JP6166050B2 - Ether dimer composition and polymer - Google Patents

Description

  The present invention relates to an ether dimer composition and a polymer. More specifically, an ether dimer composition and an ether dimer composition that are suitably used as raw materials for various electronic information materials including resist materials and coating materials for producing color filters important as flat panel display members. Relates to a polymer obtained by polymerizing.

A compound having a structure in which α-hydroxymethylacrylic acid or an ester thereof is ether-dimerized (hereinafter also referred to as ether dimer) is a polymer (hereinafter referred to as “ether dimer”) containing a tetrahydropyran ring in the main chain by cyclization polymerization by radical polymerization. Are also known to form THP ring polymers). (For example, Non-Patent Document 1)
THP ring polymers are excellent in transparency, heat resistance, chemical stability, hardness, adhesion, colorant dispersibility, etc., so thermoplastic resins for optical applications such as optical pickup lenses, chemically amplified positive It attracts attention as a resin for various electronic information materials such as a resist resin or an alkali-soluble resin for a color filter resist.

  For example, a thermoplastic THP ring polymer is obtained by copolymerizing an ether dimer with methyl methacrylate. Such a THP ring polymer is excellent in transparency, heat resistance, low water absorption, mechanical strength, and low birefringence, so it can be used in various optical applications such as lenses such as optical pickup lenses, disks, and optical transmission bodies. It can be applied to display materials such as acrylic signs. (For example, patent document 1).

Further, for example, by copolymerizing an ether dimer with a monomer having an alicyclic skeleton and a monomer having a lactone skeleton, a THP ring polymer that is soluble in an alkaline aqueous solution by an acid is obtained. Since such a THP ring polymer has high dry etching resistance, it is suitable for a chemically amplified positive resist for DUV excimer laser lithography or electron beam lithography. (For example, Patent Document 2)
Also, for example, by copolymerizing an ether dimer with a monomer having a carboxyl group, an alkali-soluble and / or epoxy resin-curable THP ring polymer is obtained. Since such a THP ring polymer is excellent in transparency, heat resistance, and pigment dispersibility, it is an alkali developing negative resist such as a color resist for color filters, a transparent protective film resist for color filters, and a columnar spacer resist for color filters. It can be suitably used for a color filter, a thermosetting transparent protective coating material for organic EL, and the like. (For example, Patent Document 3)
Ether dimers are compounds that have a structure in which α-hydroxymethylacrylic acid or its ester is dimerized into ethers, and are classified into those that are symmetric and those that are asymmetric via etheric oxygen. it can. Symmetrical shapes have higher crystallinity and tend to be more excellent in terms of polymer performance such as transparency and heat resistance. Further, since the ether dimer has high radical polymerizability and can be copolymerized with various radical polymerizable monomers, it is possible to prepare a wide variety of THP ring polymers. It is a monomer that can be applied not only to the field but also to a wide range of technical fields.

  However, ether dimer has high radical polymerizability, but low storage stability. If it is stored near room temperature, it may generate insoluble and infusible solids in a few months even if frozen. This tendency was particularly strong for symmetrical ether dimers with excellent performance. Therefore, when the ether dimer is produced in a laboratory or factory, the actual situation is that the ether dimer is polymerized as soon as possible to be converted into a THP ring polymer. Therefore, since a large amount of ether dimer cannot be produced at one time, production efficiency is poor, and development of an ether dimer having excellent storage stability, particularly a symmetrical ether dimer having excellent storage stability has been a problem.

Takashi Tsuda, Lon J. et al. Mathias, POLYMER, 1994, 35, p. 3317-3328

Japanese Patent Laid-Open No. 11-302335 JP 2001-81139 A JP 2004-300204 A

  The present invention has been made in view of the above situation, and an object thereof is to provide an ether dimer composition excellent in storage stability, and a polymer produced using the ether dimer composition as a raw material. .

  As a result of intensive studies, the present inventors have surprisingly improved storage stability by making an ether dimer, which is a compound hardly soluble in water, into a uniform liquid composition in which water and a stabilizer coexist. I found it to improve. That is, (A) the following general formula (1):

（式（１）中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。）で表されるエーテルダイマー、（Ｂ）水、（Ｃ）安定剤、（Ｄ）非水系溶媒を含有し、（Ｂ）水の含有量が０．３〜１０質量％であることを特徴とするエーテルダイマー組成物。
特に、
（Ａ）下記一般式（１）：

(In formula (1), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent). (B) Water, (C) Stabilizer, (D) Non-aqueous solvent, (B) Water content is 0.3-10 mass%, The ether dimer composition characterized by the above-mentioned.
In particular,
(A) The following general formula (1):

（式（１）中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。）で表されるエーテルダイマー１０〜７０質量％、（Ｂ）水０．３〜１０質量％、（Ｃ）安定剤０．００１〜１質量％、（Ｄ）非水系溶媒２０〜９０質量％を含有するエーテルダイマー組成物とすることにより、高温でも低温でも長期に渡って安定貯蔵可能になることを見出し、本発明に到達したものである。

(In formula (1), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent). An ether dimer composition containing 10-70% by mass, (B) 0.3-10% by mass of water, (C) 0.001-1% by mass of a stabilizer, and (D) 20-90% by mass of a non-aqueous solvent; As a result, it has been found that stable storage is possible over a long period of time at high and low temperatures, and the present invention has been achieved.

The above (A) is preferably a symmetric ether dimer, and in the above formula (1), R ¹ and R ² are preferably the same atom or hydrocarbon group.

  The above (C) is a phenol compound, organic acid copper salt, phenothiazine, phosphite, thioether, hindered amine compound, ascorbic acid, thiocyanate, thiourea derivative, nitrite, sulfite, thiosulfate And at least one selected from the group consisting of a hydroxylamine derivative and an N-oxyl compound.

  The above (D) is an organic solvent capable of uniformly dissolving the above (A), (B), and (C), and is an alcohol solvent, an ether solvent, an ester solvent, a ketone solvent, an aromatic solvent. It is preferably a solvent selected from the group consisting of amide solvents, nitrile solvents, sulfoxide solvents, monoalcohols, cyclic ethers, glycol monoethers, glycol ethers, esters of glycol monoether, alkyl Particularly preferred is at least one selected from the group consisting of esters, ketones, aromatic hydrocarbons and amides.

  The present invention includes a monomer composition comprising the above-mentioned ether dimer composition, (A) an unsaturated monomer copolymerizable with the ether dimer, and a tetrahydropyran ring formed by polymerizing the monomer composition. It is also a copolymer. The tetrahydropyran ring-containing copolymer preferably has an acid group, and therefore (A) the unsaturated monomer copolymerizable with the ether dimer preferably contains a monomer having an acid group. The tetrahydropyran ring-containing copolymer having an acid group is further added with a compound containing a polymerizable unsaturated double bond and at least one selected from the group consisting of an epoxy group, an oxazoline group, and a hydroxyl group. It is more preferable to use a tetrahydropyran ring-containing copolymer.

  The present invention is also a photosensitive resin composition containing the above-mentioned tetrahydropyran ring-containing copolymer having an acid group and a photopolymerization initiator, and is preferably a color filter resist. The present invention is also a cured product obtained by curing the photosensitive resin composition, and a color filter formed by forming the cured product on a substrate.

  Since the ether dimer composition of the present invention has high storage stability, it can be stored for a long period of time and is easy to handle. For example, since the ether dimer can be mass-produced and stored at once in a factory, the production efficiency is greatly improved. In addition, since the storage stability is high, the quality is stabilized when the copolymer is synthesized. In particular, it can be used as a raw material for a photosensitive resin composition that requires a reduction in the amount of impurities.

The present invention is described in detail below. The description of the constituent requirements described below is an example (representative example) of the embodiment of the present invention, and is not limited to these contents.

<Ether dimer composition>
The ether dimer composition of the present invention is
(A) The following general formula (1):

（式（１）中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。）で表されるエーテルダイマー、（Ｂ）水、（Ｃ）安定剤、（Ｄ）非水系溶媒を含有し、（Ｂ）水の含有量が０．３〜１０質量％であることを特徴とする。
特に、下記一般式（１）

(In formula (1), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent). And (B) water, (C) a stabilizer, (D) a non-aqueous solvent, and (B) the content of water is 0.3 to 10% by mass.
In particular, the following general formula (1)

（式（１）中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。）
で表される（Ａ）エーテルダイマーを含有する組成物であって、（Ａ）エーテルダイマー１０〜７０質量％、（Ｂ）水０．３〜１０質量％、（Ｃ）安定剤０．００１〜１質量％、（Ｄ）非水系溶媒２０〜９０質量％を含有する組成物が好ましい。また、更に液状組成物であることが好ましい。

(In Formula (1), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)
(A) A composition containing an ether dimer (A) 10 to 70% by mass of an ether dimer, (B) 0.3 to 10% by mass of water, (C) a stabilizer 0.001 to A composition containing 1% by mass and (D) 20 to 90% by mass of a non-aqueous solvent is preferred. Further, it is preferably a liquid composition.

  As a method for improving the storage stability of the radically polymerizable monomer, it is common to include a stabilizer, and a water-insoluble radically polymerizable monomer, especially a radically polymerizable monomer that is solid at room temperature, is used. It is also common to improve handleability as a uniform solution form by dissolving in a non-aqueous organic solvent together with a stabilizer. In order to improve the storage stability of the ether dimer composition of the present invention, a three-component system of an ether dimer, a stabilizer, and a non-aqueous solvent is insufficient, and it is important that an appropriate amount of water coexists. The reason is unknown, but sufficient storage stability can be obtained with a small amount of stabilizer by coexisting an appropriate amount of water.

In particular, by setting the ratio of each component within the above range, a uniform liquid composition having high storage stability and good handleability can be obtained. The content ratios of the components (A) to (D) can be appropriately combined within the above range, but more preferable content ratios are (A) ether dimer 15 to 40% by mass, and (B) water 0.5. -7% by mass, (C) stabilizer 0.002-0.1% by mass, (D) non-aqueous solvent 50-85% by mass, particularly preferred content ratio is (A) ether dimer 20-35% by mass, (B) Water 1-5 mass%, (C) Stabilizer 0.003-0.05 mass%, (D) Non-aqueous solvent 55-75 mass% is contained. By adjusting to the said range, the storage stability of an ether dimer composition will become higher.
Below, the said (A)-(D) component is explained in full detail. In addition, about the adjustment of the composition containing each component, although a conventionally well-known mixing method and a purification method can be employ | adopted, it is preferable to refine | purify and adjust a composition after the synthesis reaction of the said (A) component in this invention. .

(A) Ether dimer The ether dimer in the present invention is the following general formula (1).

（式（１）中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。）で表される化合物であり、
下記一般式（２）

(In formula (1), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent). Yes,
The following general formula (2)

（式（２）中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。）で表される化合物である、α−ヒドロキシメチルアクリル酸あるいはそのエステルがエーテル２量化した構造を有する化合物であって、分子中に少なくとも１つのエーテル結合を有するものを意味する。

(In formula (2), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent). It means a compound having a structure in which α-hydroxymethylacrylic acid or its ester is ether-dimerized and having at least one ether bond in the molecule.

  The ether dimer polymerizes while cyclizing to give the following general formula (3)

（式（３）中、Ｒ^１およびＲ^２は、それぞれ独立して、水素原子または置換基を有していてもよい炭素数１〜２５の炭化水素基を表す。）
で表されるエーテルダイマー由来のテトラヒドロピラン環構造を構成単位として有する重合体を生じることができる。

(In Formula (3), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)
The polymer which has the tetrahydropyran ring structure derived from the ether dimer represented by these as a structural unit can be produced.

In the general formula (1) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl; and the like. Among these, a primary or secondary carbon substituent which is difficult to be removed by an acid or heat such as methyl, ethyl, cyclohexyl, benzyl and the like is preferable in terms of further improving the heat resistance of the obtained polymer. Preferably it is methyl.

R ¹ and R ² may be the same substituent or different substituents. R ¹ and R ² are preferably the same substituent in that the transparency and heat resistance of the polymer can be further improved, that is, a symmetrical ether dimer, but from the viewpoint of storage stability of the ether dimer. Are preferably different substituents, ie asymmetrical ether dimers. The reason why the symmetrical ether dimer is inferior in storage stability is not clear, but it is presumed that the symmetrical ether dimer is more likely to be polymerized because of its higher crystallinity. In the present invention, even a symmetrical ether dimer having poor storage stability can be made into an ether dimer composition having high storage stability. Therefore, as the ether dimer, a symmetrical ether dimer, that is, 2, 2 ′-[oxybis (methylene)] bisacrylic acid or dialkyl 2,2 ′-[oxybis (methylene)] bis-2-propenoate is more preferable.

  Specific examples of the symmetrical ether dimer include, for example, 2,2 ′-[oxybis (methylene)] bisacrylic acid, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl- 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′ -[Oxybis (methylene)] bis-2-propenoate, di (n-butyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis ( Methylene)] bis-2-propenoate, di (t-butyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis ( Methylene)] bis-2-propenoate, di (2-ethylhexyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene) )] Bis-2-propenoate, di (1-ethoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2- Propenoate, diphenyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene) ] Bis-2-propenoate, di (t-butylcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene )] Bis-2-propenoate, di (tricyclodecanyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2 ′-[oxybis (methylene)] bis 2-propenoate, diadamantyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 ′-[oxybis (methylene)] bis-2 -Propenoates and the like. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred, most preferably dimethyl-2,2 ′-[oxybis (methylene)] bis -2-propenoate. These ether dimers may be used alone or in combination of two or more.

  The ether dimer content in the ether dimer composition of the present invention is preferably 10 to 70% by mass, more preferably 15 to 40% by mass, and still more preferably 20 to 35% by mass. The higher the ether dimer content, the lower the storage stability. When the ether dimer content is low, the storage stability is improved, but the tetrahydropyran ring content in the polymer is reduced, and a polymer having sufficient heat resistance and transparency cannot be obtained.

(B) Aqueous water is an essential component of the ether dimer composition of the present invention, and there is an appropriate amount range. The content thereof is required to be 0.3 to 10% by mass, more preferably 0.5. -7% by mass, more preferably 1-5% by mass. The reason is not known, but if the water content is too small, the storage stability at high temperatures, which is supposed to be stored in the summer, tends to decrease. Moreover, when there is too much content of water, it exists in the tendency for the storage stability in the low temperature which assumed storage in winter.
The water is preferably pure water. In view of cost, ion exchange water through generally used ion exchange resins is more preferable.
(C) Stabilizer The stabilizer in the present invention is a compound having a function of preventing radical polymerization and oxidative degradation, and one or more kinds of commonly used polymerization inhibitors and antioxidants can be used, and are particularly limited. It is not something. Examples of such compounds include phenolic compounds, organic acid copper salts, phenothiazines, phosphites, thioethers, hindered amine compounds, ascorbic acids, thiocyanates, thiourea derivatives, nitrites, sulfites, thiols, and the like. Examples thereof include sulfates, hydroxylamine derivatives, N-oxyl compounds, and the like. Among these, hydroxy group-containing compounds having a ring structure, particularly phenolic compounds, are preferred in terms of coloring and compatibility. Specifically, hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, methoquinone, 6-t-butyl-2,4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2'-methylenebis (4-methyl-6- t-butylphenol) and the like. N-oxyl compounds are also preferable, and specifically, derivatives of 2,2,6,6-tetramethylpiperidine-1-oxyl, among them 4-hydroxy-2,2,6,6-tetramethylpiperidine-1 -Oxyl and the like.

  Only 1 type may be used for the said stabilizer and it may use 2 or more types together. Since the storage stability of the ether dimer composition of the present invention can be most improved, it is particularly preferable to use the phenol compound and the N-oxyl compound in combination. The mass ratio of the phenolic compound / N-oxyl compound is preferably 15/1 to 5/1, more preferably 10/1 to 7/1, and more preferably 8/1. Most preferred.

  The content of the stabilizer in the ether dimer composition of the present invention is preferably 0.001 to 1% by mass, more preferably 0.002 to 0.1% by mass, and still more preferably 0.003 to 0%. 0.05% by mass. When the content is too small, the storage stability tends to be lowered, and when it is too much, the color is remarkably colored during storage, or the polymerizability is lowered and problems tend to occur in the process of obtaining the polymer.

(D) Non-aqueous solvent The non-aqueous solvent in the present invention is an organic solvent that can uniformly dissolve ether dimer, water, and stabilizer, and is not particularly limited as long as it is such an organic solvent.
The non-aqueous solvent is preferably a solvent selected from the group consisting of alcohol solvents, ether solvents, ester solvents, ketone solvents, aromatic solvents, amide solvents, nitrile solvents, sulfoxide solvents. You may use 1 type, or 2 or more types. Specific examples include the following solvents.
(Alcohol solvent)
For example, monoalcohols such as methanol, ethanol, isopropanol, n-butanol and s-butanol; glycols such as ethylene glycol and propylene glycol; polyhydric alcohols such as glycerin;
(Ether solvent)
Cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Glycol monoethers such as glycol monobutyl ether and 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ether Methyl ether, propylene glycol dimethyl ether, glycol ethers such as propylene glycol diethyl ether (ester solvent)
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Esters of glycol monoethers such as monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Alkyl esters (ketone solvents) such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl acetoacetate and ethyl acetoacetate
Ketones (aromatic solvents) such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone
Aromatic hydrocarbons (amide solvents) such as benzene, toluene, xylene, and ethylbenzene
Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone (nitrile solvents)
Acetonitrile, propionitrile, benzonitrile, etc. (sulfoxide solvents)
Dimethyl sulfoxide The type and amount of the non-aqueous solvent may be appropriately selected according to the purpose and application, the production conditions of the ether dimer composition, the production conditions of the THP ring copolymer, and the like. For example, when a THP ring copolymer is used as a resist resin, if the same non-aqueous solvent as the solvent constituting the resist is used, the non-aqueous solvent is not removed when preparing the resist. The process can be simplified because it can be used, and examples of such solvents include propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ester solvents such as ethyl lactate, ketone solvents such as cyclohexanone, ethylene glycol dimethyl ether, Examples include ether solvents such as ethylene glycol diethyl ether, but are not limited thereto. Further, a solvent having a low boiling point which is easy to remove, such as methyl acetate, ethyl acetate, acetone, methyl ethyl ketone, is also preferable. Further, for example, when obtaining a THP ring copolymer having an acid group, alcohol solvents such as methanol, ethanol, isopropanol, propylene glycol monomethyl ether are used from the viewpoint of lowering the solution viscosity during polymerization and facilitating molecular weight control. Preferably, when a THP ring copolymer is used as a resist resin, an alcohol solvent having a low boiling point such as methanol, ethanol or isopropanol that is easy to remove is more preferable. Therefore, particularly when the THP ring copolymer is used as a resin for an alkali developing negative resist such as a resist for a color filter, as the non-aqueous solvent, the resist solvent (propylene glycol monomethyl ether acetate, 3-methoxybutyl) is used. An ester solvent such as acetate and ethyl lactate, a ketone solvent such as cyclohexanone, an ether solvent such as ethylene glycol dimethyl ether and ethylene glycol diethyl ether) and an alcohol solvent are preferable.
In the ether dimer composition of the present invention, the content of the non-aqueous solvent (D) is preferably 20 to 90% by mass, more preferably 50 to 85% by mass, and still more preferably 55 to 75% by mass. . If the content is too small, the ether dimer and water cannot be dissolved sufficiently uniformly. If the content is too large, the tetrahydropyran ring content in the polymer will decrease, and a polymer having sufficient heat resistance and transparency will be obtained. It becomes impossible.
<Method for producing ether dimer composition>
The method for producing the ether dimer contained in the ether dimer composition of the present invention is not particularly limited, but from the viewpoint of obtaining a symmetrical ether dimer in high yield and purity, α-hydroxymethyl acrylate is a tertiary amine. A method of removing impurities (such as the catalyst and side reaction products shown in FIG. 1) after dehydration and dimerization with a catalyst is preferable.

  In particular, from the viewpoint of improving the stability of the ether dimer composition and preventing gelation during subsequent polymerization, a side reaction product containing a polymerizable unsaturated double bond (crosslinkable compound: ester dimer, trimer) is used. , 0.001% by mass or less, preferably below the detection limit. Further, from the viewpoint of preventing coloring, it is preferable to remove the tertiary amine catalyst to 0.01% by mass or less, preferably 0.001% by mass or less, and more preferably 0.0005% by mass or less.

  As a method for removing these impurities, known purification methods such as extraction, crystal folding, and distillation can be appropriately selected, but crystal bending is preferred because a high-purity ether dimer can be obtained in a high yield. Crystallization means that crystals are precipitated from a liquid phase or the like.

  As a method for producing the ether dimer composition of the present invention, (A) an ether dimer, (B) water, (C) a stabilizer, and (D) a non-aqueous solvent are uniformly mixed in a predetermined ratio and liquid. You just have to.

<Monomer composition containing ether dimer composition>
The present invention is also a monomer composition containing an ether dimer composition and an unsaturated monomer. As the unsaturated monomer, a monomer composition can be polymerized as long as it is a monomer having a radical polymerizable unsaturated bond copolymerizable with ether dimer (hereinafter also simply referred to as a copolymerizable group). May be appropriately selected according to the use of the polymer obtained by the method, and is not particularly limited. The unsaturated monomer may be a compound having only one copolymerizable group in the same molecule (hereinafter also referred to as a monofunctional monomer), or a compound having two or more (hereinafter referred to as a polyfunctional monomer). However, from the viewpoint of obtaining a soluble polymer, a monofunctional monomer is preferable.

  The copolymerizable group is preferably a carbon-carbon double bond or a carbon-carbon triple bond, more preferably a carbon-carbon double bond, and still more preferably a carbon-carbon double bond activated by an adjacent functional group. It is a double bond.

  Examples of the carbon-carbon double bond activated by the adjacent functional group include, for example, a carbon-carbon double bond activated by an adjacent conjugated carbon-carbon double bond (1,3-conjugated diene structure), Carbon-carbon double bonds activated by adjacent conjugated carbonyl groups, carbon-carbon double bonds activated by adjacent conjugated cyano groups, carbon-carbon double bonds activated by adjacent conjugated aromatic rings A carbon-carbon double bond activated by an adjacent ester group, a carbon-carbon double bond activated by an adjacent halogen atom, a carbon-carbon double bond activated by an adjacent ether group, etc. Although mentioned, this invention is not limited only to this illustration.

The monofunctional monomer will be specifically described below, but the present invention does not exclude the use of the polyfunctional monomer, and may be appropriately selected depending on the application.
Examples of the monofunctional monomer include (meth) acrylic acid ester, α-allyloxymethyl acrylic acid ester, (meth) acrylamide, unsaturated monocarboxylic acid, unsaturated polycarboxylic acid, and unsaturated group. Monocarboxylic acid, unsaturated acid anhydride, aromatic vinyl, N-substituted maleimide, α-olefin, halogenated vinyl, conjugated diene, vinyl ester, vinyl ether, N-vinyl Examples include compounds, unsaturated isocyanates, and acetylenes, but the present invention is not limited to such examples. These monofunctional monomers may be used alone or in combination of two or more.

  Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (Meth) acrylic acid sec-butyl, (meth) acrylic acid tert-butyl, (meth) acrylic acid n-amyl, (meth) acrylic acid sec-amyl, (meth) acrylic acid tert-amyl, (meth) acrylic acid n-hexyl, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, octyl (meth) acrylate, ( (Meth) lauryl acrylate, stearyl (meth) acrylate, (meth) acrylic Benzyl, phenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- (meth) acrylic acid 2- Hydroxypropyl, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methacrylic acid 2- Methoxyethyl, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (meth) Β-ethylglycidyl acrylate, (meth) acrylic acid 3,4-epoxycyclohexyl) methyl, N, N-dimethylaminoethyl (meth) acrylate, methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, etc., but the present invention is only such examples It is not limited to. These (meth) acrylic acid esters may be used alone or in combination of two or more.

  Examples of the α-allyloxymethyl acrylate ester include methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, n-propyl α-allyloxymethyl acrylate, and isopropyl α-allyloxymethyl acrylate. , Α-allyloxymethyl acrylate n-butyl, α-allyloxymethyl acrylate sec-butyl, α-allyloxymethyl acrylate tert-butyl, α-allyloxymethyl acrylate n-amyl, α-allyloxymethyl Sec-amyl acrylate, tert-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate, n-hexyl α-allyloxymethyl acrylate, sec-hexyl α-allyloxymethyl acrylate, α- Allyloxymethyl N-heptyl acrylate, n-octyl α-allyloxymethyl acrylate, sec-octyl α-allyloxymethyl acrylate, tert-octyl α-allyloxymethyl acrylate, 2-ethylhexyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylate capryl, α-allyloxymethyl acrylate nonyl, α-allyloxymethyl acrylate decyl, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl acrylate, α-allyloxymethyl Tridecyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, α-allyloxymethyl Stearyl crylate, nonadecyl α-allyloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, ceryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate, crotyl α-allyloxymethyl acrylate, α -1,1-dimethyl-2-propenyl allyloxymethyl acrylate, 2-methylbutenyl α-allyloxymethyl acrylate, 3-methyl-2-butenyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid 3 -Methyl-3-butenyl, α-allyloxymethyl acrylate 2-methyl-3-butenyl, α-allyloxymethyl acrylate oleyl, α-allyloxymethyl acrylate linole, α-allyloxymethyl acrylate linolene, α -Allyloxymethyl Cyclopentyl lylate, α-allyloxymethyl acrylate cyclopentyl methyl, α-allyloxymethyl acrylate acrylate, α-allyloxymethyl acrylate acrylate methyl, α-allyloxymethyl acrylate 4-methylcyclohexyl acrylate, α-allyloxymethyl 4-tert-butylcyclohexyl acrylate, tricyclodecanyl α-allyloxymethyl acrylate, isobornyl α-allyloxymethyl acrylate, adamantyl α-allyloxymethyl acrylate, dicyclopentanyl α-allyloxymethyl acrylate , Α-allyloxymethyl acrylate dicyclopentenyl, α-allyloxymethyl acrylate phenyl, α-allyloxymethyl acrylate methyl phenyl, α-allyloxymethyl acrylate Methylphenyl, α-allyloxymethyl acrylate trimethylphenyl, α-allyloxymethyl acrylate 4-tert-butylphenyl, α-allyloxymethyl benzyl benzyl, α-allyloxymethyl acrylate diphenylmethyl, α-allyloxy Diphenylethyl methyl acrylate, triphenylmethyl α-allyloxymethyl acrylate, cinnamyl α-allyloxymethyl acrylate, naphthyl α-allyloxymethyl acrylate, anthranyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic Acid methoxyethyl, α-allyloxymethyl acrylate methoxyethoxyethyl, α-allyloxymethyl acrylate methoxyethoxyethoxyethyl, α-allyloxymethyl acrylate 3-methoxybutyl , Ethoxyethyl α-allyloxymethyl acrylate, ethoxyethoxyethyl α-allyloxymethyl acrylate, cyclopentoxyethyl α-allyloxymethyl acrylate, cyclohexyloxyethyl acrylate α-allyloxymethyl, α-allyloxymethyl Cyclopentoxyethoxyethyl acrylate, cyclohexyloxyethoxyethyl α-allyloxymethyl acrylate, dicyclopentenyloxyethyl α-allyloxymethyl acrylate, phenoxyethyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid Phenoxyethoxyethyl, α-allyloxymethyl acrylate glycidyl, α-allyloxymethyl acrylate β-methyl glycidyl, α-allyloxymethyl acrylate β-ethyl glycidyl Α-allyloxymethyl acrylate 3,4-epoxycyclohexylmethyl, α-allyloxymethyl acrylate 2-oxetanemethyl, α-allyloxymethyl acrylate 3-methyl-3-oxetanemethyl, α-allyloxymethylacrylic 3-ethyl-3-oxetanemethyl acid, tetrahydrofuranyl α-allyloxymethyl acrylate, tetrahydrofurfuryl α-allyloxymethyl acrylate, tetrahydropyranyl α-allyloxymethyl acrylate, dioxazolanyl, α-allyloxymethyl acrylic Although dioxanyl acid etc. are mentioned, this invention is not limited only to this illustration. These α-allyloxymethyl acrylates may be used alone or in combination of two or more.

  Examples of (meth) acrylamide include N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, acryloylmorpholine, and the like, but the present invention is not limited to such examples. These (meth) acrylamides may be used alone or in combination of two or more.

  Examples of unsaturated monocarboxylic acids include (meth) acrylic acid, crotonic acid, cinnamic acid, vinyl benzoic acid, and the like, but the present invention is not limited to such examples. These unsaturated monocarboxylic acids may be used alone or in combination of two or more.

  Examples of the unsaturated polyvalent carboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and the like, but the present invention is not limited to such examples. These unsaturated polyvalent carboxylic acids may be used alone or in combination of two or more.

  Examples of the unsaturated monocarboxylic acid in which the chain between the unsaturated group and the carboxyl group is extended include 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meta ) Acryloyloxyethyl hexahydrophthalic acid and the like are mentioned, but the present invention is not limited to such examples. These unsaturated monocarboxylic acids in which the chain between the unsaturated group and the carboxyl group is extended may be used alone or in combination of two or more.

  Examples of unsaturated acid anhydrides include maleic anhydride and itaconic anhydride, but the present invention is not limited to such examples. These unsaturated acid anhydrides may be used alone or in combination of two or more.

  Examples of the aromatic vinyl include styrene, α-methylstyrene, vinyltoluene, methoxystyrene, 2-vinylpyridine, 4-vinylpyridine and the like, but the present invention is not limited only to such examples. . These aromatic vinyls may be used alone or in combination of two or more.

  Examples of the N-substituted maleimide include methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide, and the like, but the present invention is not limited to such examples. These N-substituted maleimides may be used alone or in combination of two or more.

  Examples of the α-olefin include ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-octene, and the like, but the present invention is not limited to such examples. These α-olefins may be used alone or in combination of two or more.

  Examples of the vinyl halide include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, trifluoroethylene, and tetrafluoroethylene, but the present invention is not limited to such examples. These vinyl halides may be used alone or in combination of two or more.

  Examples of the conjugated diene include 1,3-butadiene, isoprene, chloroprene, neoprene, cyclopentadiene, and the like, but the present invention is not limited to such examples. These conjugated dienes may be used alone or in combination of two or more.

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and the like, but the present invention is not limited to such examples. These vinyl esters may be used alone or in combination of two or more.

  Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol. Although vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, etc. are mentioned, this invention is not limited only to this illustration. These vinyl ethers may be used alone or in combination of two or more.

  Examples of the N-vinyl compound include N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl imidazole, N-vinyl morpholine, N-vinyl acetamide, etc., but the present invention is limited to such examples. It is not something. These N-vinyl compounds may be used alone or in combination of two or more.

  Examples of the unsaturated isocyanate include isocyanatoethyl (meth) acrylate and allyl isocyanate, but the present invention is not limited to such examples. These unsaturated isocyanates may be used alone or in combination of two or more.

  The content of the ether dimer composition in the monomer composition of the present invention may be appropriately selected depending on the application, but the polymer derived from the tetrahydropyran ring has sufficient characteristics such as heat resistance and transparency. From the viewpoint of imparting and suppressing gelation during polymerization, the content is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 20 to 70% by mass. In the case of obtaining a polymer for use in a color filter, the content of the ether dimer itself is 2 to 60% by mass, preferably 5 to 55% by mass, more preferably 5 to 50% by mass, particularly preferably in all monomer components. It is preferable to mix the ether dimer composition of the present invention with another monomer so that the amount of the monomer becomes 5 to 30% by mass.

  A preferred mode of use of the polymer obtained by polymerizing the monomer composition of the present invention is a polymer having an acid group (at least a part of the unsaturated monomer in the monomer composition has an acid group). And a usage mode used as a crosslinking agent in a binder resin of an alkali developing negative resist or a thermosetting epoxy resin composition. The alkali-developable negative resist is generally a composition containing at least an alkali-soluble resin, a photocurable compound, and a photoinitiator, and is applied to a substrate, formed into a film, exposed through a photomask, and then exposed to an alkali. This is for obtaining a fine pattern by washing away unexposed portions with a developer. The thermosetting epoxy resin composition generally contains at least an epoxy resin and an acid group-containing polymer, preferably further contains a curing catalyst, and is cured by heating.

  The alkali-developable negative resist and the thermosetting epoxy resin composition are used in various applications, but color filter applications are preferred in that the characteristics of the tetrahydropyran ring-containing polymer in the present invention can be utilized. . Hereinafter, although the monomer composition for obtaining the polymer suitable for a color filter use is explained in full detail, this invention is not limited to this.

  The monomer composition of the present invention preferably contains the ether dimer composition and an unsaturated monomer having an acid group. As the unsaturated monomer having an acid group, any monomer having a functional group capable of neutralizing with an alkali to form an alkali salt, such as a carboxyl group, a carboxylic acid anhydride group, a phosphoric acid group, or a sulfonic acid group. Although it does not specifically limit, the monomer which has a carboxyl group and a carboxylic anhydride group is preferable, and the monomer which has a carboxyl group is more preferable. Examples of the monomer having a carboxyl group or a carboxylic acid anhydride group include the above-described unsaturated monocarboxylic acid, unsaturated polycarboxylic acid, and unsaturated monocarboxylic acid in which the chain between the unsaturated group and the carboxyl group is extended. And unsaturated acid anhydrides.

The content of the monomer having an acid group in the monomer composition of the present invention is preferably from 3 to 70% by mass in the monomer composition from the viewpoint of being suitably used for color filter applications. Preferably it is 5-60 mass%, More preferably, it is 7-50 mass%.
The monomer composition of the present invention may contain other copolymerizable monomers as required in addition to the ether dimer and the unsaturated monomer having an acid group. Examples of other copolymerizable monomers include the monomers described above. Among other copolymerizable monomers, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, styrene, vinyltoluene, N-benzylmaleimide have good transparency, From the viewpoint that heat resistance is not easily impaired, and from the viewpoint of being suitably used in color filter applications, 3 to 80% by mass is preferable in the monomer composition, more preferably 5 to 75% by mass, and further preferably 7 to 7%. 70% by mass.

<Tetrahydropyran ring-containing copolymer>
The present invention is also a polymer obtained by polymerizing the monomer composition containing the ether dimer composition and the unsaturated monomer, that is, a tetrahydropyran ring-containing copolymer (THP ring copolymer).

  The THP ring copolymer of the present invention can be obtained by radical polymerization of the monomer composition of the present invention. Although a polymerization mechanism other than radical polymerization can be employed, it is advantageous for industrial production, and a radical polymerization mechanism is preferable in terms of improving the cyclopolymerization rate of the ether dimer. As the polymerization method, a known polymerization method such as a bulk polymerization method, a precipitation polymerization method, a solution polymerization method, a dispersion polymerization method, a suspension polymerization method, and an emulsion polymerization method can be used, and it can be appropriately selected according to the purpose and application. The solution polymerization method is preferable from the viewpoint of reaction control and improvement of the cyclopolymerization rate.

  When applying the solution polymerization method to obtain the THP ring copolymer of the present invention, a solvent for polymerization may be newly prepared and used, or the monomer composition of the present invention may be used as an ether dimer composition. Since the derived non-aqueous solvent is included, it is not necessary to newly prepare a solvent for polymerization. That is, a separate solvent may be prepared as the polymerization solvent, or a non-aqueous solvent contained in the monomer composition may be used as the polymerization solvent. The polymerization solvent may be appropriately selected according to the use and polymerization conditions, and examples of the non-aqueous solvent for the ether dimer composition include those described above.

  When polymerizing the monomer component, a commonly used polymerization initiator may be added as necessary. Although it does not specifically limit as a polymerization initiator, For example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amyl Organic peroxides such as peroxy-2-ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexane Carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo compounds such as dimethyl 2,2′-azobis (2-methylpropionate), and the like. These polymerization initiators may be used alone or in combination of two or more. The amount of initiator used may be set as appropriate according to the combination of monomers used, reaction conditions, target polymer molecular weight, etc., and is not particularly limited, but the weight average molecular weight without gelation. Is from 0.1 to 15% by mass, more preferably from 0.5 to 10% by mass, based on the total monomer components, in that a polymer of several thousand to several tens of thousands can be obtained.

  When polymerizing the monomer component, a chain transfer agent that is usually used may be added, if necessary, for adjusting the molecular weight. Examples of the chain transfer agent include mercaptan chain transfer agents such as n-dodecyl mercaptan, mercaptopropionic acid, mercaptoacetic acid, and methyl mercaptoacetate, and α-methylstyrene dimer. Preferably, the chain transfer effect is high. N-dodecyl mercaptan and mercaptopropionic acid, which can reduce residual monomers and are easily available, are preferred. When a chain transfer agent is used, the amount used may be set as appropriate according to the combination of monomers used, reaction conditions, the molecular weight of the target polymer, etc., and is not particularly limited. And 0.1 to 15% by mass, more preferably 0.5 to 10% by mass with respect to all monomer components, in that a polymer having a weight average molecular weight of several thousand to several tens of thousands can be obtained. Is preferred.

  In the present invention, a THP ring copolymer is obtained by solution polymerization of the monomer component. The polymerization temperature and polymerization time vary depending on the type and ratio of the monomer component used, but preferably the polymerization temperature is 0 to 150 ° C., the polymerization time is 0.5 to 20 hours, and more preferably the polymerization temperature is 80. It is good that they are -150 degreeC, superposition | polymerization time 1-15 hours, More preferably, superposition | polymerization temperature 80-140 degreeC and superposition | polymerization time 1-10 hours.

  The charging method of the monomer component at the time of the polymerization reaction is not particularly limited, and the whole amount may be charged all at once, a part may be charged all at once and the rest may be dropped, or the whole amount may be dropped. Although it is good, from the viewpoint of controlling the amount of heat generation, it is preferable to charge a part and drop the rest, or drop the whole amount.

  Although the weight average molecular weight of the THP ring copolymer is not particularly limited, it is 2000 to 200000, more preferably 5000 to 100000, and still more preferably 5000 to 50000 from the viewpoint that it can be suitably used for color filter applications. Good. When the weight average molecular weight exceeds 200,000, the viscosity becomes too high to form a coating film. On the other hand, when the weight average molecular weight is less than 2,000, the alkali solubility is too strong. There is a tendency that sufficient heat resistance is difficult to be exhibited.

The acid value of the THP ring copolymer is not particularly limited, but is preferably 3 to 350 mgKOH / g, more preferably 5 to 350 mgKOH / g, from the viewpoint that it can be suitably used for color filter applications. More preferably, it is 40-300 mgKOH / g. When the acid value of the polymer is less than 3 mgKOH / g, the solubility may be insufficient when the solubility by an alkaline substance is required. When it exceeds 350 mgKOH / g, it tends to be too viscous to form a coating film.
The polymer of the present invention may further contain a polymerizable double bond in the side chain. By giving a polymerizable double bond to the side chain, it can be cured by heat or light. Therefore, the sensitivity to light when a photocurable resin composition (photosensitive resin composition) is obtained is improved, the composition is cured with a smaller amount of light, and the mechanical strength after curing is also increased. Examples of the method for introducing a polymerizable double bond into the side chain include a method of adding a compound containing a polymerizable unsaturated double bond and at least one selected from the group consisting of an epoxy group, an oxazoline group, and a hydroxyl group. . As a polymerizable unsaturated double bond, the double bond which a (meth) acryloyl group has from a reactive point of the polymer obtained is mentioned preferably.
Specific examples of the compound containing a polymerizable unsaturated double bond selected from the group consisting of an epoxy group, an oxazoline group, and a hydroxyl group include 2-hydroxyethyl (meth) acrylate and (meth) acrylic. Compounds having a hydroxyl group and a double bond such as 2-hydroxypropyl acid and allyl alcohol; Epoxy groups and a double bond such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and allyl glycidyl ether A compound having a double bond with an oxazoline group such as vinyl oxazoline and isopropenyl oxazoline; among these, among them, the reactivity is high, the reaction can be easily controlled, and the acquisition is easy. Not only radical polymerizable double bonds but also hydroxyl groups can be introduced at the same time From the point, glycidyl (meth) acrylate and (meth) acrylic acid 3, 4-epoxycyclohexyl methyl.
The addition amount of the compound containing a polymerizable unsaturated double bond and at least one selected from the group consisting of an epoxy group, an oxazoline group, and a hydroxyl group is preferably 5 to 120 parts by mass with respect to 100 parts by mass of the polymer. More preferably, it is good to set it as 10-80 mass parts. If the amount is too small, the curability with the curable resin composition is insufficient and the strength after curing is insufficient. On the other hand, if the amount is too large, the storage stability of the polymer having a polymerizable double bond in the side chain is lowered. There is a case.
As reaction conditions for adding a compound containing a polymerizable unsaturated double bond and at least one selected from the group consisting of an epoxy group, an oxazoline group, and a hydroxyl group, the temperature is preferably 50 ° C to 150 ° C, and 80 ° C. ˜140 ° C. is more preferred, and 90 ° C. to 120 ° C. is most preferred. If the temperature is lower than the above range, the addition reaction may not proceed sufficiently. On the other hand, if the temperature is higher than the above range, gelation tends to occur during the addition reaction. The reaction time is preferably 0.5 to 24 hours, and more preferably 1 to 15 hours. In the addition reaction, a known catalyst can be used as necessary. As the catalyst, for example, when the compound to be added has an epoxy group, a tertiary amine such as triethylamine is preferable. The amount of the catalyst used is preferably 0.01 to 30% by mass, more preferably 0.05 to 5% by mass, and most preferably 0.1 to 2% by mass with respect to the polymer. If the amount of the catalyst used is less than the above range, the addition reaction may not proceed sufficiently. On the other hand, if the amount exceeds the above range, the resulting polymer may be colored, or the catalyst content may be precipitated without being dissolved. There is a fear.
Furthermore, at the time of the addition reaction, a gas having an inhibitory effect may be introduced into the reaction system, or an inhibitor may be added. By introducing a gas having a prohibiting effect into the reaction system or adding an inhibitor, gelation during the addition reaction can be prevented.

The polymer of the present invention may further contain an epoxy group. Thereby, it can be cured by heat or light. In order to introduce an epoxy group into the polymer, for example, a monomer having an epoxy group may be polymerized as a monomer component. Examples of the monomer having an epoxy group include glycidyl (meth) acrylate and (meth) acrylic acid-3,4-epoxycyclohexyl. These monomers for introducing an epoxy group may be only one type or two or more types.
<Photosensitive resin composition>
The present invention is also a photosensitive resin composition containing the tetrahydropyran ring-containing copolymer of the present invention.
In particular, it can be suitably used for a photosensitive resin composition for a color filter. Usually, the photosensitive resin composition for a color filter contains a photopolymerization initiator and a colorant in addition to the copolymer of the present invention.
Known photopolymerization initiators can be used. Specifically, benzoin such as benzoin, benzoin methyl ether, and benzoin ethyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t- Acetophenones such as butyldioxy-1-methylethyl) acetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4- Thioxanthones such as diisopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; Benzophenone, 4- (1-t-butyldioxy-1-methyl Benzophenones such as til) benzophenone and 3,3 ′, 4,4′-tetrakis (t-butyldioxycarbonyl) benzophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinyl-1- Propane (“Irgacure 907”; manufactured by Ciba Japan), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acylphosphine oxides and xanthones,
In addition, 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropane- 1-one, 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan-1-one, 2-dimethylamino-1- (4-ethylphenyl) -2-methylpropan-1-one, 2-dimethylamino-1- (4-isopropylphenyl) -2-methylpropan-1-one, 1- (4-butylphenyl) -2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino -1- (4-methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylthiophenyl) propane- -One, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one 2-benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) -butan-1-one, 2-dimethylamino-2-[(4-methylphenyl) methyl] -1- [4- (4 Α-aminoketone compounds such as -morpholinyl) phenyl] -1-butanone;
2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-phenylbutan-1-one, 1- (4-methylphenyl) -2-hydroxy-2-methyl Propan-1-one, 1- (4-isopropylphenyl) -2-methylpropan-1-one, 1- (4-butylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy- 2-methyl-1- (4-octylphenyl) propan-1-one, 1- (4-dodecylphenyl) -2-methylpropan-1-one, 1- (4-methoxyphenyl) -2-methylpropane- 1-one, 1- (4-methylthiophenyl) -2-methylpropan-1-one, 1- (4-chlorophenyl) -2-hydroxy-2-methylpropan-1-one, 1- 4-Bromophenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-1- (4-hydroxyphenyl) -2-methylpropan-1-one, 1- (4-dimethylaminophenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4-carboethoxyphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1- [4- ( 2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl [Alpha] -hydroxy ketone compounds such as phenyl} -2-methyl-propan-1-one.
These photopolymerization initiators are used as one kind or a mixture of two or more kinds, a polymer obtained by polymerizing the ether dimer composition of the present invention as an essential component, and a radical polymerizable compound (described later) used as necessary. It is preferable that 0.5-30 mass parts is contained with respect to a total of 100 mass parts. When the amount of the photopolymerization initiator is less than 0.5 parts by mass, it is necessary to increase the light irradiation time or it is difficult for polymerization to occur even if light irradiation is performed. It becomes impossible. In addition, even if it mixes a photoinitiator exceeding 30 mass parts, there is no merit which uses it in large quantities.

  The photosensitive resin composition for a color filter of the present invention uses a dye / pigment as a colorant. From the viewpoint of heat resistance and light resistance, organic or inorganic pigments are preferable. Specifically, organic pigments such as organic compounds classified as pigments in the color index CI (published by The Society of Dyers and Colorists). And inorganic pigments such as metal oxides or composite oxides.

  Moreover, when using dye as a coloring agent, it melt | dissolves uniformly in the photosensitive resin composition, and can obtain the photosensitive resin composition for color filters. The dye that can be used is not particularly limited, and conventionally known dyes for color filters can be used.

These colorants are used singly or in combination of two or more, and are a polymer obtained by polymerizing the ether dimer composition of the present invention as an essential component, and a radically polymerizable compound used as necessary (described later). It is preferable to use 10 to 150 parts by mass with respect to 100 parts by mass in total. More preferably, it is 20-100 mass parts.
The photosensitive resin composition for a color filter of the present invention may contain a radical polymerizable compound other than a polymer obtained by polymerizing the ether dimer composition as an essential component. Examples of the radical polymerizable compound include a radical polymerizable oligomer and a radical polymerizable monomer. For example, as the radically polymerizable oligomer, unsaturated polyester, epoxy acrylate, urethane acrylate, polyester acrylate, or the like can be used.
Examples of radically polymerizable monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallylbenzenephosphonate; vinyl ester monomers such as vinyl acetate and vinyl adipate Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, (2-oxo-1,3-dioxolan-4-yl) -methyl (meth) acrylate, (Di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate of (meth) acrylic monomer; triallyl cyanurate and the like can be used. These are appropriately selected according to the required characteristics, and one or more can be used.
In the photosensitive resin composition for a color filter of the present invention, when the polymer obtained by polymerizing the ether dimer composition of the present invention as an essential component and the radical polymerizable compound are used in combination, the total of both is 100 parts by mass. In this case, it is preferable to use 15 parts by mass or more, more preferably 30 parts by mass or more, of a polymer obtained by polymerizing the ether dimer composition as an essential component. If the amount is small, various effects based on the radical polymerizable copolymer (A) may not be sufficiently exhibited.

From the viewpoint of workability when applying the photosensitive resin composition for a color filter of the present invention to a base material (preferably a substrate), a solvent may be blended in the composition. Solvents include hydrocarbons such as toluene and xylene; cellosolves such as cellosolve and butylcellosolve; carbitols such as carbitol and butylcarbitol; cellosolve acetate, carbitol acetate, (di) propylene glycol monomethyl ether acetate, etc. Esters; ketones such as methyl isobutyl ketone and methyl ethyl ketone; (di) ethers such as ethylene glycol dimethyl ether. These solvents can be used singly or in combination of two or more, and may be used in an appropriate amount so that the composition has an optimum viscosity during the coating operation. In addition, the copolymer solution obtained by solution polymerization can be used in the composition as it is, diluted or concentrated.
If necessary, the photosensitive resin composition for a color filter of the present invention may be added with known additives such as a dispersant, a sensitizer, a polymerization inhibitor, an adhesion improver, a filler, and a plasticizer. May be.
<Hardened product obtained by curing photosensitive resin composition, and color filter>
The present invention is also a cured product obtained by curing the photosensitive resin composition, and a color filter in which the cured product is formed on a substrate.
The photosensitive resin composition of the present invention is usually applied to a base material (preferably a substrate) by a known method and then pre-baked to evaporate the solvent to form a coating film (cured product). Subsequently, after exposing this coating film through a photomask, an unexposed portion is dissolved in an alkaline aqueous solution to perform alkali development. Next, after washing as necessary, post-baking is performed. In this way, a predetermined cured product is formed.
The color filter formed by forming the cured product on a substrate is specifically a color filter having segments formed by curing the photosensitive resin composition. Examples of methods for forming color filter segments (black matrix, red, green and blue pixels, photo spacers, protective layers, orientation control ribs, etc.) include photolithographic methods, printing methods, electrodeposition methods, and ink jet methods. Photolithographic methods include mainstream negative acrylic photosensitive resin composition (photosensitive acrylic method), non-photosensitive polyimide resin composition and positive resist (nonphotosensitive polyimide). Law). Specifically, in the photosensitive acrylic method, a negative photosensitive resin composition is applied onto a support substrate and dried, and then a photomask is overlaid on the formed coating film, and exposure is performed through this photomask. In this method, the exposed portions are photocured, the unexposed portions are developed, washed as necessary, and further heat-cured or photocured to form segments of each color filter. When the photosensitive resin composition of the present invention is used as this negative photosensitive resin composition, high quality color filter segments can be formed with high yield.
As a form of the color filter, it is a necessary requirement that a pixel is formed on a transparent substrate in the case of a liquid crystal display device, and a photoelectric conversion element substrate in the case of an imaging tube element. Forming a black matrix that isolates each pixel, forming a protective film on the pixel, forming a photo spacer on the black matrix region, forming a transparent electrode such as ITO on the pixel or protective film, In some cases, an alignment film and an alignment control structure are formed. In some cases, a black matrix and pixels, and a protective film, a photospacer, and the like are formed on a transparent substrate on which TFTs (thin film transistors) are formed.
The color filter of the present invention only needs to have at least one segment formed using the photosensitive resin composition of the present invention, but preferably the color of all pixels, more preferably a black matrix. And a pixel is formed using the photosensitive resin composition of this invention. The photosensitive resin composition of the present invention is particularly suitable for pixels that need to be colored and black matrix, but is also suitable for forming segments that do not require coloring, such as photo spacers and protective layers.
Transparent substrates include glass, thermoplastic sheets such as polyesters, polycarbonates, polyolefins, polysulfones, cyclic olefin ring-opening polymers and their hydrogenated products, and thermosetting plastic sheets such as epoxy resins and unsaturated polyester resins. From the viewpoint of heat resistance, a glass plate and a heat resistant plastic sheet are preferable. The transparent substrate may be subjected to chemical treatment with a corona discharge treatment, an ozone treatment, a silane coupling agent, or the like, if necessary.
The black matrix is formed on a transparent substrate using a metal thin film or a photosensitive colored resin composition for black matrix. The black matrix using a metal thin film is formed of, for example, a chromium single layer or two layers of chromium and chromium oxide. In this case, first, the metal or metal / metal oxide thin film is formed on the transparent substrate by vapor deposition, sputtering, or the like. Next, after forming a positive photosensitive film thereon, the photomask is exposed and developed using the photomask to form a black matrix image. Thereafter, the thin film is etched to form a black matrix. When using the photosensitive coloring resin composition for black matrix, a black matrix is formed according to segment formation by said photosensitive acrylic method.
The pixels are usually three colors of red, green, and blue. For example, first, green pixels are formed according to the above-described segment formation by the photosensitive acrylic method using a green photosensitive coloring composition. This operation is performed for the remaining two colors to form pixels of three colors. The order of forming the pixels of each color is not particularly limited.
The protective film is formed on the pixels according to the above-described segment formation by the photosensitive acrylic method using the transparent photosensitive resin composition for the protective film after forming the pixels as necessary. In some cases, a protective film is not formed in order to reduce costs and simplify processes.
When forming a transparent electrode on a pixel or a protective film, sputtering method, vacuum deposition method, CVD using indium tin oxide (ITO), zinc oxide (ZnO), tin oxide (SnO), etc., and alloys thereof. A thin film is formed by a method or the like, and if necessary, a predetermined pattern can be formed by etching using a positive resist or using a jig. In some liquid crystal driving methods such as a planar alignment driving method (IPS mode), a transparent electrode may not be formed. Examples of the method for applying the photosensitive resin composition to the substrate include spin coating, slit coating, roll coating, casting coating, and the like. Particularly, when using the photosensitive resin composition of the present invention, a method by slit coating is used. preferable. The coating conditions for slit coating vary depending on the slit-and-spin method, the spinless method, the size of the transparent substrate, the target film thickness, and the like, and the ejection amount from the nozzle and the moving speed of the slit head are appropriately selected. The lip width at the nozzle tip is usually 30 to 500 μm, and the distance between the nozzle tip and the substrate is usually 30 to 300 μm. In addition, the photosensitive resin composition of this invention is preferably applicable also to the method by spin coating, roll coating, and cast coating. The thickness of the coating film is usually 0.3 to 3.5 μm in the case of a black matrix, a pixel and a protective film, and is usually 1 to 10 μm in the case of a photospacer.
The coating film after being applied to the substrate is dried using a hot plate, IR oven, convection oven or the like. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of the curing component, the film thickness, the performance of the dryer, and the like.
The exposure is a step of irradiating the coating film with actinic rays through a predetermined mask pattern. Examples of active light sources include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, fluorescent lamps, argon ion lasers, YAG Laser light sources such as laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser are used. Examples of the exposure system include a proximity system, a mirror projection system, and a stepper system, but the proximity system is preferably used.
After the exposure, the film is developed with a developer to remove unexposed portions and form a pattern. Any developer can be used as long as it dissolves the photosensitive resin composition of the present invention. Usually, an organic solvent or an alkaline aqueous solution is used. When an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development. In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffering agent, a dye, a pigment, and the like as necessary. Alkaline agents include inorganic alkali agents such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, and sodium bicarbonate. ; Amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, etc., and these may be used alone or in combination of two or more; Also good. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan acid alkyl esters, monoglyceride alkyl esters; alkylbenzene sulfonates, alkylnaphthalene sulfonates, and the like. Anionic surfactants such as alkyl sulfates, alkyl sulfonates and sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids. These may be used alone or in combination of two or more. Good. Examples of the organic solvent include alcohols such as isopropanol, benzyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol, and these may be used alone or in combination of two or more. The development treatment is usually performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, or ultrasonic development.
After the development, it is usually heated at a temperature of 150 to 250 ° C. for 5 to 60 minutes using a heating device such as a hot plate, a convection oven, a high-frequency heater, etc., and subjected to a thermosetting treatment.
A liquid crystal display panel including the color filter can be manufactured, for example, by forming an alignment film on the inner surface side of the color filter, and laminating a liquid crystal compound in a gap portion by bonding to a counter substrate.
As the alignment film, a resin film such as polyimide is suitable, and usually a surface treatment is performed by ultraviolet treatment or rubbing treatment after coating and heat baking. The liquid crystal compound is not particularly limited, and conventionally known liquid crystal compounds can be used. The counter substrate is preferably a TFT substrate, and a substrate manufactured by a normal method can be used. The bonding gap between the color filter and the counter substrate is usually in the range of 2 to 8 μm. After the opposing substrates are bonded together, the liquid crystal display panel is completed by sealing with a sealing material.

EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example. Unless otherwise specified, “part” means “part by mass”, and “%” means “% by mass”.
(Preparation of ether dimer composition)
[Example 1]
1. In a reactor equipped with a reaction stirrer, a temperature sensor, and a cooling pipe, 450.0 parts of methyl α-hydroxymethyl acrylate (RHMA-M), 1,4-diazabicyclo [2,2,2] octane (DABCO) 13.5 parts and p-methoxyphenol (MEHQ) 0.9 parts were charged and heated to 90 ° C. with stirring. After the internal temperature reached 85 ° C., the reaction was continued for 9 hours while maintaining 90 ± 5 ° C. in a state of normal pressure in the reactor.
2. Dilution with methanol After confirming that the reaction solution temperature was 40 ° C. or lower, 355.0 parts of methanol (MeOH) was added for dilution (conditions: normal pressure, 35 ± 5 ° C.).

3. Crystallization The MeOH dilution was dropped into a different reactor containing 1485.0 parts of water to crystallize the RHMA ether dimer (conditions: normal pressure, 30 ° C. or lower).
4). Filtration The slurry containing the RHMA ether dimer was filtered using a pressure filter (conditions: normal pressure to 0.1 MPa, 15 ° C. or lower).
5. Cake washing The filter cake of the RHMA ether dimer was washed with water (conditions: normal pressure to 0.1 MPa, room temperature). In the washing, washing was repeated 3 times using 380.0 parts of water at one time.
6). 184.0 parts of propylene glycol monomethyl ether acetate (PGMEA) was added to the cake of RHMA ether dimer cake and dissolved (conditions: normal pressure, 60 ° C.).
7). The oil layer was separated into an oil layer and an aqueous layer containing an RHMA ether dimer, and the aqueous layer was removed (conditions: normal pressure, 60 ° C.). The oil layer was 412.5 parts, and the removed aqueous layer was 141.9 parts.
8). Solution preparation (concentration adjustment)
In the oil layer (solution containing RHMA ether dimer and PGMEA), PGMEA (180.0 parts), isopropanol (IPA) 340.0 parts, MEHQ 0.049 parts, 4-hydroxy-2,2,6,6-tetramethyl Piperidine-1-oxyl (4H-TEMPO) 0.006 part was added, and 932.5 parts of compositions were obtained. In addition, the amount of the crosslinkable compound (ester dimer, trimer) as a side reaction product was below the detection limit.
It shows in Table 1 about each composition.
9. Composition analysis Each composition was analyzed by gas chromatography, Karl Fischer moisture meter, spectrophotometer. The analysis results are shown in Table 1.
[Example 2]
After adding 1.9 parts of water to 100 parts of the ether dimer composition obtained in Example 1, the water content was measured with a Karl Fischer moisture meter. The amount of components other than water was calculated from the amount of water added. The results are shown in Table 1.
[Example 3]
An ether dimer composition was prepared and analyzed in the same manner as in Example 2 except that the amount of water added was 4.1 parts. The results are shown in Table 1.
[Comparative Example 1]
IPA was distilled off from 100 parts of the ether dimer composition obtained in Example 1 while blowing dry air under normal pressure, and azeotropic dehydration with IPA was performed. During azeotropic dehydration, dry IPA (water content of 100 ppm or less) equivalent to distilled IPA was supplied.
After dehydration for 2 hours, the mixture was cooled while flowing dry air to obtain a dehydrated ether dimer composition. The amount of water was measured with a Karl Fischer moisture meter, and the amount of components other than water was calculated from the amount of IPA distilled off and the amount of IPA added. The results are shown in Table 1.
[Comparative Example 2]
An ether dimer composition was prepared and analyzed in the same manner as in Example 2 except that the amount of water added was 15 parts. The results are shown in Table 1.
[Comparative Example 3]
In the same manner as in Example 1, Step 5. The cake was washed. 20 parts of the cake was spread on a vat and dried in a vacuum dryer at room temperature for 24 hours to obtain a white powder. The analysis results are shown in Table 1.

[High temperature storage stability test of ether dimer composition]
[Example 4]
25 parts of the ether dimer composition obtained in Example 1 was sealed in a 50 ml glass screw tube bottle and stored in a dryer at 50 ° C. It was taken out every other month, and it was determined whether or not a polymer was generated in the following manner.
-It was determined by visual observation that a polymer was formed when solidified or white powder was generated.
-When there was no problem in visual observation, the ether dimer composition was dropped into n-hexane, and when a white precipitate was formed, it was determined that a polymer was formed.
Storage at 50 ° C. is continued for up to 6 months, and Table 1 shows in what month a polymer was formed. In addition, when the polymer was not produced even in the 6th month, it was marked as “good” because the high temperature stability was sufficient.
[Example 5]
High temperature storage stability was evaluated in the same manner as in Example 4 except that the ether dimer composition obtained in Example 2 was used. The results are shown in Table 1.
[Example 6]
High temperature storage stability was evaluated in the same manner as in Example 4 except that the ether dimer composition obtained in Example 3 was used. The results are shown in Table 1.
[Comparative Example 4]
High temperature storage stability was evaluated in the same manner as in Example 4 except that the ether dimer composition obtained in Comparative Example 1 was used. The results are shown in Table 1.
[Comparative Example 5]
High temperature storage stability was evaluated in the same manner as in Example 4 except that the ether dimer composition obtained in Comparative Example 2 was used. The results are shown in Table 1.
[Comparative Example 6]
High temperature storage was performed in the same manner as in Example 4 except that the white powder obtained in Comparative Example 3 was used. The determination was made by stirring and mixing 0.1 part of white powder and 10 parts of tetrahydrofuran and whether or not insoluble matter remained. The results are shown in Table 1.

[Low temperature storage stability test of ether dimer composition]
[Example 7]
25 parts of the ether dimer composition obtained in Example 1 was put in a 50 ml glass screw tube bottle, sealed, and stored in a refrigerator adjusted to 5 ° C. for 18 months. After 18 months, it was taken out and placed in a bath at 30 ° C. to melt and homogenize the crystal, and then dropped into n-hexane, but no white precipitate was formed. The results are shown in Table 1.
[Example 8]
The low-temperature storage stability was evaluated in the same manner as in Example 7 except that the ether dimer composition obtained in Example 2 was used. The results are shown in Table 1.
[Example 9]
The low-temperature storage stability was evaluated in the same manner as in Example 7 except that the ether dimer composition obtained in Example 3 was used. The results are shown in Table 1.
[Comparative Example 7]
The low-temperature storage stability was evaluated in the same manner as in Example 7 except that the ether dimer composition obtained in Comparative Example 1 was used. The results are shown in Table 1.
[Comparative Example 8]
Except that the ether dimer composition obtained in Comparative Example 2 was used, the low-temperature storage stability was evaluated in the same manner as in Example 7. When the crystals were dissolved in a bath at 30 ° C., a solid that did not dissolve remained. Therefore, the low-temperature storage stability was determined as x. The results are shown in Table 1.
[Comparative Example 9]
The low temperature storage stability was evaluated in the same manner as in Example 7 except that the ether dimer composition obtained in Comparative Example 3 was used. When the crystals were dissolved in a bath at 30 ° C., a solid that did not dissolve remained. Therefore, the low-temperature storage stability was determined as x. The results are shown in Table 1.

表１に示す結果から、本発明の構成とすることによる効果が優れたものであることが確認された。例えば、実施例１〜３のエーテルダイマー組成物については、高温貯蔵安定性および低温貯蔵安定性の何れも高いことが確認された。水の含有量が本発明の範囲より少ない比較例１のエーテルダイマー組成物については高温貯蔵安定性が低く、水の含有量が多い比較例２のエーテルダイマー組成物については低温貯蔵安定性が低いものであった。水の含有量が本発明の範囲内であっても、非水系溶媒や安定剤を含まない比較例３のエーテルダイマー組成物については高温貯蔵安定性および低温貯蔵安定性の何れも低いものであった。
これらの結果から、本発明の構成とすることによって初めて、優れた貯蔵安定性（高温貯蔵安定性と低温貯蔵安定性の両立）を発現できることが確認されたといえる。

From the results shown in Table 1, it was confirmed that the effect of the configuration of the present invention was excellent. For example, about the ether dimer composition of Examples 1-3, it was confirmed that both high-temperature storage stability and low-temperature storage stability are high. The ether dimer composition of Comparative Example 1 having a water content less than the range of the present invention has low high-temperature storage stability, and the ether dimer composition of Comparative Example 2 having a large water content has low low-temperature storage stability. It was a thing. Even if the water content is within the range of the present invention, the high temperature storage stability and the low temperature storage stability of the ether dimer composition of Comparative Example 3 containing no non-aqueous solvent or stabilizer were low. It was.
From these results, it can be said that it was confirmed that excellent storage stability (coexistence of high temperature storage stability and low temperature storage stability) can be expressed only by using the configuration of the present invention.

(Preparation of tetrahydropyran ring-containing copolymer)
<Measurement of molecular weight>
The number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) are all gel permeation chromatography (GPC) apparatus HLC-8220GPC manufactured by Tosoh Corporation using tetrahydrofuran (THF) as a mobile phase. And measured in terms of polystyrene.
<Polymer concentration in polymer solution>
A solution prepared by adding 4 g of acetone to 1 g of the polymer solution was naturally dried at room temperature, further dried under reduced pressure (160 ° C./5 mmHg) for 5 hours, and then allowed to cool in a desiccator, and the weight was measured. Then, the nonvolatile content of the polymer solution was calculated from the weight loss, and this was used as the polymer concentration.
<Acid value>
To 0.5-1 g of the polymer solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly. An automatic titrator ("COM-555" Hiranuma Sangyo Co., Ltd.) uses 0.1 mol / L KOH aqueous solution as the titrant. And the acid value of the solution was measured. Then, the acid value of the polymer was calculated from the acid value of the solution and the polymer concentration.
[Synthesis of binder resin]
A separable flask equipped with a cooling tube as a reaction tank was prepared, and on the other hand, 80 parts by mass of the ether dimer composition obtained in Example 1, 34 parts by mass of methacrylic acid, 146 parts by mass of cyclohexyl methacrylate, t -Butyl peroxy-2-ethylhexanoate (Nippon Yushi "Perbutyl O") prepared by thoroughly stirring and mixing 5.2 parts by mass, as a chain transfer agent dropping tank, 14 parts by mass of n-dodecanethiol, What stirs and mixes 30 parts by mass of PGMEA was prepared.
The reaction vessel was charged with 428 parts by mass of PGMEA and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropwise addition was performed for 135 minutes each while maintaining the temperature at 90 ° C. Sixty minutes after the completion of dropping, the temperature was raised and the reaction vessel was brought to 110 ° C. Maintained 110 ° C. for 3 hours. Next, after removing IPA under reduced pressure at 110 ° C., cooling to room temperature and adjusting the concentration by adding PGMEA, the weight-average molecular weight of the copolymer containing a tetrahydropyran ring is 8000, A polymer solution having a concentration of 33.3% by mass and an acid value of 71 mgKOH / g was obtained.

[Preparation of photosensitive resin composition and evaluation of color filter suitability]
(Preparation of pigment dispersion)
7.24 parts of brominated zinc phthalocyanine as a green pigment and C.I. I. 2.54 parts of Pigment Yellow 150, 60.00 parts of PGMEA, 2 parts of a dispersant (“DISPERBYK-2000” manufactured by BYK-Chemie) in terms of solid content, and 3.3 parts of binder resin in terms of solid content, zirconia beads A stainless steel container was charged with 225 parts and dispersed for 6 hours with a paint shaker to prepare a green pigment dispersion.
[Adjustment of photosensitive resin composition]
Green content dispersion 57.78 parts, PGMEA 23.40 parts, ethyl 3-ethoxypropionate 8 parts, binder resin 5.47 parts, dipentaerythritol hexaacrylate 3.63 parts, 2,2'-bis (o-chlorophenyl) ) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole 0.38 parts, 4,4'-bis-diethylaminobenzophenone 0.19 parts, 2-mercaptobenzothiazole 0.38 parts , 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one 0.76 parts is mixed well and a tetrahydropyran ring-containing copolymer and a photopolymerization initiator are contained. The resin composition was prepared.
[Production of color filters]
The photosensitive resin composition was applied on a 50 mm square glass substrate having a thickness of 0.7 mm using a spin coater, and then dried at 80 ° C. for 3 minutes. Subsequently, the whole surface exposure process was performed with the exposure amount of 300 mJ / cm <2> with the 2kW high pressure mercury lamp, and the colored application board | substrate with which the photosensitive resin composition was formed on the glass substrate was created. Then, the thermosetting process for 30 minutes was performed at the temperature of 230 degreeC. With respect to the obtained coated substrate, the spectral transmittance was measured with a spectrophotometer manufactured by Hitachi, Ltd. (“U-3310” manufactured by Hitachi, Ltd.), and the chromaticity (C light source) in the XYZ surface light system was calculated. The results were x0.280, y0.600, Y57.4.
From the above, it was possible to produce a good color filter by synthesizing a binder resin and preparing a photosensitive resin composition using the ether dimer composition of the present invention having high storage stability as a raw material.

The present invention relates to an ether dimer composition and a polymer. More specifically, an ether dimer composition used in a wide range of fields as a raw material for a photosensitive resin composition for color filters and other curing materials necessary for production of liquid crystal displays, and a polymer using the ether dimer composition as a raw material About.

It is the figure which showed the impurity (a catalyst and a side reaction product) at the time of the synthetic reaction of an ether dimer.

Claims (10)

(A) The following general formula (1):

(In formula (1), R ¹ and R ² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent). , (B) water, (C) a stabilizer, (D) contains a non-aqueous solvent, Ri is 0.3 to 10% by mass content of (B) water,
The (C) stabilizer includes at least one selected from the group consisting of phenolic compounds and N-oxyl compounds,
The content of the (A) ether dimer is 10 to 70% by mass, the content of the (C) stabilizer is 0.001 to 1% by mass, and the content of the (D) non-aqueous solvent is 20 to 90% by mass. (However, the total amount of (A), (B), (C) and (D) is 100% by mass).
An ether dimer composition characterized by the above. The ether dimer composition according to claim 1, wherein the (C) stabilizer contains a phenol-based compound and an N-oxyl compound. The ether dimer composition according to claim 2 , wherein a mass ratio of the phenolic compound and the N-oxyl compound (phenolic compound / N-oxyl compound) is 15/1 to 5/1. Formula (1), R ¹ and R ² are ether dimer composition according to any one of claims 1 to 3, characterized in that the same atom or a hydrocarbon group. A monomer composition comprising the ether dimer composition according to any one of claims 1 to 4 and an unsaturated monomer. The monomer composition according to claim 5 , wherein the unsaturated monomer includes an unsaturated monomer having an acid group. A tetrahydropyran ring-containing copolymer obtained by polymerizing the monomer composition according to claim 5 . A photosensitive resin composition comprising the tetrahydropyran ring-containing copolymer according to claim 7 and a photopolymerization initiator. A cured product obtained by curing the photosensitive resin composition according to claim 8 . A color filter in which the cured product according to claim 9 is formed on a substrate.

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