JP2007063531A - Curable resin composition, column spacer and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition for a column spacer having excellent developability and solubility which enables to form a column spacer of a clear pattern without leaving a developer residue during the formation of the pattern of a column spacer used for production of a liquid crystal display device which can effectively suppress the occurrence of color unevenness by the failure owing to gravity, and also to provide a column spacer and a liquid crystal display device using the curable resin composition. <P>SOLUTION: The curable resin composition comprises a compound having two or more polymerizable unsaturated bonds in its molecule, an alkali-soluble polymer compound and a photoreaction initiator. The compound having two or more polymerizable unsaturated bonds in its molecule has, in its molecule, one or more carboxy groups and two or more polymerizable unsaturated bonds. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention has excellent developability and solubility, and when used for a column spacer used in the production of a liquid crystal display element, does not produce a development residue during pattern formation, and forms a column spacer with a clear pattern. And a curable resin composition capable of obtaining a liquid crystal display element capable of effectively suppressing the occurrence of color unevenness due to poor gravity without causing low-temperature foaming, and the curable resin composition. The present invention relates to a column spacer and a liquid crystal display element.

In general, a liquid crystal display element includes a spacer for maintaining a constant gap between two glass substrates, and includes a transparent electrode, a polarizing plate, an alignment layer for aligning a liquid crystal substance, and the like. At present, fine particle spacers having a particle diameter of about several μm are mainly used as spacers. However, in the conventional method for manufacturing a liquid crystal display element, since the fine particle spacers are randomly distributed on the glass substrate, the fine particle spacers may be disposed in the pixel portion. If there is a fine particle spacer in the pixel portion, there is a problem that image quality may be deteriorated, for example, light leaks from disturbance of liquid crystal alignment around the spacer and image contrast is lowered. On the other hand, various arrangement methods of the fine particle spacer in which the fine particle spacer is not arranged in the pixel portion have been studied. However, all of them are complicated and impractical.

In recent years, one drop fill technology (ODF method) has been proposed in order to increase the productivity of liquid crystal display elements. In this method, a predetermined amount of liquid crystal is dropped on the liquid crystal sealing surface of a glass substrate, and the other liquid crystal panel substrate is held in a state where a predetermined cell gap can be maintained under vacuum, and bonded together to display a liquid crystal display. This is a method of manufacturing an element. According to this method, even when the liquid crystal display element has a larger area than the conventional method and the cell gap is narrowed, it is easy to enclose the liquid crystal. It will be mainstream.
However, when fine particle spacers are used in the ODF method, the fine particle spacers scattered when the liquid crystal is dropped or bonded to the counter substrate are flowed along with the flow of the liquid crystal, resulting in a non-uniform distribution of the fine particle spacers on the substrate. Occurs. If the distribution of the fine particle spacers is non-uniform, there is a problem that the cell gap of the liquid crystal cell varies and color unevenness occurs in the liquid crystal display.

On the other hand, instead of the conventional fine particle spacer, a column spacer in which a convex pattern for holding the cell gap uniformly on a liquid crystal substrate by a photolithographic technique is proposed and put into practical use. (For example, Patent Document 1, Patent Document 2, etc.).
By using such a column spacer, the problem that the spacer is arranged in the pixel portion and the problem that the spacer unevenness occurs in the ODF method can be solved.

Further, in a large liquid crystal display element manufactured by an ODF method using a column spacer made of a conventional resin composition for column spacers, the liquid crystal in the liquid crystal cell flows downward during use of the display device. A defect called “gravity failure” in which color unevenness occurs on the upper half surface and the lower half surface has been a big problem. The phenomenon of “gravity failure” is that the liquid crystal in the liquid crystal cell expands due to the heat generated from the backlight and widens the cell gap. At that time, the substrate rises from the column spacer and is not held by this spacer. It is thought that a volume of liquid crystal is generated by flowing downward due to gravity.
In order to eliminate such “gravity failure”, when the liquid crystal in the liquid crystal cell expands due to the heat generated from the backlight and expands the cell gap, the column spacer once compressed is removed from the compression deformation. It is considered that the problem can be solved by making it possible to follow the change of the cell gap by elastic recovery so that no gap is generated between the substrate and the column spacer.

However, in the conventional method, in order to give the column spacer a high deformation recovery force, it is necessary to highly crosslink the resin forming the column spacer to make it difficult to cause plastic deformation during compression. Resins having a crosslinked structure generally have a high compression modulus and tend to be hard. When the column spacer is formed of such a hard resin, a large pressure is required in the process of compressing and deforming the column spacer. In the obtained liquid crystal display element, the liquid crystal cell by the compressed column spacer is pushed. It contains a great force to spread. When the column spacer has a large force to push the liquid crystal cell, if the volume shrinkage of the liquid crystal in the liquid crystal cell occurs at a low temperature, the internal pressure in the liquid crystal cell rapidly decreases and bubbles are generated. ”Has occurred.
JP 2001-91954 A JP 2002-251007 A

In view of the above-mentioned present situation, the present invention has excellent developability and solubility, and when used for a column spacer used in the production of a liquid crystal display element, does not produce a development residue at the time of pattern formation and has a clear pattern. Curable resin composition capable of forming a liquid crystal display element capable of effectively preventing color unevenness due to poor gravity without causing low-temperature foaming, and the curable resin composition An object of the present invention is to provide a column spacer and a liquid crystal display element using the object.

The present invention is a curable resin composition containing a compound having two or more polymerizable unsaturated bonds in the molecule, an alkali-soluble polymer compound, and a photoreaction initiator, wherein the molecule has two or more in the molecule. The compound having a polymerizable unsaturated bond is a curable resin composition having one or more carboxyl groups and two or more polymerizable unsaturated bonds in the molecule.
The present invention is described in detail below.

As a result of intensive studies, the present inventors have determined that, as a curable resin composition, a compound having two or more polymerizable unsaturated bonds in a molecule having a specific structure and an alkali-soluble polymer compound are used in combination. When used for spacer applications, it is possible to form column spacers with excellent resolution at the time of pattern formation and a clear pattern, and to obtain column spacers having excellent flexibility and high compression recovery characteristics. As a result, the present invention has been completed.
According to such a column spacer using the curable resin composition of the present invention, it is possible to simultaneously suppress “gravity failure” due to liquid crystal expansion during heating and “low temperature foaming” due to liquid crystal shrinkage at low temperatures. In addition, when a pattern to be a column spacer is formed by a photolithographic technique, a sharp resolution can be obtained without generating a development residue.
In addition, it does not specifically limit as a use of the curable resin composition of this invention, Although it can use for various uses, It can use especially suitably for the column spacer use of a liquid crystal display element especially.

The curable resin composition of the present invention contains a compound having two or more polymerizable unsaturated bonds in the molecule, an alkali-soluble polymer compound, and a photoreaction initiator.
In the curable resin composition of the present invention, the compound having two or more polymerizable unsaturated bonds in the molecule has one or more carboxyl groups and two or more polymerizable unsaturated bonds in the molecule (hereinafter referred to as the present invention). Also referred to as a polymerizable compound according to the invention).
Although it does not specifically limit as a polymeric compound which concerns on the said invention, For example, carboxylic acid is obtained by carrying out addition reaction of the compound which has a carboxyl group to a part of (meth) acryl group of the (meth) acrylate compound more than trifunctional. A (meth) acrylate compound into which is introduced (hereinafter also referred to as a polyfunctional (meth) acrylate compound having a carboxyl group) is preferable. By containing such a polyfunctional (meth) acrylate compound having a carboxyl group, the curable resin composition of the present invention can be rapidly polymerized to obtain exposure sensitivity during pattern formation by a photolithographic technique. The reactivity and the affinity with an alkaline developer necessary for obtaining the resolution at the time of development are excellent. In the present specification, (meth) acrylate means acrylate or methacrylate.

The amount of carboxyl group modification to the compound having one or more carboxyl groups and two or more polymerizable unsaturated bonds in the molecule is not particularly limited as long as it can be quickly dissolved in an alkali developer, but the acid value is preferable. The lower limit is 5 mgKOH / g, the preferred upper limit is 80 mgKOH / g, the more preferred lower limit is 10 mgKOH / g, and the more preferred upper limit is 50 mgKOH / g.

The trifunctional or higher functional (meth) acrylate compound is not particularly limited. For example, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Examples include erythritol hexa (meth) acrylate. Among them, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, or dipentaerythritol penta (meth) acrylate is preferable. Used for.
Trifunctional or higher functional urethane (meth) acrylate, epoxy (meth) acrylate, and polyester (meth) acrylate are also suitable. Examples of such urethane (meth) acrylate and epoxy (meth) acrylate include UA-306H, UA-306T, UA-306I (above, manufactured by Kyoeisha Chemical Co., Ltd.), EB9260, EB8210, EB1290, EB1290K, EB5129, and EB810. , EB450, EB830, EB870, EB1870 (manufactured by Daicel Cytec), M-1960, M-7100, M-8030, M-8060, M-8100, M-8530, M-8560, M-9050 (and above) , Manufactured by Toagosei Co., Ltd.).
These trifunctional or higher functional (meth) acrylate compounds may be used alone or in combination of two or more.

In the curable resin composition of the present invention, when the polymerizable compound according to the present invention is a (meth) acrylate compound having a carboxyl group, the polymerization reaction proceeds quickly and the exposure sensitivity is easily improved. The preferred lower limit of the number of (meth) acrylic groups is 3. In the polyfunctional (meth) acrylate compound having a carboxyl group, the preferable upper limit of the carboxyl group in the molecule is 2. When it is 3 or more, the solubility / swellability in the developer is increased. For example, when the curable resin composition of the present invention is used for a column spacer, the development pattern is peeled off or the resolution is lowered due to the swelling property. Is likely to occur.

The compound having a carboxyl group is not particularly limited, and examples thereof include compounds having a carboxyl group and a thiol group, such as thiosalicylic acid, mercaptoacetic acid, mercaptosuccinic acid, and 3-mercaptopropionic acid.

It does not specifically limit as a method to obtain the polyfunctional (meth) acrylate compound which has the said carboxyl group, For example, thiol groups, such as thiosalicylic acid, are added to the (meth) acryl group of the (meth) acrylate compound more than trifunctional mentioned above. Examples thereof include a method of adding a compound having a carboxyl group by an ene-thiol reaction.

In the curable resin composition of the present invention, the polymerizable compound according to the present invention is preferably a polyfunctional (meth) acrylate compound having a lactone-modified and / or oxide-modified carboxyl group. The cured product obtained by curing the curable resin composition of the present invention has excellent flexibility, and when the curable resin composition of the present invention is used for a column spacer, it has excellent flexibility and high compression recovery characteristics. This is because a column spacer having the above can be suitably obtained.
In the present specification, lactone modification means that a lactone ring-opening polymer or a ring-opening polymer is introduced between the alcohol-derived portion of the (meth) acrylate compound and the (meth) acryloyl group. To do. The oxide modification means that an oxide ring-opened structure and / or a ring-opened polymer structure is introduced between the alcohol-derived portion of the (meth) acrylate compound and the (meth) acryloyl group. .

In the curable resin composition of the present invention, when the polymerizable compound according to the present invention is a polyfunctional (meth) acrylate compound having a lactone-modified carboxyl group, as the polyfunctional (meth) acrylate compound, It does not specifically limit, For example, the trifunctional or more than (meth) acrylate compound mentioned above etc. are mentioned. Among them, caprolactone-modified pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, or dipentaerythritol penta (meth) A compound obtained by adding a compound having a carboxyl group to acrylate is preferably used.

The degree of lactone modification of the lactone-modified polyfunctional (meth) acrylate is 2 or more polymerizable unsaturated bonds in the molecule, where n is the number of functional groups of the base polyfunctional (meth) acrylate compound. The preferable lower limit is 0.5 nmol and the preferable upper limit is 5 nmol with respect to 1 mol of the compound having azobenzene. If it is less than 0.5 nmol, the flexibility of the column spacer to be produced may be insufficient, and if it exceeds 5 nmol, the reactivity during exposure when producing the column spacer is reduced, and the column to be produced is produced. Spacer patterning may be difficult. A more preferable lower limit is 1 nmol, and a more preferable upper limit is 3 nmol.

The specific method for modifying the polyfunctional (meth) acrylate compound with lactone is not particularly limited. For example, after reacting polyhydric alcohol with lactone to synthesize lactone-modified alcohol, ester with (meth) acrylic acid. A method of reacting (meth) acrylic acid and lactone to synthesize lactone-modified (meth) acrylic acid and then esterifying with alcohol; (meth) acrylic acid, lactone and polyhydric alcohol are collectively The method of making it react is mentioned.

Further, when the polymerizable compound according to the present invention is a polyfunctional (meth) acrylate compound having an oxide-modified carboxyl group, the polyfunctional (meth) acrylate compound is not particularly limited. Trifunctional or higher functional (meth) acrylate compounds and the like can be mentioned. Among them, oxide-modified pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, or dipentaerythritol penta (meth) A compound obtained by adding a compound having a carboxyl group to acrylate is preferably used.

As the modification degree of the oxide modification of the polyfunctional (meth) acrylate, when the number of functional groups of the polyfunctional (meth) acrylate compound as a base is n, a preferable lower limit is 1 mol per mol of the polyfunctional (meth) acrylate compound. 0.5 nmol, the preferred upper limit is 15 nmol. If it is less than 0.5 nmol, the flexibility of the column spacer to be produced may be insufficient. If it exceeds 15 nmol, the affinity for an alkaline developer will be high, and the resolution will be lowered due to swelling. It tends to happen. A more preferable lower limit is 3 nmol, and a more preferable upper limit is 10 nmol.

The specific method for oxide-modifying the polyfunctional (meth) acrylate compound is not particularly limited. For example, after reacting a polyhydric alcohol and oxide to synthesize the oxide-modified alcohol, the oxide-modified alcohol and (meta ) Method of esterification reaction with acrylic acid; Method of reacting (meth) acrylic acid and oxide to synthesize oxide-modified (meth) acrylic acid and then esterification reaction with alcohol; (meth) acrylic acid, oxide And a method of reacting polyhydric alcohols at once.

In the curable resin composition of the present invention, the above-described polymerizable compound according to the present invention may further have one or more hydroxyl groups in the molecule. When the curable resin composition of the present invention containing the polymerizable compound according to the present invention is used for a column spacer, the developability and solubility during pattern formation can be further improved, and the development residue Generation can be further suppressed, and sharp resolution can be obtained.

The polymerizable compound according to the present invention having a hydroxyl group in the molecule is, for example, a (meth) acrylic acid compounding ratio and / or reaction that is reacted with a polyhydric alcohol when the (meth) acrylate compound is produced. It can be obtained by adjusting the ratio.

The polymerizable compound according to the present invention having a hydroxyl group in the molecule is a carboxylic acid compound having two or more carboxyl groups in a compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule, and / or An acid anhydride may be subjected to an addition reaction.
The compound having two or more polymerizable unsaturated bonds in the molecule and a hydroxyl group is not particularly limited, and examples thereof include pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, and dipentaerythritol tri (meth). Examples include acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and lactone-modified and / or oxide-modified products thereof.

A method for obtaining such a compound having two or more polymerizable unsaturated bonds in the molecule and a hydroxyl group is not particularly limited. For example, a (meth) acrylate compound (or a compound obtained by oxide-modifying a (meth) acrylate compound) and A method of reacting with a polyhydric alcohol; a compound having three or more polymerizable unsaturated bonds in the molecule, or a lactone-modified and / or oxide-modified product having a hydroxyl group and a primary or secondary amino group A method of reacting a compound; a method of reacting an oxide-modified polyhydric alcohol and a (meth) acrylate compound.

The compound having 3 or more polymerizable unsaturated bonds in the molecule is not particularly limited, and examples thereof include pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

The compound having a hydroxyl group and a primary or secondary amino group is not particularly limited, and examples thereof include monoethanolamine, n-propanolamine, isopropanolamine, diethanolamine, and diisopropanolamine.

When a compound having a hydroxyl group and a primary or secondary amino group is reacted with a compound having three or more polymerizable unsaturated bonds in the molecule, three or more polymerizations are carried out in the molecule by a so-called Michael addition reaction. The amino group of the compound having a hydroxyl group and a primary or secondary amino group is added to the unsaturated double bond portion of the compound having a polymerizable unsaturated bond.

In the Michael addition reaction between a compound having three or more polymerizable unsaturated bonds in the molecule and a compound having a hydroxyl group and a primary or secondary amino group, the hydroxyl group diluted with a solvent or a solvent and the primary Alternatively, a method of slowly dropping a compound having a secondary amino group while stirring into a compound having 3 or more polymerizable unsaturated bonds in the molecule is suitably used.

The solvent for diluting the compound having a hydroxyl group and a primary or secondary amino group is not particularly limited. For example, the solvent does not react with the compound having a hydroxyl group and a primary or secondary amino group, and A compound having compatibility with a compound having three or more polymerizable unsaturated bonds in the molecule and a compound having a hydroxyl group and a primary or secondary amino group is appropriately selected. Preferably, it is a water-soluble solvent having a boiling point of 64 to 200 ° C.
In addition, the concentration of the compound having the hydroxyl group and the primary or secondary amino group in the solvent when dropped into the compound having 3 or more polymerizable unsaturated bonds in the molecule is not particularly limited. A preferred lower limit is 5% by weight, a preferred upper limit is 30% by weight, a more preferred lower limit is 10% by weight, and a more preferred upper limit is 20% by weight.

The Michael addition reaction proceeds promptly even under normal temperature and no catalyst conditions, but may be performed using a catalyst if necessary, or may be performed by heating in a temperature range from normal temperature to about 80 ° C.
The catalyst is not particularly limited, and examples thereof include alkali metal alcoholates, organometallic compounds such as tin and titanium, metal hydroxides, and tertiary amines.

The reaction time for the Michael addition reaction is not particularly limited, but the preferred lower limit is 1 hour, the preferred upper limit is about 10 hours, the more preferred lower limit is 3 hours, and the more preferred upper limit is about 7 hours.

Although it does not specifically limit as a reaction solvent used for the said Michael addition reaction, The compound etc. which have a 3 or more polymerizable unsaturated bond in the said molecule | numerator, and these raw materials do not react with a hydroxyl group and a primary or secondary amino group It is preferable that it is a water-soluble solvent which can melt | dissolve uniformly.
Specifically, for example, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, tert-butyl alcohol, N-methylpyrrolidone, ε-caprolactam, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoacetate , Ethylene glycol monomethyl ether acetate, 2- (methoxymethoxy) ethanol, 2-isopropoxyethanol, 2-isopentyloxyethanol, 2-butoxyethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, tetrahydrofuran, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, Reethylene glycol, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, glycerin ethers, glycerin monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydropyran , Trioxane, dioxane, 1,2,6-hexanetriol, 2-methyl-2,4-pentanediol, 2-butene-1,4-diol, 2,3-butanediol, 1,3-butanediol, 1 , 3-propanediol, 1,2-propanediol, propargyl alcohol, N, N-dimethylethanolamine, N, N-die Examples include tilethanolamine, N-ethylmorpholine, methyl lactate, and ethyl lactate.

In the Michael addition reaction, it is preferable to use a polymerization inhibitor.
The polymerization inhibitor is not particularly limited, and examples thereof include conventionally known ones such as quinone derivatives such as hydroquinone, methylhydroquinone and p-benzoquinone, and phenol derivatives such as 2,6-di-tert-butyl-p-cresol. Can be mentioned.

Examples of the carboxylic acid compound having two or more carboxyl groups include oxalic acid, maleic acid, succinic acid, tartaric acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, ethyltetrahydrophthalic acid, and hexahydrophthalic acid. And dicarboxylic acid compounds such as methylhexahydrophthalic acid, ethylhexahydrophthalic acid and chlorendic acid, and tricarboxylic acid compounds such as trimellitic acid. Preferably, a dicarboxylic acid compound or a tricarboxylic acid compound is used.

The acid anhydride is not particularly limited. For example, oxalic anhydride, maleic anhydride, succinic anhydride, tartaric acid, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydroanhydride. Phthalic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, etc. Of the carboxylic anhydride compound.

Carboxylic acid compounds and / or acid anhydrides having two or more of these carboxyl groups are subjected to an addition reaction with the hydroxyl group of the compound having two or more polymerizable unsaturated bonds and hydroxyl groups in the above-described molecule, and carboxyls in the molecule. The polymerizable compound according to the present invention having a group is obtained.

Examples of the reaction in which the carboxylic acid compound having two or more carboxyl groups is added to the hydroxyl group of the compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule include a conventional dehydration esterification reaction. It is done.
Specifically, in a reactor equipped with a stirrer, a thermometer and a water separator, a compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule, a carboxylic acid compound having two or more carboxyl groups, and a solvent And heated in the presence of an acidic catalyst. The water generated as the reaction proceeds distills out of the system. After completion of the reaction, the reaction solution is washed with water, the aqueous layer is separated, and then the solvent is distilled off under reduced pressure.

As a solvent in an esterification reaction in which a carboxylic acid compound having two or more carboxyl groups is added to a hydroxyl group of a compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule, water can be easily distilled. A carboxylic acid compound having two or more carboxyl groups, a compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule, and any compound that does not react with an acidic catalyst are not particularly limited, but are produced. Preference is given to aliphatic hydrocarbons such as n-hexane and n-heptane that form an azeotrope with water, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane.

The acidic catalyst in the esterification reaction between the carboxylic acid compound having two or more carboxyl groups and the compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule is either an inorganic acid or an organic acid. Well, specific examples of the inorganic acid include hydrochloric acid, sulfuric acid and phosphoric acid. Specific examples of the organic acid include p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, and the like. Of these, organic sulfonic acids such as p-toluenesulfonic acid are particularly preferable because of their low corrosivity. As the addition amount of the acidic catalyst, a preferable lower limit is 0.5% by weight and a preferable upper limit is 5% by weight with respect to the total amount of the reaction solution.

Reaction of esterification reaction between a carboxylic acid compound having two or more carboxyl groups, two or more polymerizable unsaturated bonds in the molecule, and a compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule As a temperature, a preferable lower limit is 70 ° C., and a preferable upper limit is 150 ° C. By heating at a temperature within this range, the dehydration esterification reaction can be easily performed. A more preferable lower limit is 80 ° C., and a more preferable upper limit is 120 ° C.

Furthermore, in the esterification reaction between the carboxylic acid compound having two or more carboxyl groups and a compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule, the reaction may be performed by adding a polymerization inhibitor. preferable. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, phenothiazine, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, 4-t-butylcatechol, copper salt and the like. As the use amount thereof, the preferable lower limit is usually 0.01% by weight and the preferable upper limit is 1% by weight with respect to the total amount of the reaction solution.

The reaction for adding the acid anhydride to the hydroxyl group of a compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule is a general esterification reaction, and the preferred lower limit of the reaction temperature is 60 ° C., the preferred upper limit. Is 150 ° C., and the preferred lower limit of the reaction time is 1 hour, and the preferred upper limit is 12 hours.
In addition, when the above acid anhydride is subjected to addition reaction with a hydroxyl group of a compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule, a tertiary amine such as triethylamine, 4 such as triethylbenzylammonium chloride as a catalyst. A phosphorus compound such as a quaternary ammonium salt, a 2-ethyl-4-methylimidazole compound, or triphenylphosphine may be used.
Further, as a polymerization inhibitor, for example, conventionally known ones such as quinone derivatives such as hydroquinone, methylhydroquinone and p-benzoquinone, and phenol derivatives such as 2,6-di-tert-butyl-p-cresol may be added. Good.

Furthermore, the reaction for adding the acid anhydride to the hydroxyl group of a compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule may be performed without a solvent, but may be performed in a solvent if necessary. May be. The solvent that can be used for the reaction is not particularly limited as long as it does not inhibit the reaction. For example, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve and methylcellosolve Cellosolves such as butyl cellosolve; Carbitols such as carbitol, methyl carbitol and butyl carbitol; Glycol ethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether; Ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate , Acetic acid such as butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate Ester ethers; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, petroleum solvents such as solvent naphtha.

The polymerizable compound according to the present invention includes a carboxylic acid compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule, a lactone-modified and / or oxide-modified compound having two or more carboxyl groups, and It is preferable that the acid anhydride is an addition reaction.
The lactone-modified and / or oxide-modified compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule is not particularly limited. For example, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri Examples include lactone-modified and / or oxide-modified products such as (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

As a method of synthesizing a compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule and modified with lactone and / or oxide, for example, a reaction between a polyhydric alcohol and a lactone is performed to modify the lactone. After synthesizing polyhydric alcohol, this lactone-modified polyhydric alcohol and (meth) acrylic acid are esterified (1); (meth) acrylic acid and lactone are reacted to produce lactone-modified (meth) acrylic acid And a method (2) of esterifying the lactone-modified (meth) acrylic acid with an alcohol; a method (3) of reacting (meth) acrylic acid, a lactone and a polyhydric alcohol at once.

In the above method (1), as a method of synthesizing a lactone-modified polyhydric alcohol by reacting a polyhydric alcohol and a lactone, for example, a polyhydric alcohol and the above lactone in a reactor equipped with a stirrer, a thermometer and a cooler. And heating and reacting in the presence of an acidic catalyst.
As the acidic catalyst used when synthesizing the lactone-modified polyhydric alcohol, for example, stannous chloride, stannous octylate, dibutyltin dilaurate and the like are preferably used. Moreover, as the usage-amount, a preferable minimum is 0.005 weight% and a preferable upper limit is 0.5 weight% with respect to the whole quantity of a reaction liquid.
As the reaction conditions for the synthesis of the lactone-modified polyhydric alcohol, the preferable lower limit of the reaction temperature is 80 ° C., the preferable upper limit is 200 ° C., the preferable lower limit of the reaction time is 1 hour, and the preferable upper limit is 20 hours.

The polyhydric alcohol is not particularly limited, for example, selected from the group consisting of pentaerythritol, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, trimethylolethane, ditrimethylolethane, trimethylolpropane, and ditrimethylolpropane. At least one trihydric or higher polyhydric alcohol compound is preferably used.

The lactone is not particularly limited, and examples thereof include ε-caprolactone, δ-caprolactone, γ-caprolactone, and among them, ε-caprolactone is preferable.

Examples of the method of esterifying the lactone-modified polyhydric alcohol and (meth) acrylic acid include a conventional dehydration esterification reaction.
Specifically, a lactone-modified polyhydric alcohol, (meth) acrylic acid and a solvent are charged into a reactor equipped with a stirrer, a thermometer and a water separator, and heated in the presence of an acidic catalyst. The water generated as the reaction proceeds distills out of the system. After completion of the reaction, the reaction solution is washed with water, the aqueous layer is separated, and then the solvent is distilled off under reduced pressure.

The solvent in the esterification reaction is not particularly limited as long as it facilitates the outflow of water and does not react with the lactone-modified polyhydric alcohol, (meth) acrylic acid, and acidic catalyst. Preferred are aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as benzene, toluene and xylene, and alicyclic hydrocarbons such as cyclohexane.

The acidic catalyst may be either an inorganic acid or an organic acid, and specific examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid, and the like. Specific examples of the organic acid include p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, and the like. Of these, organic sulfonic acids such as p-toluenesulfonic acid are particularly preferable because of their low corrosivity. As the addition amount of the acidic catalyst, a preferable lower limit is 0.5% by weight and a preferable upper limit is 5% by weight with respect to the total amount of the reaction solution.

Moreover, as a reaction temperature of the said esterification reaction, a preferable minimum is 70 degreeC and a preferable upper limit is 150 degreeC. By heating at a temperature within this range, the dehydration esterification reaction can be easily performed. A more preferable lower limit is 80 ° C., and a more preferable upper limit is 120 ° C.

Furthermore, it is normal that a polymerization inhibitor has already been added to the (meth) acrylic acid, but in the esterification reaction, it is preferable to carry out the reaction by adding a polymerization inhibitor again. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, phenothiazine, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, 4-t-butylcatechol, copper salt and the like. As the use amount thereof, the preferable lower limit is usually 0.01% by weight and the preferable upper limit is 1% by weight with respect to the total amount of the reaction solution.

In the above method (2), as a method of synthesizing lactone-modified (meth) acrylic acid by reacting (meth) acrylic acid and lactone, specifically, for example, a stirrer, a thermometer and a reflux condenser are provided. The reactor is charged with (meth) acrylic acid and lactone and heated in the presence of an acidic catalyst. After completion of the reaction, there may be mentioned a method in which the reaction solution is neutralized, adsorbed or the like to remove the catalyst, and if necessary, operations such as washing with water and distillation are performed.

The acidic catalyst used when synthesizing the lactone-modified (meth) acrylic acid may be either an inorganic acid or an organic acid, and specifically, the same as the acidic catalyst in the esterification reaction of the method (1) described above. As for the addition amount thereof, the preferred lower limit is 0.5% by weight, the preferred upper limit is 5% by weight, the more preferred lower limit is 0.8% by weight, and the more preferred upper limit with respect to the total amount of the reaction solution. Is 3% by weight.

The reaction temperature for synthesizing the lactone-modified (meth) acrylic acid is preferably a lower limit of 60 ° C. and a preferable upper limit of 120 ° C., more preferably a lower limit of 70 ° C. from the viewpoint of shortening the reaction time and preventing polymerization. The upper limit is more preferably 100 ° C.

When synthesizing the lactone-modified (meth) acrylic acid, it is preferable to use a solvent in order to facilitate temperature control during the reaction. The solvent that can be used is not particularly limited as long as it does not react with (meth) acrylic acid, lactone, and an acidic catalyst, but aromatic hydrocarbons such as benzene, toluene, and xylene are preferable.

In addition, a polymerization inhibitor is usually added to the (meth) acrylic acid, but when synthesizing the lactone-modified (meth) acrylic acid, a polymerization inhibitor is added again to react. It is preferable to carry out. As said polymerization inhibitor, the thing similar to the polymerization inhibitor in the esterification reaction of the method (1) mentioned above is mentioned, for example, As the addition amount, the preferable minimum with respect to the whole quantity of a reaction liquid is 0 normally. 0.01% by weight, and a preferred upper limit is 1% by weight.

Examples of the method for esterifying the lactone-modified (meth) acrylic acid and alcohol include a conventional dehydration esterification reaction.
Specifically, a lactone-modified (meth) acrylic acid, a polyhydric alcohol, and a solvent are charged into a reactor equipped with a stirrer, a thermometer, and a water separator, and heated in the presence of an acidic catalyst. The water generated as the reaction proceeds distills out of the system. After completion of the reaction, the reaction solution is washed with water, the aqueous layer is separated, and then the solvent is distilled off under reduced pressure.
The hydroxyl group in the (meth) acrylate molecule in the esterification reaction of the above method (2) can be obtained by adjusting the charged molar ratio of lactone-modified (meth) acrylic acid to the polyhydric alcohol and the reaction rate.

In the esterification reaction of the above method (2), as the molar ratio of the lactone-modified (meth) acrylic acid to the polyhydric alcohol, the preferred lower limit is 0.6, the preferred upper limit is 1.2, and the more preferred lower limit is 0. .7, and a more preferable upper limit is 1.0.

The solvent in the esterification reaction of the above method (2) is not particularly limited as long as it makes it easy to distill water and does not react with lactone-modified (meth) acrylic acid, polyhydric alcohol and acidic catalyst. Aromatic hydrocarbons such as benzene, toluene and xylene that form an azeotrope with water are preferred.

As the acidic catalyst in the esterification reaction of the above method (2), an organic sulfonic acid such as p-toluenesulfonic acid is suitable. As the addition amount of the acidic catalyst, a preferable lower limit is 0.5% by weight and a preferable upper limit is 5% by weight with respect to the total amount after the reaction.

Furthermore, as a reaction temperature of the esterification reaction of the method (2), a preferable lower limit is 70 ° C., and a preferable upper limit is 150 ° C. By heating at a temperature within this range, the dehydration esterification reaction can be easily performed. A more preferable lower limit is 80 ° C., and a more preferable upper limit is 120 ° C.

In the esterification reaction of the above method (2), it is preferable to add a polymerization inhibitor. Examples of the polymerization inhibitor include the same polymerization inhibitors as those in the esterification reaction of the above-described method (1). As for the amount used, the preferred lower limit is usually 0.01% by weight and the preferred upper limit is 1% by weight with respect to the total amount of the reaction solution.

In the above method (3), examples of the method of collectively reacting (meth) acrylic acid, lactone and polyhydric alcohol include a conventional dehydration esterification reaction.
Specifically, (meth) acrylic acid, lactone, polyhydric alcohol and solvent are charged into a reactor equipped with a stirrer, a thermometer and a water separator, and heated in the presence of an acidic catalyst. The water generated as the reaction proceeds distills out of the system. The end point of the reaction is determined by the amount of by-product water. After completion of the reaction, the reaction solution is washed with water, the aqueous layer is separated, and then the solvent is distilled off under reduced pressure.

The acid catalyst in the method (3) may be either an inorganic acid or an organic acid, and specifically, the same acid catalyst as that in the esterification reaction of the method (1) described above may be mentioned. As for the addition amount, the preferable lower limit is 0.5% by weight and the preferable upper limit is 5% by weight with respect to the total amount of the reaction solution.

As the reaction temperature of the above method (3), from the viewpoint of shortening the reaction time and preventing polymerization, the preferred lower limit is 70 ° C., the preferred upper limit is 150 ° C., the more preferred lower limit is 100 ° C., and the more preferred upper limit is 120 ° C. is there.

In the method (3), it is preferable to use a solvent in order to facilitate temperature control during the reaction. The solvent that can be used is not particularly limited as long as it does not react with (meth) acrylic acid, lactone, polyhydric alcohol, and acidic catalyst, but aromatic hydrocarbons such as benzene, toluene, and xylene are preferable.

Furthermore, it is normal that a polymerization inhibitor has already been added to the (meth) acrylic acid. However, in the method (3), it is preferable to carry out the reaction by adding a polymerization inhibitor again. As said polymerization inhibitor, the thing similar to the polymerization inhibitor in the esterification reaction of the method (1) mentioned above is mentioned, for example, As the usage-amount, normally a preferable minimum with respect to the whole quantity of a reaction liquid is 0. 0.01% by weight, and a preferred upper limit is 1% by weight.

The method for synthesizing an oxide-modified compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule is not particularly limited. For example, a polyhydric alcohol and an oxide are reacted to generate an oxide-modified polyoxygen. Examples thereof include a method (4) of esterifying this oxide-modified polyhydric alcohol and (meth) acrylic acid after synthesizing the monohydric alcohol.

In the method (4), the polyhydric alcohol and oxide are reacted to synthesize an oxide-modified polyhydric alcohol. For example, the polyhydric alcohol and the basic catalyst are charged into an autoclave equipped with a stirrer, and nitrogen is used. After pressurization, the autoclave is heated and reacted while introducing oxides sequentially. After completion of the reaction, the reaction solution is neutralized and filtered, and then the solvent is distilled off under reduced pressure.

As the basic catalyst in the synthesis of the oxide-modified polyhydric alcohol, alkali metal hydroxides, alkaline earth metal hydroxides, and the like are suitable. Specifically, for example, sodium hydroxide, hydroxide Potassium etc. are mentioned.

Further, the solvent for synthesizing the oxide-modified polyhydric alcohol is not particularly limited as long as it is inert to the reactants. For example, aromatic hydrocarbons such as benzene, toluene, xylene, n-hexane, n- Examples thereof include aliphatic hydrocarbons such as heptane, and alicyclic hydrocarbons such as cyclohexane and cyclopentane.

In addition, it does not specifically limit as said polyhydric alcohol, For example, the polyhydric alcohol compound more than trivalence similar to what was mentioned above is mentioned.

Examples of the method of esterifying the oxide-modified polyhydric alcohol and (meth) acrylic acid include a conventional dehydration esterification reaction.
Specifically, the above oxide-modified polyhydric alcohol, (meth) acrylic acid and solvent are charged into a reactor equipped with a stirrer, a thermometer and a water separator, and heated in the presence of an acidic catalyst. The water generated as the reaction proceeds distills out of the system. After completion of the reaction, the reaction solution is washed with water, the aqueous layer is separated, and then the solvent is distilled off under reduced pressure.

The solvent in the esterification reaction of the above method (4) is not particularly limited as long as it facilitates the distillation of water and does not react with (meth) acrylic acid, oxide-modified polyhydric alcohol and acidic catalyst. The same solvent as that used in the epoxidation reaction of method (1) is preferably used.

Moreover, as an acidic catalyst in the esterification reaction of the said method (4), the thing similar to the acidic catalyst in the method (1) epoxidation reaction mentioned above is mentioned, As the addition amount, with respect to the whole quantity of a reaction liquid A preferred lower limit is 0.5% by weight and a preferred upper limit is 5% by weight.

Moreover, as a reaction temperature of the epoxidation reaction of the said method (4), a preferable minimum is 70 degreeC and a preferable upper limit is 150 degreeC. By heating at a temperature within this range, the dehydration esterification reaction can be easily performed. A more preferable lower limit is 80 ° C., and a more preferable upper limit is 120 ° C.

Furthermore, in the esterification reaction in the above method (4), it is preferable to carry out the reaction by adding a polymerization inhibitor. Examples of the polymerization inhibitor include those similar to the polymerization inhibitor in the esterification reaction of the above-described method (1). The amount of the polymerization inhibitor is usually preferably 0.01 to the total amount of the reaction solution. Part by weight, the preferred upper limit is 1% by weight.
The target (meth) acrylate can also be obtained by reacting the oxide-modified polyhydric alcohol with an acid halide such as (meth) acrylic acid chloride.

To the carboxylic acid compound having two or more carboxyl groups, an acid anhydride, and a compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule and modified with lactone and / or oxide As a method for addition reaction of a carboxylic acid compound having two or more carboxyl groups and / or an acid anhydride, a compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the above-described molecule is added with 2 carboxyl groups. Examples thereof include the same methods and methods as those described in the addition reaction of two or more carboxylic acid compounds and / or acid anhydrides.

In the curable resin composition of the present invention, the content of the polymerizable compound according to the present invention is not particularly limited, but the preferred lower limit is 20% by weight with respect to the solid content of the curable resin composition of the present invention. A preferred upper limit is 90% by weight. When it is less than 20% by weight, the curable resin composition of the present invention is not sufficiently photocured, and when used for a column spacer, a column spacer pattern may not be formed by a photolithographic technique. . When the content exceeds 90% by weight, when the curable resin composition of the present invention is used for a column spacer, the solubility of the column spacer in an alkaline developer used for manufacturing the column spacer is insufficient, and the pattern of the column spacer to be manufactured The developability of the ink may be insufficient. A more preferred lower limit is 40% by weight, and a more preferred upper limit is 80% by weight.

In addition to the above-described polymerizable compound according to the present invention, the curable resin composition of the present invention is a polymerizable unsaturated compound having no carboxyl group in the molecule in order to adjust reactivity, developability, and the like. A compound having a bond (hereinafter, also simply referred to as a polymerizable unsaturated bond-containing compound), for example, when the curable resin composition of the present invention is used for a column spacer, the flexibility and developability of the column spacer to be produced. You may use together in the range which does not impair.

The polymerizable unsaturated bond-containing compound is not particularly limited, and examples thereof include neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and 2 -Butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, diethylene glycol (meta ) Acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate such as nonaethylene glycol (meth) acrylate Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, etc. (Meth) acrylate etc. are mentioned.

Examples of the tri- or higher functional group include trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra. Examples thereof include polyfunctional (meth) acrylate compounds such as (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

When the curable resin composition of the present invention contains the polymerizable unsaturated bond-containing compound, the blending amount is not particularly limited, but is less than 40% by weight of the total amount with the polymerizable compound according to the present invention. Preferably there is. If it exceeds 40% by weight, when the curable resin composition of the present invention is used for a column spacer, the flexibility of the obtained column spacer may be impaired, and the effect of suppressing poor gravity and low-temperature foaming may be reduced. A more preferred upper limit is 30% by weight.

The curable resin composition of the present invention contains an alkali-soluble polymer compound.
The alkali-soluble polymer compound is not particularly limited, but is preferably an alkali-soluble carboxyl group-containing polymer compound containing a carboxyl group. Examples of the alkali-soluble carboxyl group-containing polymer compound include a copolymer obtained by copolymerizing a carboxyl group-containing monofunctional unsaturated compound and a monofunctional compound having a reactive functional group such as an unsaturated double bond or an epoxy group. Examples thereof include polymers (hereinafter also simply referred to as copolymers). Further, for example, a commercially available product such as “Cyclomer P” manufactured by Daicel Chemical Industries, Ltd. may be used.

The carboxyl group-containing monofunctional unsaturated compound is not particularly limited, and examples thereof include acrylic acid and methacrylic acid.
The monofunctional compound having an unsaturated double bond is not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, Examples include (meth) acrylic acid ester monomers such as (meth) acrylic acid 2-ethylhexyl and (meth) acrylic acid hydroxyethyl.

The monofunctional compound having an epoxy group is not particularly limited. For example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, Acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7- Examples thereof include epoxy heptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and a compound represented by the following general formula (1). Among them, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether are copolymerization reactivity and strength of the obtained column spacer. It is preferably used from the standpoint of increasing. These may be used independently and 2 or more types may be used together.

式（１）中、Ｒは、水素原子又は炭素数１〜５のアルキル基を表し、ｎは、０〜１０の整数である。

In formula (1), R represents a hydrogen atom or a C1-C5 alkyl group, and n is an integer of 0-10.

Moreover, it does not specifically limit as said copolymer, For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t -(Meth) acrylic acid alkyl esters such as butyl (meth) acrylate; (meth) acrylic acid alkyl esters such as methyl (meth) acrylate and isopropyl (meth) acrylate; cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) (Meth) acrylic acid cyclic alkyl esters such as acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isoboronyl (meth) acrylate; cyclohexyl (meth) acrylate, 2-methyl (Meth) acrylic acid cyclic alkyl esters such as lucyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentaoxyethyl (meth) acrylate, isobornyl (meth) acrylate; phenyl (meth) acrylate, benzyl ( (Meth) acrylate acrylic esters such as (meth) acrylate; phenyl (meth) acrylate, (meth) acrylic aryl esters such as benzyl (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene , Vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. Is mentioned. Among them, styrene, t-butyl (meth) acrylate, dicyclopentanyl (meth) acrylate, p-methoxystyrene, 2-methylcyclohexyl (meth) acrylate, 1,3-butadiene and the like are copolymerized and alkaline aqueous solution. From the viewpoint of solubility in These may be used independently and 2 or more types may be used together.

In the above copolymer, the preferred lower limit of the ratio of the components attributable to the carboxyl group-containing monofunctional unsaturated compound is 10% by weight, and the preferred upper limit is 40% by weight. When it is less than 10% by weight, it is difficult to impart alkali solubility, and when it exceeds 40% by weight, when the curable resin composition of the present invention is used for a column spacer, the column spacer is produced. The swelling at the time of development is remarkable, and it may be difficult to form a column spacer pattern. A more preferred lower limit is 15% by weight, and a more preferred upper limit is 30% by weight.

Although it does not specifically limit as a weight average molecular weight of the said copolymer, A preferable minimum is 3000 and a preferable upper limit is 100,000. When it is less than 3000, when the curable resin composition of the present invention is used for a column spacer, the developability at the time of producing the column spacer may be lowered, and when it exceeds 100,000, the curability of the present invention. When the resin composition is used for a column spacer application, the resolution at the time of manufacturing the column spacer may be lowered. A more preferred lower limit is 5000, and a more preferred upper limit is 50,000.

The method for copolymerizing the carboxyl group-containing monofunctional unsaturated compound and the monofunctional compound having a reactive functional group such as an unsaturated double bond or an epoxy group is not particularly limited. For example, a radical polymerization initiator And the method of superposing | polymerizing by conventionally well-known methods, such as block polymerization, solution polymerization, suspension polymerization, dispersion polymerization, and emulsion polymerization, using a molecular weight regulator as needed. Of these, solution polymerization is preferred.

Examples of the solvent for producing the copolymer by the solution polymerization method include aliphatic alcohols such as methanol, ethanol, isopropanol and glycol; cellosolves such as cellosolve and butylcellosolve; and carbitols such as carbitol and butylcarbitol. Tolls; esters such as cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate; ethers such as diethylene glycol dimethyl ether; cyclic ethers such as tetrahydrofuran, ketones such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone; dimethyl sulfoxide, dimethylformamide An organic solvent having a polarity such as can be used.

Examples of the medium for producing the copolymer by non-aqueous dispersion polymerization such as suspension polymerization, dispersion polymerization, and emulsion polymerization include, for example, liquid hydrocarbons such as benzene, toluene, hexane, and cyclohexane, and others. These nonpolar organic solvents can be used.

It does not specifically limit as a radical polymerization initiator used when manufacturing the said copolymer, For example, conventionally well-known radical polymerization initiators, such as a peroxide and an azo initiator, can be used.
The amount of the radical polymerization initiator used is not particularly limited. For example, the preferable lower limit is 0.001 part by weight and the preferable upper limit is 5.0 parts by weight with respect to 100 parts by weight of the total monomer components of the copolymer. A more preferred lower limit is 0.5 parts by weight, and a more preferred upper limit is 3.0 parts by weight.

Examples of the molecular weight modifier include α-methylstyrene dimer, mercaptan chain transfer agent, and the like. Of these, a long-chain alkyl mercaptan having 8 or more carbon atoms is preferable in terms of odor and little coloring.

In the curable resin composition of the present invention, the content of the alkali-soluble polymer compound is not particularly limited, but a preferred lower limit is 10% by weight and a preferred upper limit is 80% by weight. When it is less than 10% by weight, when the curable resin composition of the present invention is used for a column spacer, the solubility in an alkaline developer used for producing the column spacer is insufficient, and the column spacer to be produced The developability of the pattern may be insufficient, and if it exceeds 80% by weight, the curable resin composition of the present invention is not sufficiently photocured, and when used for a column spacer application, the column spacer is formed by photolithography. A pattern may not be formed. A more preferred lower limit is 20% by weight, and a more preferred upper limit is 60% by weight.

The curable resin composition of the present invention contains a photoreaction initiator.
The photoreaction initiator is not particularly limited, and examples thereof include conventionally known photoreaction initiators such as benzoin, benzophenone, benzyl, thioxanthone, and derivatives thereof. Specifically, for example, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, Michler ketone, (4- (methylphenylthio) phenyl) failmethanone, 2,2-dimethoxy-1,2-diphenylethane-1- ON, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2 -Methyl-1-propan-1-one, 2-methyl-1 (4-methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphospho Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, 2-chloro Examples include thioxanthone.
Also, for example, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (4-ethylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 2- (4-i-propylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, etc. Examples of such commercially available products include “Irgacure 369”, “Irgacure 379” (manufactured by Ciba Specialty Chemicals), and the like.
Further, for example, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2-methyl-2 -(4-methylphenylsulfinyl) propan-1-one, 2,4-diethylthioxanthone, isopropylthioxanthone, diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide, 4-benzoyl-4'-methyldiphenylsulfate Fido, methylbenzoiformate, 4-phenylbenzophenone, ethyl-4- (dimethylamino) benzoate, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-phenyl-1-propanone, hydroxycyclohexylphenylketone, 2- Methyl-1- [4- (me Tylthio) -phenyl] -2-morpholinopropan-1-one, methyl-2-benzoylbenzoate, 4-methylbenzophenone, 2,2′-bis- (2-chlorophenyl) -4,5,4 ′, 5′- Tetraphenyl-2'H- <1,2 '> biimidazoloyl, (4,4'-bis (diethylamino) benzophenone, 2,2'-bis (o-700 phenyl) -4,4', 5,5'- 1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -octane-1-oneoxime-O-acetate, such as tetraphenyl-1,2′-biimidazole, 1- [9- Ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9 .H -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9.H.-carbazol-3-yl]- Ethan-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, etc. Among them, oxime ester compounds such as 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate Examples of commercially available products of such oxime ester compounds that can be suitably used include “Irgacure OXE02” (manufactured by Ciba Specialty Chemicals). It is.
These photoinitiators may be used independently and 2 or more types may be used together.

In the curable resin composition of the present invention, the content of the photoinitiator is not particularly limited, but a preferred lower limit is 1% by weight and a preferred upper limit is 20% by weight. If it is less than 1% by weight, the curable resin composition of the present invention may not be photocured, and if it exceeds 20% by weight, it may not be able to be alkali-developed in photolithography when used for a column spacer. A more preferred lower limit is 5% by weight, and a more preferred upper limit is 15% by weight.

The curable resin composition of the present invention may contain a reaction aid in order to reduce reaction disturbance due to oxygen. By using such a reaction aid and a hydrogen abstraction type photoreaction initiator in combination, the curing rate when irradiated with light can be improved.

Examples of the reaction aid include amines such as n-butylamine, di-n-butylamine, triethylamine, triethylenetetramine, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate; tri-n-butylphosphine, etc. Phosphinic compounds such as sulphonic acid such as s-benzylisothiouronium-p-toluenesulfinate can be used. These reaction aids may be used alone or in combination of two or more.

The curable resin composition of the present invention preferably further contains a compound having two or more blocked isocyanate groups. The compound having two or more blocked isocyanate groups acts as a thermal crosslinking agent, and imparts thermosetting to the curable resin composition of the present invention by containing such a compound having two or more blocked isocyanate groups. can do.

The compound having two or more blocked isocyanate groups is not particularly limited. For example, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethyl Examples thereof include those obtained by blocking hexamethylene diisocyanate and polyfunctional isocyanates composed of these oligomers with blocking agents such as active methylene, oxime, lactam, and alcohol. These compounds having two or more blocked isocyanate groups may be used alone or in combination of two or more.

Moreover, as what is marketed among the compounds which have such a 2 or more block isocyanate group, Duranate 17B-60PX, Duranate E-402-B80T (above, Asahi Kasei Chemicals make) etc. are mentioned, for example.

When the curable resin composition of the present invention contains the compound having two or more blocked isocyanate groups, the blending amount thereof is preferably 0.01 to 100 parts by weight of the alkali-soluble polymer compound. Part by weight, the preferred upper limit is 50 parts by weight. If it is less than 0.01 part by weight, the curable resin composition of the present invention may not be sufficiently cured by heat, and if it exceeds 50 parts by weight, the degree of cross-linking of the resulting cured product becomes too high and will be described later. May not meet the characteristics. A more preferred lower limit is 0.05 parts by weight, and a more preferred upper limit is 20 parts by weight.

The curable resin composition of the present invention may be diluted with a diluent in order to adjust the viscosity.
The diluent is not particularly limited as long as it is selected in consideration of compatibility with the curable resin group of the present invention, coating method, film uniformity during drying, drying efficiency, and the like. When the resin group is applied using a spin coater or a slit coater, for example, an organic solvent such as methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, diethylene glycol dimethyl ether, propylene glycol monoethyl ether acetate, isopropyl alcohol is used. Is preferred. These diluents may be used alone or in combination of two or more.

The curable resin composition of this invention may contain conventionally well-known additives, such as a silane coupling agent for improving adhesiveness with a board | substrate as needed.

By using the curable resin composition of the present invention, it is possible to produce a column spacer that achieves both high recovery from compression deformation and flexibility and low elastic modulus by photocuring (and thermosetting). In addition, it is possible to obtain a sharp resolution without generating a development residue during pattern formation. Further, if such a column spacer is used, a liquid crystal display element can be obtained in which the occurrence of color unevenness due to poor gravity is effectively suppressed without causing low-temperature foaming.

In such a curable resin composition of the present invention, the preferable lower limit of the elastic modulus at 15% compression at 25 ° C. of the cured product when cured by light irradiation (and heating) is 0.2 GPa, and the preferable upper limit is 1. 0.0 GPa. When it is less than 0.2 GPa, it is too soft, and when the curable resin composition of the present invention is used for a column spacer, it may be difficult to maintain a cell gap. When it exceeds 1.0 GPa, it is too hard. When the curable resin composition of the present invention is used for a column spacer, the color filter layer may be plunged when the substrates are bonded together, or sufficient elastic deformation necessary for recovery may not be obtained. . A more preferred lower limit is 0.3 GPa, a more preferred upper limit is 0.9 GPa, a still more preferred lower limit is 0.5 GPa, and a still more preferred upper limit is 0.7 GPa.

In the present specification, the cured product means a cured product when the curable resin composition of the present invention is almost completely cured by light irradiation (and heating). The conditions for almost complete curing are that at least 50 mJ / cm ² of ultraviolet light is irradiated, and when heating, the film can be cured almost completely by applying a heat treatment at a temperature of 200 to 250 ° C. for about 20 minutes. .
Further, in this specification, 15% compression means compression so that the deformation rate of the height of the column spacer is 15%. Further, the elastic modulus and the recovery rate are measured by the following methods.
That is, first, the column spacer formed on the substrate is compressed at a load application speed of 10 mN / s, and is compressed to a height corresponding to 85% of the initial height H ₀ . Here, the column spacer height when a load of 1 mN is applied is H ₁ , the column spacer height corresponding to 85% of H ₀ is H ₂ , and the load when F ₂ reaches H ₂ is F. Next, the load F is held for 5 seconds, and after deformation at a constant load, the load is removed at a load application speed of 10 mN / sec, and the recovery deformation of the column spacer height due to elastic recovery is measured. The height of the column spacer at the time when the compression deformation during this time becomes maximum is H _3, and the height of the column spacer when a load of 1 mN is applied in the process of recovering the deformation of the column spacer is H ₄ . The elastic count and the recovery rate can be calculated by the following formula (1) and the following formula (2).

Elastic modulus E = F / (D × S) (1)
Recovery rate R = (H ₄ −H ₃ ) / (H ₁ −H ₃ ) × 100 (2)

In formula (1), F represents the load (N), D represents the deformation rate of the column spacer height, and S represents the cross-sectional area (m ² ) of the column spacer.

The method for producing the curable resin composition of the present invention is not particularly limited. For example, a compound having two or more polymerizable unsaturated bonds in the molecule, an alkali-soluble polymer compound, a photoreactive initiator, And the method of mixing the polymerizable unsaturated bond containing compound added as needed, the compound which has a 2 or more block isocyanate group, a diluent, etc. by a conventionally well-known method is mentioned.

Next, a method for producing a column spacer using the curable resin composition of the present invention will be described.
When manufacturing a column spacer using the curable resin composition of the present invention, first, the curable resin composition of the present invention is coated on a substrate to form a film to form a film. .
The coating method is not particularly limited, and conventionally known coating methods such as spin coating, slit coating, spray coating, dip coating, and bar coating can be used.

Next, actinic rays such as ultraviolet rays are irradiated on the formed film through a mask on which a predetermined pattern is formed. Thereby, in a light irradiation part, the compound and photoreaction initiator which have a 2 or more polymerizable unsaturated bond in the molecule | numerator contained in the curable resin composition of this invention react, and it photocures.
The irradiation amount of the active light is not particularly limited, but is preferably 100 mJ / cm ² or more in the case of ultraviolet rays. If it is less than 100 mJ / cm ² , the photocuring is insufficient and the subsequent alkali treatment may dissolve the exposed area and a pattern may not be formed.

Next, the photocured product after photocuring is alkali-developed to form a column spacer having a predetermined pattern made of the photocured product of the curable resin composition of the present invention on the substrate.
Since the curable resin composition of the present invention contains a compound having two or more polymerizable unsaturated groups in the molecule having the specific structure described above, almost no residue remains when a predetermined pattern is formed in this step. It is possible to form a column spacer with a sharp pattern that does not occur and has excellent resolution. Further, when the above-described polymerizable compound according to the present invention is lactone-modified and / or oxide-modified, the column spacer formed using the curable resin composition of the present invention further has high recoverability from compression deformation. It is flexible and has a low elastic modulus.

When the curable resin composition of the present invention contains a compound having two or more blocked isocyanate groups, the alkali-soluble composition is further contained by heating the patterned photocured product after the development treatment. A molecular compound reacts with a compound having two or more blocked isocyanate groups.
The heating condition may be appropriately determined in consideration of the size and thickness of the pattern, but is preferably at least 200 ° C. for 20 minutes or more.
A column spacer using the curable resin composition of the present invention is also one aspect of the present invention.

In the column spacer of the present invention, the preferable lower limit of the elastic modulus at 15% compression at 25 ° C. is 0.2 GPa, and the preferable upper limit is 1.0 GPa. If it is less than 0.2 GPa, it may be too soft and it may be difficult to maintain the cell gap. If it exceeds 1.0 GPa, it may be too hard to enter the color filter layer when bonding the substrates, or necessary for recovery. Sufficient elastic deformation may not be obtained. A more preferred lower limit is 0.3 GPa, a more preferred upper limit is 0.9 GPa, a still more preferred lower limit is 0.5 GPa, and a still more preferred upper limit is 0.7 GPa.

The column spacer of the present invention is designed so that its height is slightly higher than the cell gap, and is manufactured by a conventionally known method such as the ODF method, thereby generating color unevenness due to poor gravity without causing low-temperature foaming. It is possible to obtain a liquid crystal display element that can effectively suppress the above.
The curable resin composition of the present invention or a liquid crystal display device using the column spacer of the present invention is also one aspect of the present invention.

Since the curable resin composition of the present invention contains a compound having one or more carboxyl groups and two or more polymerizable unsaturated bonds in the molecule, the affinity with the developer is improved and the polymerization reaction is improved. Proceeding promptly, when used for a column spacer, the exposure sensitivity during pattern formation by a photolithographic technique is excellent. In addition, the column spacer using the curable resin composition of the present invention has excellent flexibility and high compression recovery characteristics. According to such a column spacer, “gravity due to liquid crystal expansion during heating is achieved. It is possible to provide a liquid crystal display element capable of simultaneously suppressing “bad” and “low temperature foaming” due to shrinkage of liquid crystal at low temperatures.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
(1) Synthesis of a compound having a polymerizable unsaturated bond In a 1 L eggplant-shaped flask, 100 parts by weight of methanol as a solvent and caprolactone-modified dipentaerythritol hexaacrylate (DPCA-120, Nippon Kayaku) as a polyfunctional (meth) acrylate compound 40 parts by weight, thiosalicylic acid (manufactured by Wako Pure Chemical Industries) 4 parts by weight, benzyltrimethylammonium hydroxide 40% aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) 0.05 parts by weight as a catalyst, and hydroquinone 0.4% by weight as a polymerization inhibitor. 4 parts by weight were charged and reacted at room temperature for 1 hour with stirring.
Thereafter, methanol was removed by an evaporator to obtain a caprolactone-modified dipentaerythritol hexaacrylate having a carboxyl group.

(2) Synthesis of alkali-soluble polymer compound A 3 L separable flask was charged with 60 parts by weight of diethylene glycol dimethyl ether as a solvent, heated to 90 ° C. in a nitrogen atmosphere, and then 10 parts by weight of methyl methacrylate and 8 parts of methacrylic acid. Parts by weight, 12 parts by weight of n-butyl methacrylate, 10 parts by weight of 2-ethylhexyl acrylate, 0.4 parts by weight of azobisvaleronitrile, and 0.8 parts by weight of n-dodecyl mercaptan continuously over 3 hours It was dripped.
Then, after hold | maintaining for 30 minutes at 90 degreeC, temperature was heated up to 105 degreeC and superposition | polymerization was continued for 3 hours and the alkali-soluble high molecular compound solution was obtained.
The obtained alkali-soluble polymer compound was sampled and the molecular weight was measured by gel permeation chromatography (GPC). As a result, the weight average molecular weight (Mw) was about 20,000.

(3) Preparation of curable resin composition 100 parts by weight of the obtained alkali-soluble polymer compound solution (solid content: 40 wt%), 60 parts by weight of carboxyl group-containing caprolactone-modified dipentaerythritol hexaacrylate, Irga as a photoreaction initiator A curable resin composition was prepared by mixing 10 parts by weight of Cure 907 (manufactured by Ciba Specialty Chemicals), 10 parts by weight of DETX-S (manufactured by Nippon Kayaku) and 70 parts by weight of diethylene glycol dimethyl ether as a solvent.

(Example 2)
(1) Synthesis of compound having polymerizable unsaturated bond In a 1 L eggplant-shaped flask, 100 parts by weight of methanol as a solvent, caprolactone-modified pentaerythritol tetraacrylate as a polyfunctional (meth) acrylate compound (1 mol of acrylic acid and 2 mol of caprolactone) 40 parts by weight of a compound obtained by reacting 4 moles of the resulting compound with 1 mole of pentaerythritol by esterification), 4 parts by weight of mercaptopropionic acid (manufactured by Wako Pure Chemical Industries, Ltd.), and 40% aqueous solution of benzyltrimethylammonium hydroxide as a catalyst 0.05 part by weight (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.4 part by weight of hydroquinone as a polymerization inhibitor were added and reacted at room temperature for 1 hour with stirring.
Thereafter, methanol was removed by an evaporator to obtain caprolactone-modified pentaerythritol tetraacrylate having a carboxyl group.

(2) Preparation of curable resin composition As alkali-soluble polymer compound, cyclomer P, ACA-230AA (manufactured by Daicel Chemical Industries) 100 parts by weight (solid content 40 wt%), polymerizable unsaturated bond-containing compound, 60 parts by weight of caprolactone-modified pentaerythritol tetraacrylate having a carboxyl group obtained in (1), 10 parts by weight of Irgacure 907 (manufactured by Ciba Specialty Chemicals) and DETX-S (manufactured by Nippon Kayaku) as a photoinitiator 10 A curable resin composition was prepared by mixing parts by weight and 70 parts by weight of diethylene glycol dimethyl ether as a solvent.

(Example 3)
100 parts by weight of the alkali-soluble polymer compound solution obtained in Example 1, 120 parts by weight of the carboxyl group-containing caprolactone-modified pentaerythritol triacrylate obtained in Example 2, a photoreaction initiator (manufactured by Ciba Specialty Chemicals, Irgacure) 369) 15 parts by weight, 8 parts by weight of a thermal crosslinking agent (Duranate E-402-B80T, manufactured by Asahi Kasei Chemicals) and 60 parts by weight of diethylene glycol dimethyl ether as a solvent were mixed to prepare a curable resin composition.

Example 4
(1) Synthesis of a compound having a polymerizable unsaturated bond In a 1 L eggplant-shaped flask, 100 parts by weight of methanol as a solvent and ethylene oxide / caprolactone-modified dipentaerythritol tetraacrylate (acrylic acid 1) as a polyfunctional (meth) acrylate compound 40 parts by weight of a compound obtained by reacting 6 mol of a compound obtained by reacting 2 mol of caprolactone with 1 mol of a compound obtained by reacting 12 mol of ethylene oxide with 1 mol of dipentaerythritol, and mercaptosuccinic acid ( Wako Pure Chemical Industries, Ltd.) 4 parts by weight, benzyltrimethylammonium hydroxide 40% aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) 0.05 parts by weight as a catalyst, and hydroquinone 0.4 parts by weight as a polymerization inhibitor were charged with stirring. The reaction was carried out at 1 ° C. for 1 hour.
Thereafter, methanol was removed by an evaporator to obtain ethylene oxide / caprolactone-modified dipentaerythritol tetraacrylate having a carboxyl group.

(2) Preparation of curable resin composition 100 parts by weight of the alkali-soluble polymer compound solution obtained in Example 1 and the polymerizable unsaturated bond-containing compound as a compound having an ethylene oxide / carboxyl group obtained in (1) 60 parts by weight of caprolactone-modified dipentaerythritol tetraacrylate, 10 parts by weight of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a photoinitiator, 10 parts by weight of DETX-S (manufactured by Nippon Kayaku), and diethylene glycol dimethyl ether 70 as a solvent A curable resin composition was prepared by mixing parts by weight.

(Example 5)
20 parts by weight (9.8 mmol) of a compound obtained by adding diethanolamine to caprolactone-modified dipentaerythritol hexaacrylate having the structure represented by the following chemical formula (2) as a raw material monomer (1), and 1.48 weight of tetrahydrophthalic anhydride as an acid anhydride Part (9.8 mmol), 0.01 part by weight of hydroquinone as a polymerization inhibitor, and 20 parts by weight of propylene glycol methyl ether (PGMEA) as a solvent were charged in a flask and heated while flowing nitrogen.

Next, when tetrahydrophthalic anhydride was completely dissolved, 0.02 part by weight of triethylamine was added as a catalyst, followed by reaction in a 120 ° C. oil bath for 6 hours in a nitrogen atmosphere, and then allowed to cool to room temperature. A compound (A) having a structure represented by the chemical formula (3) was obtained. In addition, the result of having performed NMR measurement of the obtained compound (A) is shown in FIG. Further, NMR measurement of tetrahydrophthalic anhydride was also performed, and the result is shown in FIG.

Thereafter, a curable resin composition for a column spacer was prepared in the same manner as in Example 1 except that the obtained compound (A) was used in place of the carboxyl group-containing caprolactone-modified dipentaerythritol hexaacrylate.

(Example 6)
20 parts by weight (9.4 mmol) of a compound obtained by adding 2 mol of diethanolamine to 1 mol of caprolactone-modified dipentaerythritol hexaacrylate having a structure represented by the following chemical formula (4-1) as a raw material monomer (1), tetrahydrophthalic anhydride as an acid anhydride 2.86 parts by weight (18.8 mmol), 0.01 part by weight of hydroquinone as a polymerization inhibitor, and 20 parts by weight of propylene glycol methyl ether (PGMEA) as a solvent were placed in a flask and heated while flowing nitrogen. .

Next, when tetrahydrophthalic anhydride was completely dissolved, 0.02 part by weight of triethylamine was added as a catalyst, followed by reaction in a 120 ° C. oil bath for 6 hours in a nitrogen atmosphere, and then allowed to cool to room temperature. A compound (B) having a structure represented by the chemical formula (4-2) was obtained. In addition, the result of having performed NMR measurement of the obtained compound (B) is shown in FIG.

Thereafter, a curable resin composition for a column spacer was prepared in the same manner as in Example 1 except that the obtained compound (B) was used in place of the carboxyl group-containing caprolactone-modified dipentaerythritol hexaacrylate.

(Example 7)
20 parts by weight (9.0 mmol) of a compound obtained by adding 3 mol of diethanolamine to 1 mol of caprolactone-modified dipentaerythritol hexaacrylate having the structure represented by the following chemical formula (5-1) as a raw material monomer (1), tetrahydrophthalic anhydride as an acid anhydride A flask was charged with 4.01 parts by weight (27.0 mmol), 0.01 parts by weight of hydroquinone as a polymerization inhibitor, and 20 parts by weight of propylene glycol methyl ether (PGMEA) as a solvent, and heated while flowing nitrogen. .

Next, when tetrahydrophthalic anhydride was completely dissolved, 0.02 part by weight of triethylamine was added as a catalyst, followed by reaction in a 120 ° C. oil bath for 6 hours in a nitrogen atmosphere, and then allowed to cool to room temperature. A compound (C) having a structure represented by the chemical formula (5-2) was obtained. In addition, the result of having performed NMR measurement of the obtained compound (C) is shown in FIG.

Thereafter, a curable resin composition for a column spacer was prepared in the same manner as in Example 1 except that the obtained compound (C) was used in place of the carboxyl group-containing caprolactone-modified dipentaerythritol hexaacrylate.

(Example 8)
As raw material monomer (2), 20 parts by weight (15.2 mmol) of a compound obtained by adding diethanolamine to caprolactone-modified pentaerythritol triacrylate having a structure represented by the following chemical formula (6), and 2.31 weight by weight of tetrahydrophthalic anhydride as an acid anhydride Part (15.2 mmol), hydroquinone 0.01 part by weight as a polymerization inhibitor, and propylene glycol methyl ether (PGMEA) 20 part by weight as a solvent were charged in a flask and heated while flowing nitrogen.

Next, when tetrahydrophthalic anhydride was completely dissolved, 0.02 part by weight of triethylamine was added as a catalyst, followed by reaction in a 120 ° C. oil bath for 6 hours in a nitrogen atmosphere, and then allowed to cool to room temperature. A compound (D) having a structure represented by the chemical formula (7) was obtained. In addition, the result of having performed NMR measurement of the obtained compound (D) is shown in FIG.

Thereafter, a curable resin composition for a column spacer was prepared in the same manner as in Example 1 except that the obtained compound (D) was used in place of the carboxyl group-containing caprolactone-modified dipentaerythritol hexaacrylate.

Example 9
As a raw material monomer (3), caprolactone-modified dipentaerythritol pentaacrylate having a structure represented by the following chemical formula (8) (5 mol of a compound obtained by reacting 1 mol of dipentaerythritol with 2 mol of caprolactone with 1 mol of acrylic acid) is esterified. 20 parts by weight (12.0 mmol), 1.20 parts by weight (12.0 mmol) of succinic anhydride as an acid anhydride, 0.01 parts by weight of hydroquinone as a polymerization inhibitor, and propylene acetate as a solvent 20 parts by weight of glycol methyl ether (PGMEA) was charged into a flask and heated while flowing nitrogen.

Next, when the succinic anhydride was completely dissolved, 0.02 part by weight of triethylamine was added as a catalyst, and then the reaction was performed in a 120 ° C. oil bath for 6 hours in a nitrogen atmosphere, followed by cooling to room temperature. The compound (E) having the structure shown in (9) was obtained.

Thereafter, a curable resin composition for a column spacer was prepared in the same manner as in Example 1 except that the obtained compound (E) was used in place of the carboxyl group-containing caprolactone-modified dipentaerythritol hexaacrylate.

次に、無水コハク酸が完全に溶けたところで、触媒としてトリエチルアミン０．０２重量部を添加した後、窒素雰囲気下、１２０℃油浴で６時間反応させた後、室温まで放冷し、下記化学式（１１）に示す構造の化合物（Ｆ）を得た。 (Example 10)
As a raw material monomer (4), caprolactone-modified pentaerythritol triacrylate having a structure represented by the following chemical formula (10) (reacted by esterification of 3 mol of a compound obtained by reacting 1 mol of pentaerythritol with 2 mol of caprolactone with 1 mol of acrylic acid) Compound) 20 parts by weight (16.5 mmol), 16.5 parts by weight (16.5 mmol) of succinic anhydride as an acid anhydride, 0.01 parts by weight of hydroquinone as a polymerization inhibitor, and propylene glycol methyl acetate as a solvent 20 parts by weight of ether (PGMEA) was charged into a flask and heated while flowing nitrogen.

Next, when the succinic anhydride was completely dissolved, 0.02 part by weight of triethylamine was added as a catalyst, and then the reaction was performed in a 120 ° C. oil bath for 6 hours in a nitrogen atmosphere, followed by cooling to room temperature. The compound (F) having the structure shown in (11) was obtained.

Thereafter, a curable resin composition for a column spacer was prepared in the same manner as in Example 1 except that the obtained compound (F) was used in place of the carboxyl group-containing caprolactone-modified dipentaerythritol hexaacrylate.

(Comparative Example 1)
Preparation of Curable Resin Composition 100 parts by weight of the alkali-soluble polymer compound solution obtained in Example 1, and caprolactone-modified dipentaerythritol hexaacrylate (DPCA-120, manufactured by Nippon Kayaku Co., Ltd.) as a polymerizable unsaturated bond-containing compound ) 60 parts by weight, 10 parts by weight of Irgacure 907 (manufactured by Ciba Specialty Chemicals) and 10 parts by weight of DETX-S (manufactured by Nippon Kayaku) as a photoinitiator, and 70 parts by weight of diethylene glycol dimethyl ether as a solvent A curable resin composition was prepared.

(Evaluation)
The curable resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 and 2 were evaluated by the following methods. The results are shown in Table 1.

(1) Preparation of column spacer On the glass substrate on which the transparent conductive film was formed, the curable resin composition obtained in each example and comparative example was applied by spin coating, and dried at 100 ° C. for 2 minutes to apply. A membrane was obtained. The resulting coating film was irradiated with 100 mJ / cm ² ultraviolet rays through a 20 μm square dot pattern mask, developed with 0.04% KOH solution for 40 seconds, washed with pure water for 30 seconds, and column spacers. Pattern was formed.
Thereafter, after baking at 220 ° C. for 30 minutes, the cross-sectional area of the column spacer was 20 μm × 20 μm (400 μm ² ) and the height was 3.0 μm.

(Evaluation of column spacer)
(Resolution)
The sharpness (resolution) of the edge of the column spacer pattern and the roughness of the pattern surface (pattern formation state) were observed with an optical microscope and evaluated according to the following criteria.
Evaluation of resolution ○: Edge is sharp ×: Edge is uneven or residue is observed Pattern formation state ○: Pattern surface is smooth ×: Pattern surface is rough

(Alkali soluble)
By dissolving 1 part by weight of a polymerizable compound (solid content) in 200 parts by weight of a 0.04 wt% KOH aqueous solution and visually evaluating the dissolved state, alkali solubility was evaluated according to the following criteria.

A: Completely dissolved without turbidity and precipitate of solution. ○: Although turbidity of solution was not present. △: With turbidity of solution and precipitate. X: Precipitation without dissolution.

(Compression characteristics)
In a room adjusted to a temperature of 25 ° C., the column spacer was compressed at a load application speed of 10 mN / s until it reached a height corresponding to 85% of the initial height H ₀ . Here, the column spacer height when a load of 1 mN was applied was H ₁ , the column spacer height corresponding to 85% of H ₀ was H ₂ , and the load when F reached H ₂ was F.
Next, the load F was held for 5 seconds and subjected to deformation at a constant load. Then, the load was removed at a load application speed of 10 mN / sec, and the recovery deformation of the column spacer height due to elastic recovery was measured. The height of the column spacer at the time when the compression deformation during this period reached the maximum was H _3, and the height of the column spacer when a load of 1 mN was applied in the process of recovering the deformation of the column spacer was H ₄ . Using the obtained values, the compression elastic modulus E at 15% compression and the recovery rate R when 15% compression deformed were calculated by the following formula (1) and the following formula (2). In the formula (1), E represents the compression elastic modulus (Pa), F represents the load (N), and D represents the column spacer height deformation rate = (H ₀ −H ₂ ) / H _0. S represents the cross-sectional area (m ² ) of the column spacer.

E = F / (D × S) (1)
R = (H ₄ −H ₃ ) / (H ₁ −H ₃ ) × 100 (2)

(2) Manufacture of liquid crystal display element The sealing agent (made by Sekisui Chemical Co., Ltd.) was apply | coated with the dispenser so that the rectangular frame might be drawn on the glass substrate in which the column spacer obtained was formed.
Subsequently, fine droplets of liquid crystal (manufactured by Chisso Co., Ltd., JC-5004LA) are dropped on the entire surface of the glass substrate, and the other glass substrate is immediately overlaid, and a high-pressure mercury lamp is used as a seal portion to apply ultraviolet light at 50 mW / Irradiated with cm ² for 60 seconds.
Thereafter, liquid crystal annealing was performed at 120 ° C. for 1 hour for thermosetting to produce a liquid crystal display element.

(Evaluation of liquid crystal display elements)
The liquid crystal display element was turned on and the uniformity of the cell gap was visually observed on the display screen and evaluated according to the following criteria.
Further, the liquid crystal display element was left standing under a condition of 60 ° C. for 60 hours in a vertically standing state. After being allowed to stand, a liquid crystal display device was installed between the crossed Nicols, and the display image was visually observed, and the occurrence of poor gravity was evaluated according to the following criteria.
Further, the liquid crystal display element was left under the condition of −20 ° C. for 24 hours. After being allowed to stand, a liquid crystal display device was installed between the crossed Nicols and observed visually, and the occurrence of low temperature foaming was evaluated according to the following criteria.
Evaluation of cell gap ○: Uniform ×: Color unevenness Evaluation of poor gravity ○: Uniform ×: Color unevenness Evaluation of low-temperature foaming ○: No foaming ×: With foaming

(Example 11)
As a raw material monomer, a caprolactone-modified dipentaerythritol pentaacrylate having a structure represented by the following chemical formula (12) (compound obtained by reacting 1 mol of dipentaerythritol with 12 mol of ε-caprolactone and further reacting with 5 mol of acrylic acid by esterification) ) 20 parts by weight (10.8 mmol), 1.28 parts by weight (10.8 mmol) of succinic anhydride as the acid anhydride, 0.01 parts by weight of hydroquinone as the polymerization inhibitor, and propylene glycol methyl ether acetate (PGMEA) as the solvent ) 20 parts by weight were charged into a flask and heated while flowing nitrogen. In addition, the result of having performed the NMR measurement of the caprolactone modified dipentaerythritol pentaacrylate of the structure shown by Chemical formula (12) used as a raw material monomer is shown in FIG.

Next, when the succinic anhydride was completely dissolved, 0.02 part by weight of triethylamine was added as a catalyst, and then the reaction was performed in a 120 ° C. oil bath for 6 hours in a nitrogen atmosphere, followed by cooling to room temperature. The compound (G) having the structure shown in (13) was obtained. In addition, the result of having performed NMR measurement of the obtained compound (G) is shown in FIG.

Thereafter, a curable resin composition for a column spacer was prepared in the same manner as in Example 1 except that the obtained compound (K) was used instead of the carboxyl group-containing caprolactone-modified dipentaerythritol hexaacrylate.

(Example 12)
As a raw material monomer, caprolactone-modified pentaerythritol triacrylate having a structure represented by the following chemical formula (14) (a compound obtained by reacting 1 mol of pentaerythritol with 8 mol of ε-caprolactone and further reacting with 3 mol of acrylic acid by esterification) 20 weight Parts (16.8 mmol), 1.98 parts by weight (16.8 mmol) of succinic anhydride as an acid anhydride, 0.01 parts by weight of hydroquinone as a polymerization inhibitor, and 20 parts by weight of propylene glycol methyl ether (PGMEA) as a solvent The portion was placed in a flask and heated with a nitrogen flow. In addition, the result of having performed the NMR measurement of the caprolactone modified pentaerythritol triacrylate of the structure shown to Chemical formula (14) used as a raw material is shown in FIG.

Next, when the succinic anhydride was completely dissolved, 0.02 part by weight of triethylamine was added as a catalyst, and then the reaction was performed in a 120 ° C. oil bath for 6 hours in a nitrogen atmosphere, followed by cooling to room temperature. The compound (H) having the structure shown in (15) was obtained. In addition, the result of having performed NMR measurement of the obtained compound (H) is shown in FIG.

Thereafter, a curable resin composition for a column spacer was prepared in the same manner as in Example 1 except that the obtained compound (H) was used instead of the carboxyl group-containing caprolactone-modified dipentaerythritol hexaacrylate.

(Example 13)
As a raw material monomer, ethylene oxide-modified pentaerythritol triacrylate having a structure represented by the following chemical formula (16) (compound obtained by reacting 20 mol of ethylene oxide with 1 mol of pentaerythritol and further reacting 3 mol of acrylic acid by esterification) 20 Parts by weight (18.3 mmol), 2.16 parts by weight (18.3 mmol) of succinic anhydride as an acid anhydride, 0.01 parts by weight of hydroquinone as a polymerization inhibitor, and propylene glycol methyl ether (PGMEA) 20 as a solvent A part by weight was charged in a flask and heated while flowing nitrogen.

Next, when the succinic anhydride was completely dissolved, 0.02 part by weight of triethylamine was added as a catalyst, and then the reaction was performed in a 120 ° C. oil bath for 6 hours in a nitrogen atmosphere, followed by cooling to room temperature. Compound (I) having the structure shown in (17) was obtained.

Thereafter, a curable resin composition for a column spacer was prepared in the same manner as in Example 1 except that the obtained compound (I) was used in place of the carboxyl group-containing caprolactone-modified dipentaerythritol hexaacrylate.

(Evaluation)
The curable resin compositions obtained in Examples 11 to 13 were evaluated by the same method as in Example 1. The results are shown in Table 1.

According to the present invention, a column spacer having a clear pattern has excellent developability and solubility, and does not generate a development residue when forming a pattern when used for a column spacer used for manufacturing a liquid crystal display element. A curable resin composition capable of forming a liquid crystal display element capable of effectively suppressing the occurrence of color unevenness due to poor gravity without causing low-temperature foaming, and using the curable resin composition Column spacers and liquid crystal display elements can be provided.

6 is a graph showing the NMR measurement result of the compound (A) obtained in Example 5. 4 is a graph showing the NMR measurement result of the compound (B) obtained in Example 6. 4 is a graph showing the NMR measurement result of the compound (C) obtained in Example 7. 6 is a graph showing the NMR measurement result of the compound (D) obtained in Example 8. It is a graph which shows the NMR measurement result of the tetrahydro phthalic anhydride used in the Example. 4 is a graph showing NMR measurement results of raw material monomers used in Example 11. 4 is a graph showing the NMR measurement results of the compound (G) obtained in Example 11. 6 is a graph showing NMR measurement results of raw material monomers used in Example 12. 4 is a graph showing NMR measurement results of the compound (H) obtained in Example 12.

Claims (11)

A curable resin composition comprising a compound having two or more polymerizable unsaturated bonds in the molecule, an alkali-soluble polymer compound, and a photoinitiator,
The curable resin composition, wherein the compound having two or more polymerizable unsaturated bonds in the molecule has one or more carboxyl groups and two or more polymerizable unsaturated bonds in the molecule. The compound having two or more polymerizable unsaturated bonds in the molecule is a compound having one or more carboxyl groups and two or more polymerizable unsaturated bonds in the lactone-modified and / or oxide-modified molecule. The curable resin composition according to claim 1. A compound having two or more polymerizable unsaturated bonds in a lactone-modified and / or oxide-modified molecule is a polyfunctional (meth) acrylate having one or more carboxyl groups in the lactone-modified and / or oxide-modified molecule. The curable resin composition according to claim 1, wherein the curable resin composition is a compound. The polyfunctional (meth) acrylate compound having one or more carboxyl groups in the lactone-modified and / or oxide-modified molecule is a lactone-modified and / or oxide-modified trimethylolpropane tri (meth) acrylate, trimethylolethanetri ( (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate, carboxyl 3. The curable resin composition, wherein the a compound compound was added with. 5. The curable resin composition according to claim 1, wherein the compound having two or more polymerizable unsaturated bonds in the molecule further has one or more hydroxyl groups in the molecule. A compound having two or more polymerizable unsaturated bonds in the molecule can be obtained by subjecting a compound having three or more polymerizable unsaturated bonds in the molecule to an addition reaction of a compound having a carboxyl group and a thiol group. The curable resin composition according to claim 1, 2, 3, 4 or 5. The compound having two or more polymerizable unsaturated bonds in the molecule is obtained by adding an acid anhydride to a compound having two or more polymerizable unsaturated bonds and a hydroxyl group in the molecule. Item 6. The curable resin composition according to item 1, 2, 3, 4 or 5. Furthermore, the compound which has a 2 or more block isocyanate group is contained, The curable resin composition of Claim 1, 2, 3, 4, 5, 6 or 7 characterized by the above-mentioned. A column spacer comprising the curable resin composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8. 10. The column spacer according to claim 9, wherein the elastic modulus at the time of 15% compression at 25 ° C. is 0.2 to 1.0 GPa. A curable resin composition according to claim 1, 2, 3, 5, 6, 7, or 8, or a column spacer according to claim 9 or 10.

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