydrochloric acid was back titrated with 0.1N · KOH ethanol solution to calculate an epoxy equivalent.

<Adhesion: cross-cut test>
After the glass substrate on which the cured film was produced was subjected to a pressure cooker test (hereinafter referred to as PCT) treatment, JIS K 5600-5-6: 1999 “Paint General Test Method—Part 5: Mechanical Properties of Coating Film—No. Adhesion was evaluated according to “Section 6: Adhesiveness (cross-cut method)”. The PCT conditions were “temperature 120 ° C., relative humidity 100%, atmospheric pressure 2 atm, test time 6 hours”. To serve the purpose of the present application, the evaluation requires 100/100.

<Adhesion: pimple test>
The glass substrate on which the cured film was produced was cut into a 1 cm square, and an epoxy resin stud pin (product number: P / N901106, manufactured by QUAD GROUP) was set on the cured film, and then a mount clip (QUAD GROUP, Inc.). And heated in an oven at 150 ° C. for 1 hour. Then, it annealed in oven until it became 50 degrees C or less, the mount clip was removed, and the sample for evaluation was obtained. Adhesion was evaluated by measuring the adhesion after the pressure cooker test (PCT) for the sample for evaluation. The PCT conditions were “temperature 120 ° C., relative humidity 100%, atmospheric pressure 2 atm, test time 2 hours”. The measurement of the adhesive force (MPa) was performed using an autograph (model number: AG-I, manufactured by Shimadzu Corporation) at a tensile speed of 10 mm / min. In order to serve the purpose of the present application, the adhesive force needs to be 40 MPa or more.

<Wettability: Water contact angle after UV irradiation>
The glass substrate on which the cured film was produced was subjected to UV-ozone cleaning using a UV cleaning device (model eye UV-ozone cleaning device, manufactured by Iwasaki Electric Co., Ltd.) so that the irradiation dose was 1000 mJ / cm ² for evaluation. A sample was obtained. The contact angle (°) of 1 μl of water with respect to the sample surface for evaluation was measured with a contact angle measuring device (model DropMaster R500, manufactured by Kyowa Interface Chemical Co., Ltd.). In order to serve the purpose of the present application, the contact angle needs to be 60 ° or less.

<Smoothness: surface roughness>
The surface roughness (nm) of the glass substrate on which the cured film was produced was measured using a surface roughness meter (model ET4000, manufactured by Kosaka Laboratory Ltd.). For the purpose of the present application, the surface roughness is required to be 10 nm or less.

<Storage stability>
After measuring the initial viscosity of the color filter protective film resin composition, the composition is allowed to stand in a sealed container at 5 ° C., and the change in viscosity is evaluated until the viscosity becomes twice the initial viscosity ( Day). In addition, when it is left to stand for 180 days at the longest and the viscosity does not reach twice the initial viscosity after 180 days, it is indicated as “180 days” for convenience. 180 days are required to serve the purpose of this application.

  The resin compositions for color filter protective films of Examples 1 to 9 showed excellent results in all of adhesion, wettability, smoothness, and storage stability. On the other hand, in Comparative Examples 1 and 2, since only one of the alkoxysilane having an epoxy group represented by the formula (3) and the tetraalkoxysilane represented by the formula (4) is included as the C component, the adhesion is poor. In Comparative Example 2, the wettability was also poor. Although Comparative Example 3 contains an alkoxysilane having an epoxy group represented by the formula (3) and a tetraalkoxysilane represented by the formula (4) as the C component, since both are unreacted, the adhesion And the wettability was inferior. Since Comparative Examples 4-6 used the compound which does not correspond to Formula (4) for C component, adhesiveness and wettability were inferior. Since Comparative Examples 7-13 used the compound which does not correspond to Formula (3) for C component, adhesiveness was inferior, and Comparative Examples 9-13 were also inferior in smoothness. Moreover, the comparative example 13 was also inferior in storage stability. Since the comparative example 14 had too few C components, adhesiveness was inferior. Since Comparative Examples 15 and 16 had too much C component, wettability and smoothness were inferior. In Comparative Examples 17 and 18, since the carboxylic acid derivative compound not corresponding to the formula (1) or the formula (2) was used as the B component, the storage stability was inferior.

Claims (2)

A thermosetting resin composition for a color filter protective film comprising the following A component to C component, wherein B component is 10 to 130 parts by weight with respect to 100 parts by weight of A component, and C component is 1.0. The thermosetting resin composition for color filter protective films which is -4.4 weight part.
Component A: (a) 10.0 to 90.0 parts by weight of a monomer having a carbon-carbon unsaturated bond and an epoxy group, and (b) a monomer having a carbon-carbon unsaturated bond other than (a) 90.0 An epoxy group-containing polymer B component having a weight average molecular weight of 3,000 to 50,000, which is 10.0 parts by weight, and the sum of (a) and (b) is 100.0 parts by weight: ) Or a carboxylic acid derivative compound represented by formula (2)

(R ¹ , R ² and R ³ in the formula are alkyl groups having 1 to 6 carbon atoms.)

(R ⁴ , R ⁵ and R ⁶ in the formula are alkyl groups having 1 to ⁶ carbon atoms.)
Component C: Silane compound obtained by reacting an alkoxysilane having an epoxy group represented by the following formula (3) and a tetraalkoxysilane represented by the following formula (4)

(Wherein R ⁷ , R ⁸ and R ⁹ are alkyl groups having 1 or 2 carbon atoms.)

(In the formula, R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are alkyl groups having 1 or 2 carbon atoms.)   The color filter which has a protective film formed by hardening | curing the thermosetting resin composition for color filter protective films of Claim 1.