JP2008052256A - Curable composition, cured object, color filter and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition giving a cured object having excellent evenness in height when applied by die coating. <P>SOLUTION: The curable composition comprises an ethylenic unsaturated compound (ingredient A), a photopolymerization initiator (ingredient B), a polymerizable monomer (ingredient C) having a high viscosity, and a solvent (ingredient D). The curable composition has a leveling resistance (RL=μ×C<SP>3</SP>) expressed with the viscosity μ and the solid concentration C of the coating fluid, in a range of 0.01 to 0.05, and a sagging resistance (RS=μ×C<SP>2</SP>) of 0.1 or more. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a curable composition and the like, and more particularly to a curable composition suitable for forming a color filter such as a liquid crystal display device.

In recent years, with respect to color filters used in liquid crystal display devices and the like, methods for producing highly uniform color filters have been developed in order to achieve required performance.
For example, conventionally, the main process of applying a curable composition (resist) has been to drop the resist onto the center of the substrate and make it uniform by spin coating.
However, as the substrate size at the time of liquid crystal panel manufacture increases mainly for TV applications, etc., the resist usage increases, and further, restrictions on the spin coater device (motor capability, etc.) arise. Recently, a coating technique based on a die coating method has been developed and partly put into practical use (see Patent Document 1).

Japanese Patent Laying-Open No. 2005-266783

By the way, the photo spacer is used for the purpose of keeping the distance between the two substrates constant in the liquid crystal panel. If the distance between the substrates is not uniform, it may cause a display failure or the like, and the curability for other color filters. Compared to the composition, a high level of uniformity is required.
However, in the case of coating by the die coating method, the film thickness after coating depends on the uneven shape of the tip of the die, the mounting state of the die, the unevenness of the discharge flow rate, etc. Tend to form a distribution.
In addition, in the die coating method, since the viscosity of the coating solution and the solid content concentration are generally small, the resist after coating flows under the influence of gravity when there is a gradient such as the deflection of the substrate. There is a problem that the thickness distribution tends to be large.
According to our study, the film thickness distribution of these coating films becomes more conspicuous as the substrate becomes larger. When such a film thickness distribution occurs in the coating film, for example, the height required for the spacer is high. It was found that the uniformity was significantly impaired.

The present invention has been made to solve the above-described problems.
That is, an object of the present invention is to provide a curable composition from which a cured product having excellent height uniformity can be obtained in die coating.
Moreover, the other objective of this invention is to provide the hardened | cured material formed with such a curable composition.
Another object of the present invention is to provide a color filter excellent in height uniformity.
Furthermore, another object of the present invention is to provide a liquid crystal display device provided with a color filter excellent in height uniformity.

As a result of intensive studies on the above problems, the present inventors have found that the problem can be solved by adjusting the coating solution of the curable composition from the following viewpoints.
That is, according to the present invention, there is provided a curable composition characterized by satisfying the following (A) and (B).
(A) The leveling resistance value (RL) represented by the following formula (1) using the viscosity (μ) and solid content concentration (C) of the coating solution is in the range of 0.01 to 0.05.
RL = μ × C ³ (1)
(In formula (1), RL is the leveling resistance value, μ is the viscosity of the coating solution (unit: mPa · s), and C is the solid content concentration (unit: kg / kg).)
(B) The sagging resistance value (RS) represented by the following formula (2) is 0.1 or more.
RS = μ × C ² (2)
(In Formula (2), RS is a sag resistance value, μ is the viscosity of the coating solution (unit: mPa · s), and C is the solid content concentration (unit: kg / kg).)

  In addition, the curable composition to which the present invention is applied is preferably used for die coating, and is preferably used for forming a color filter such as a liquid crystal display device.

Moreover, according to this invention, the hardened | cured material characterized by hardening the curable composition mentioned above is provided.
Furthermore, according to this invention, the color filter characterized by including this hardened | cured material is provided.
Furthermore, according to the present invention, there is provided a liquid crystal display device comprising such a color filter.

  According to the curable composition of the present invention, a cured product having excellent height uniformity can be formed by die coating.

  The best mode for carrying out the present invention (hereinafter, an embodiment of the present invention) will be described in detail below. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the invention.

[1] Leveling resistance value (RL), sagging resistance value (RS)
The curable composition to which the present embodiment is applied is a leveling represented by the following formula (1) from the viscosity [μ (mPa · s)] and the solid content concentration [C (kg / kg)] of the coating solution. The resistance value (RL) is preferably in the range of 0.01 to 0.05, more preferably in the range of 0.01 to 0.045, and particularly preferably in the range of 0.01 to 0.04. It is.
RL = μ × C ³ (1)

When the coating solution is a Newtonian fluid, the resistance when the unevenness after coating is leveled is expressed by the following equation (3).
Leveling resistance ∝ (3μ) / (16πh ³ ) ∝ (3π / 16) × μ × C ³ (3)
Here, in the above formula, μ is the viscosity of the coating solution, h is the wet coating thickness, and C is the solid content concentration of the coating solution.
In the present embodiment, μ × C ³ is defined as a leveling resistance value (RL) (formula (1)). According to this formula (1), when the viscosity (μ) is low and the wet coating film thickness is thick, in other words, the solid content concentration (C) is low, the unevenness generated during die coating is leveled (smoothed). Resistance is low and leveling is improved.

Furthermore, the curable composition to which the present embodiment is applied is represented by the following formula (2) from the viscosity [μ (mPa · s)] of the coating solution and the solid content concentration [C (kg / kg)]. The sag resistance value (RS) is preferably 0.1 or more, more preferably 0.13 or more, and particularly preferably 0.15 or more.
RS = μ × C ² (2)

It is called dripping that the coating liquid applied to the inclined surface flows and causes uneven stripes and pools to partially thicken the coating film, and the cause is mainly gravity. When the coating liquid is a Newtonian fluid, the surface velocity when the flow is generated by the action of gravity is expressed by the following equation (4).
Surface velocity = (1/2) × (ρg / μ) × h ² (4)
Here, in the above formula (4), μ is the viscosity of the coating solution, h is the wet coating thickness, g is the gravitational constant, and ρ is the density. Therefore, the resistance against sagging is expressed by the following equation (5).
Sag resistance ∝2μ / (ρgh ² ) ∝μ × C ² (5)

In the present embodiment, μ × C ² is defined as a sagging resistance value (RS) (formula (2)). According to this formula (2), the higher the viscosity, the thinner the wet coating film thickness, in other words, the higher the solid content concentration, the higher the resistance to the flow caused by the action of gravity, resulting in uneven coating film. Hateful.

  For the above reasons, the means for improving the leveling property and sagging suppression are contradictory, but paying attention to the difference in the index on the solid content concentration [C (kg / kg)] of each resistance value, the viscosity of the coating solution [μ (MPa · s)] and solid content concentration [C (kg / kg)] can be adjusted to achieve both improvement in leveling properties and suppression of dripping.

[2] Lower limit of viscosity (μ), upper limit of solid content concentration (C) In the curable composition to which the present embodiment is applied, the viscosity (μ) of the coating solution is usually 1 mPa · s or more. In particular, in the case of producing a color filter having a thin coating film thickness after drying (that is, after the final step) in the die coating method, the viscosity of the coating liquid is preferably 1.5 mPa · s or more, more preferably 2 mPa · s or more, particularly preferably 2.5 mPa · s or more. However, the viscosity of the coating solution is usually 10 mPa · s or less.
Here, the coating film thickness after drying means that the coating film thickness is less than 1.5 μm (hereinafter, sometimes referred to as “thin film”).

  In addition, when a thick color filter such as a photo spacer is manufactured, for example, the viscosity of the coating liquid is preferably 3 mPa · s or more, more preferably 3.2 mPa · s. That's it. Here, the coating film thickness after drying means that the coating film thickness is 1.5 μm or more (hereinafter sometimes referred to as “thick film”).

  By making the steady viscosity of the coating solution within the above-mentioned range, there is the following advantage in the die coating method, that is, when manufacturing a color filter having a thin coating film thickness after drying, the coating limit speed is increased. Even in this case, it is possible to form a color filter in which the coating solution does not run out and the coating stripes due to the unevenness of the tip of the die lip are reduced.

  The application limit speed means an upper limit application speed at which uniform application can be performed without forming a stripe-shaped application film due to liquid breakage in the steady application part. The coating speed is usually 0.1 m / sec, preferably 0.2 m / sec, more preferably 0.3 m / sec.

  On the other hand, the solid content concentration (C) of the coating solution of the curable composition to which the present embodiment is applied is preferably 2 wt% to 50 wt%, and more preferably 10 wt% to 30 wt%. Particularly preferred is the range of 15% to 25% by weight. When the solid content concentration (C) of the curable composition is excessively high, application stripes tend to be generated. Moreover, when solid content concentration (C) is too low, there exists a tendency for a viscosity (micro) to fall.

The curable composition to which the present embodiment is applied has a leveling resistance value (RL) of 0.01 to 0 in the range of the viscosity (μ) of the coating liquid resulting from the die coating method and the solid content concentration (C). .05 and the sag resistance value (RS) is 0.1 or more, the solid content concentration (C) is decreased to reduce the leveling resistance value (RL). It is preferable to increase the sag resistance value (RS) by increasing the viscosity (μ).
That is, since the leveling resistance value (RL) is proportional to the cube of the solid content concentration (C), the leveling resistance value (RL) is greatly reduced by decreasing the solid content concentration (C).
On the other hand, since the sag resistance value (RS) is proportional to the square of the solid content concentration (C), even if the solid content concentration (C) decreases, the sag resistance value (RL) does not decrease as much as the leveling resistance value (RL). ) Is increased, it is possible to suppress a decrease in the sagging resistance value (RS).

  Examples of specific numerical values are listed in Table 1 below.

Specific methods for increasing the viscosity (μ) while lowering the solid content concentration (C) include the following methods (a) to (c).
(A) A high viscosity binder resin is used.
Here, as the binder resin having a high viscosity, a resin having a weight average molecular weight (Mw) of preferably 5000 or more, more preferably 10,000 or more, and particularly preferably 15000 or more.
In this case, the acid value is preferably 20 or more, more preferably 40 or more, and particularly preferably 60 or more.
Such a high-viscosity binder resin can be selected from (A) an ethylenically unsaturated compound described later or (H) a resin having no ethylenically unsaturated group, and more preferably [A-1]. A carboxyl group-containing vinyl resin having an ethylenically unsaturated group in the side chain, or (H) a resin not having an ethylenically unsaturated group can be selected.

(B) A high viscosity polymerizable monomer is used.
Here, as the high-viscosity polymerizable monomer, a monomer having a viscosity of preferably 10 mPa · s or more, more preferably 100 mPa · s or more, and particularly preferably 1000 mPa · s or more is exemplified.
As such a high-viscosity polymerizable monomer, among the polymerizable monomers (C) described later, from the viewpoint of polymerizability, crosslinkability, etc., a compound having preferably two or more ethylenically unsaturated groups in the molecule, Preferably, it is selected from compounds having 3 or more. Also preferred is a method of controlling only the viscosity of the curable composition by adding a small amount of a polymerizable monomer having a viscosity exceeding 10,000 mPa · s, without significantly changing various properties of the curable composition.

(C) A highly viscous solvent is used.
Here, the high-viscosity solvent is preferably a solvent having a viscosity of preferably 1 mPa · s or more, more preferably 1.2 mPa · s or more, and particularly preferably 1.5 mPa · s or more.
However, the solvent is not limited only by the viscosity, but is selected from the balance of various factors such as solubility, vapor pressure, drying speed, odor, etc. of each material used.

[3] Constituent components and composition of curable composition The curable composition to which the present embodiment is applied is not particularly limited, but includes the following components (A) to (D): If necessary, it can be obtained by blending other components (components (E) to (H)). Hereinafter, each component will be described.
(A) ethylenically unsaturated compound (B) photopolymerization initiator and / or thermal polymerization initiator (C) polymerizable monomer (D) solvent other components (E) epoxy compound (F) amino compound (G) surface activity Agent (H) Resin that does not have an ethylenically unsaturated group

  In the present embodiment, “(meth) acryl” means “acryl and / or methacryl”, and “total solids” means components of the curable composition excluding the solvent. It shall mean the total amount.

(A) Ethylenically unsaturated compound The ethylenically unsaturated compound used in the curable composition to which the present embodiment is applied is used when the curable composition is irradiated with actinic rays or heated. , At least one radically polymerizable ethylenically unsaturated bond that undergoes addition polymerization by the action of a polymerization initiation system containing a photopolymerization initiator and / or a thermal polymerization initiator, which will be described later, and may be crosslinked or cured in some cases. It is a compound that has.
For such an ethylenically unsaturated compound, the above-described leveling resistance value (RL) and sag resistance value (RS) in the curable composition of the present embodiment satisfy the requirements of the present invention, and the curable composition. From the following, it is appropriately selected and used so that the cured product obtained from the above has the necessary characteristics.
Moreover, when using the hardened | cured material obtained from the curable composition in this Embodiment as a photo spacer, in order to achieve the mechanical characteristic, this ethylenically unsaturated compound has a double bond equivalent normally 400. Hereinafter, it is preferable to contain an ethylenically unsaturated compound that is preferably 350 or less, more preferably 300 or less. The smaller the double bond equivalent, that is, the more double bonds per unit weight, the greater the elastic recovery rate and recovery rate of the resulting cured product. The lower limit of the double bond equivalent of the ethylenically unsaturated compound is usually 100 or more.

Here, the double bond equivalent is the weight per mole of the double bond of the compound, and is calculated by the following formula (6). The more double bonds per unit weight, the smaller the value of the double bond equivalent. Become.
Double bond equivalent = weight of compound (g) / number of moles containing double bond of compound (6)

  In the present embodiment, the smaller the double bond equivalent of the entire curable composition, the elastic recovery rate and recovery of the obtained cured product for the same reason as the double bond equivalent of the ethylenically unsaturated compound described above. This is preferable because the rate increases. Specifically, the double bond equivalent as a whole solid content in a state where the curable composition is dissolved or dispersed in a solvent (hereinafter sometimes referred to as “cured composition solution”) is 300 or less. And more preferably 250 or less. However, the lower limit of the double bond equivalent as the whole solid content of the curable composition solution is usually 100 or more.

Here, the double bond equivalent of the entire solid content in the curable composition solution is calculated by the above formula (6) from the charged amount of the compound having an ethylenic double bond when preparing the curable composition. You can also.
Moreover, after measuring the double bond equivalent of a curable composition solution by a well-known method, the solid content density | concentration of a curable composition can also be measured by a well-known method, and it can also calculate by following formula (7).
Double bond equivalent = double bond equivalent of the curable composition solution × solid content concentration (7)

  The ethylenically unsaturated compound preferably has an acid group particularly when the curable composition of the present invention is used as an alkali developing type. Here, “having an acid group” means having a group giving a value greater than 0 as an acid value determined by titration with KOH (potassium hydroxide). Specifically, it means having a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a phosphoric acid group, etc. Among them, it is particularly preferred to have a carboxyl group.

The content of the (A) ethylenically unsaturated compound in the curable composition to which the present embodiment is applied is usually 25% by weight or more, preferably 30% by weight with respect to the total solid content in the curable composition. % Or more, more preferably 40% by weight or more. (A) When there is too much content of an ethylenically unsaturated compound, since the viscosity of a curable composition solution will become high too much or sclerosis | hardenability will be impaired, it is unpreferable. On the other hand, if the content is excessively small, the cured product may not obtain sufficient mechanical properties.
As such an ethylenically unsaturated compound, one or more of resins having at least one ethylenically unsaturated group can be used among resins used in known resin compositions for color filters.
Examples of such a resin include a copolymer of an unsaturated carboxylic acid such as (meth) acrylic acid and a vinyl compound, an acid-modified epoxy (meth) acrylate, polyamide, polyester, polyether, polyurethane, polyvinyl butyral, Polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose and the like can be mentioned.
Among these, from the viewpoint of alkali developability and the like, [A-1] a carboxyl group-containing vinyl resin having an ethylenically unsaturated group in the side chain and [A-2] acid-modified epoxy (meth) acrylate are preferable. is there.

[A-1] Carboxyl group-containing vinyl resin having an ethylenically unsaturated group in the side chain [A-1] Carboxyl group-containing vinyl resin having an ethylenically unsaturated group in the side chain used in the present embodiment [A-1-1] reaction product of a carboxyl group-containing vinyl resin and an epoxy group-containing unsaturated compound, “A-1-2” a compound having two or more unsaturated groups and an unsaturated carboxylic acid Alternatively, a copolymer with an unsaturated carboxylic acid ester, [A-1-3] “E-R-N-T resin” may be mentioned.

[A-1-1] Reaction product of carboxyl group-containing vinyl resin and epoxy group-containing unsaturated compound As the carboxyl group-containing vinyl resin used in the present embodiment, specifically, unsaturated carboxylic acid And a copolymer of vinyl compound.
Here, examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, and the like.

  Examples of the vinyl compound include styrene, α-methylstyrene, hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl. (Meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl ( (Meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- (meth) acryloylmorpholine, (meta Acrylonitrile, (meth) acrylamide, N- methylol (meth) acrylamide, N, N- dimethyl (meth) acrylamide, N, N- dimethylaminoethyl (meth) acrylamide, vinyl acetate, and the like.

Among the carboxyl group-containing vinyl resins, a (meth) acrylate- (meth) acrylic acid copolymer and a styrene- (meth) acrylate- (meth) acrylic acid copolymer are preferable.
In the (meth) acrylate- (meth) acrylic acid copolymer, a copolymer composed of 5 to 80 mol% of (meth) acrylate and 20 to 95 mol% of (meth) acrylic acid is more preferable. A copolymer consisting of 10) to 90 mol% of acrylate and 10 to 90 mol% of (meth) acrylic acid is particularly preferred.

Moreover, in a styrene- (meth) acrylate- (meth) acrylic acid copolymer, styrene 3-60 mol%, (meth) acrylate 10-70 mol%, (meth) acrylic acid 10-60 mol%, A copolymer consisting of 5 to 50 mol% of styrene, 20 to 60 mol% of (meth) acrylate, and 15 to 55 mol% of (meth) acrylic acid is particularly preferable.
In addition, the acid value of these carboxyl group-containing vinyl resins is adjusted according to the amount of the epoxy group-containing unsaturated compound to be reacted with these and the acid value required in the resulting reaction product, Usually, it is 50 mg-KOH / g-500 mg-KOH / g. The weight average molecular weight (Mw) in terms of standard polystyrene of the carboxyl group-containing vinyl resin is preferably 1,000 to 300,000.
The weight average molecular weight (Mw) is measured as a molecular weight converted to standard polystyrene by GPC (gel permeation chromatography).
Examples of the epoxy group-containing unsaturated compound include an aliphatic epoxy group-containing unsaturated compound and an alicyclic epoxy group-containing unsaturated compound. Examples of the aliphatic epoxy group-containing unsaturated compound include allyl glycidyl ether. Glycidyl (meth) acrylate, α-ethylglycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, itaconic acid monoalkyl monoglycidyl ester, fumarate monoalkyl monoglycidyl ester, maleic acid monoalkyl A monoglycidyl ester etc. are mentioned.

  Examples of the alicyclic epoxy group-containing unsaturated compound include 3,4-epoxycyclohexylmethyl (meth) acrylate, 2,3-epoxycyclopentylmethyl (meth) acrylate, 7,8-epoxy [tricyclo [5.2. .1.0] dec-2-yl] oxymethyl (meth) acrylate and the like.

The carboxyl group-containing vinyl resin and the epoxy group-containing unsaturated compound are an epoxy group-containing unsaturated compound of 5 mol% to 90 mol%, preferably about 30 to 70 mol% of the carboxyl group of the carboxyl group-containing vinyl resin. It is made to react by the quantity ratio of. The reaction can be carried out by a known method.
[A-1-1] The acid value of the reaction product of the carboxyl group-containing vinyl resin and the epoxy group-containing unsaturated compound is preferably 30 mg-KOH / g to 250 mg-KOH / g. The weight average molecular weight (Mw) in terms of standard polystyrene is preferably 1,000 to 300,000.

"A-1-2" Copolymer of a compound having two or more unsaturated groups and an unsaturated carboxylic acid or unsaturated carboxylic acid ester [A-1] A carboxyl group having an ethylenically unsaturated group in the side chain Examples of the vinyl-containing resin include a copolymer of a compound having two or more unsaturated groups and an unsaturated carboxylic acid or unsaturated carboxylic acid ester.
Examples of the compound having two or more unsaturated groups include allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, and methallyl (meth) ) Acrylate, N, N-diallyl (meth) acrylamide, vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl crotonate, vinyl (Meth) acrylamide etc. are mentioned.

Examples of the unsaturated carboxylic acid or unsaturated carboxylic acid ester include (meth) acrylic acid or (meth) acrylic acid ester.
The proportion of the compound having two or more kinds of unsaturated groups in the entire copolymer is about 10 mol% to 90 mol%, preferably about 30 mol% to 80 mol%.
The acid value of the copolymer of “A-1-2” a compound having two or more unsaturated groups and an unsaturated carboxylic acid or unsaturated carboxylic acid ester is preferably 30 mg-KOH / g to 250 mg-KOH. / G. The weight average molecular weight (Mw) in terms of standard polystyrene is preferably 1,000 to 300,000.

[A-1-3] “E-R-N-T resin”
The E-R-N-T resin is “(E) component: epoxy group-containing (meth) acrylate” 5 mol% to 90 mol%, “(R) component: other copolymerizable with (E) component” Of 10 mol% to 95 mol% of the radically polymerizable compound of the above, and 10 mol% to 100 mol% of the epoxy group contained in the obtained copolymer was changed to “(N) component: unsaturated monobasic acid”. ”And a resin obtained by adding“ (T) component: polybasic acid anhydride ”to 10 mol% to 100 mol% of the hydroxyl group produced when the (N) component is added.
Component (E): As epoxy group-containing (meth) acrylate, for example, glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate glycidyl ether etc. are mentioned. Of these, glycidyl (meth) acrylate is preferred. These (E) components may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

As described above, the copolymerization ratio of the component (E) in the copolymer of the component (E) and the component (R) is usually 5 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more. It is. Moreover, it is 90 mol% or less normally, Preferably it is 80 mol% or less, More preferably, it is 70 mol% or less. Here, the component (R) is another radical polymerizable compound that can be copolymerized with the component (E).
When the copolymerization ratio of the component (E) is excessively large, the component (R) tends to decrease, and the heat resistance and strength tend to decrease. When the copolymerization ratio of the component (E) is excessively small, the addition amount of the polymerizable component and the alkali-soluble component tends to be insufficient.

  On the other hand, the copolymerization ratio of the (R) component in the copolymer of the (E) component and the (R) component is 10 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, as described above. It is. Moreover, it is 95 mol% normally, Preferably it is 80 mol% or less, More preferably, it is 70 mol% or less. When the copolymerization ratio of the component (R) is excessively large, the component (E) tends to decrease and the addition amount of the polymerizable component and the alkali-soluble component tends to be insufficient. Moreover, when the copolymerization ratio of the component (R) is excessively small, heat resistance and strength tend to decrease.

  Here, as the component (R), for example, one or more of mono (meth) acrylates having a partial structure represented by the following formula (13) are preferably used.

(In formula (13), R ^{1d to} R ^6d each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, etc., and R ^7d and R ^8d are Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, etc. R ^7d and R ^8d may be linked to form a ring. The ring formed by linking R ^7d and R ^8d is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

  In the above formula (13), mono (meth) acrylate having a structure represented by the following formula (14), formula (15), or formula (16) is preferable. By introducing these partial structures, it is possible to increase the heat resistance and strength of mono (meth) acrylate. In addition, 1 type may be used for these mono (meth) acrylates, and 2 or more types may be used together by arbitrary combinations and a ratio.

  As the mono (meth) acrylate having a partial structure represented by the formula (13), various known ones can be used, and those represented by the following formula (17) are particularly preferable.

(In formula (17), R ^9d represents a hydrogen atom or a methyl group, and R ^10d represents the formula (13)).

In the present embodiment, the content of the mono (meth) acrylate having a partial structure represented by the above formula (13) in the copolymer of the (E) component and the (R) component is usually 5 mol%. As mentioned above, Preferably it is 10 mol% or more, More preferably, it is 15 mol% or more. Moreover, it is 90 mol% or less normally, Preferably it is 70 mol% or less, More preferably, it is 50 mol% or less.
When the content of the mono (meth) acrylate represented by the formula (13) in the copolymer of the component (E) and the component (R) is excessively small, the heat resistance tends to be insufficient. Moreover, when there is too much content of mono (meth) acrylate shown by Formula (13), there exists a tendency for the compatibility of the components of a curable composition to worsen, and it may cause whitening at the time of film forming, etc. There is.

Moreover, in this Embodiment, as (R) component, radically polymerizable compounds other than the mono (meth) acrylate which has the partial structure represented by Formula (13) mentioned above are mentioned as shown below.
Specifically, for example, styrene; α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene;

Methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid- sec-butyl, tert-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, (meth) acrylic Isobornyl acid, adamantyl (meth) acrylate, (meth) acrylic acid Allyl sulfonate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, (meth ) Salicyl acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, (meta ) Cresyl acrylate, (meth) acrylic acid-1,1,1-trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro (meth) acrylate -Iso-propyl, triphenylmethyl (meth) acrylate, (meth (Meth) acrylic acid esters such as cumyl acrylate, (meth) acrylic acid 3- (N, N-dimethylamino) propyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl ;

(Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, (Meth) acrylic amides such as N-di-iso-propylamide, (meth) acrylic acid anthracenyl amide; (meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, fluoride Vinyl compounds such as vinyl, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate;

Unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate; mono-such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide Maleimide; N- (meth) acryloylphthalimide and the like.

Among these, in order to impart more excellent heat resistance and strength, it is effective to use at least one selected from styrene, benzyl (meth) acrylate and monomaleimide as the (R) component.
In this case, the copolymerization ratio of at least one selected from styrene, benzyl (meth) acrylate and monomaleimide is usually 1 mol% or more, preferably 3 mol% or more, and usually 70 mol% or less, preferably 50 It is less than mol%.

Next, a well-known thing can be used as (N) component (unsaturated monobasic acid) added to the epoxy group contained in the copolymer of (E) component and (R) component. Examples of such unsaturated monobasic acids include unsaturated groups having ethylenically unsaturated double bonds such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, and citraconic acid. Carboxylic acid is mentioned.
These (N) components may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

Further, the (N) component is added to the epoxy group contained in the copolymer obtained by the copolymerization reaction of the (E) component and the (R) component. The amount of the (N) component added to the copolymer is 10 mol%, preferably 30 mol% or more, more preferably 50 mol% or more of the epoxy group contained in the copolymer. When the addition ratio of the component (N) is excessively small, there is a tendency that an adverse effect due to the remaining epoxy group occurs, for example, stability with time decreases.
In addition, a well-known method is employable as a method of adding (N) component to the copolymer of (E) component and (R) component.

  Next, the (T) component (polybasic acid anhydride) is added to the hydroxyl group produced when the (N) component is added to the copolymer of the (E) component and the (R) component. The polybasic acid anhydride is not particularly limited and known ones can be used. Specific examples thereof include succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl Saturated or unsaturated dicarboxylic acid anhydrides such as endomethylenetetrahydrophthalic anhydride, phthalic anhydride, chlorendic anhydride; trimellitic anhydride; pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyl Examples thereof include tetracarboxylic acid anhydrides, biphenyl ether tetracarboxylic acid anhydrides, acid anhydrides of tetracarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid anhydride, and the like. These (T) components may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

The amount of the (T) component added is usually 10 mol% or more, preferably 20% of the hydroxyl group produced when the (N) component is added to the copolymer of the (E) component and the (R) component. The mol% or more, more preferably 30 mol% or more. Moreover, it is 100 mol% or less normally, Preferably, it is 90 mol% or less, More preferably, it is 80 mol% or less.
If the amount of component (T) added is excessively large, the remaining film rate during development tends to decrease. If the amount of component (T) added is too small, the solubility tends to be insufficient.
In addition, as a method of adding the (T) component to the hydroxyl group generated when the (N) component is added to the copolymer of the (E) component and the (R) component, a known method is arbitrarily adopted. can do.

  The E-R-N-T resin can be further improved by adding a glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group to a part of the carboxyl group generated after the addition of the (T) component. Sensitivity can be improved.

Examples of the E-R-N-T resin described above include resins described in JP-A-8-297366 and JP-A-2001-89533.
The average molecular weight of the E-R-N-T resin is not particularly limited. Usually, the weight average molecular weight (Mw) converted to standard polystyrene measured by GPC is 3,000 or more, preferably 5,000. In addition, it is usually 100,000 or less, preferably 50,000 or less. If the weight average molecular weight (Mw) of the E-R-N-T resin is too small, the heat resistance and the film strength tend to be inferior. When the weight average molecular weight (Mw) of the E-R-N-T resin is excessively large, the solubility in the developer tends to be lowered. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is preferably 2.0 to 5.0.

[A-2] Acid-modified epoxy (meth) acrylate Examples of the acid-modified epoxy (meth) acrylate in the present embodiment include compounds represented by the following general formula (AI). As the production method thereof, for example, one or more compounds selected from the group consisting of a compound having an epoxy group-containing compound and an ethylenically unsaturated group-containing carboxylic acid and further having a polyvalent carboxylic acid, its anhydride and an isocyanate group However, it is not limited to this.

[In formula (AI), R ¹¹ represents an alkylene group which may have a substituent or an arylene group which may have a substituent. R ¹² represents an ethylenically unsaturated group-containing carbonyloxy group which may have a substituent. R ¹³ and R ¹⁴ each independently represents an arbitrary substituent. n is an integer of 0-10. m is an integer of 1 or more. X represents an arbitrary organic group which may have a substituent. ]

In the general formula (AI), the alkylene group represented by R ¹¹ is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a methylene group, an ethylene group, a propylene group, or a butylene group. Moreover, as an arylene group, a C6-C10 thing is preferable and a phenylene group is still more preferable. Among these, an alkylene group is preferable in the present embodiment.

Examples of the substituent that the alkylene group or arylene group of R ¹¹ may have include, for example, a halogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, and a carbon number. Examples thereof include an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group, and a nitro group.

  N is an integer of 0 to 10, preferably 0 to 5, and more preferably 0 to 3. When n exceeds the above range, when the resulting curable composition is a cured product, there is a tendency that film loss or the like occurs as an image portion during development or heat resistance decreases.

The lower limit of the carbon number of the ethylenically unsaturated group-containing carbonyloxy group which may have a substituent for R ¹² in formula (AI) is usually 3, preferably 5, and more preferably 10. The upper limit is not particularly limited, but is preferably 50, more preferably 40, and particularly preferably 35. If the above carbon number is excessively large, or if the carbon number is excessively small, in any case, the mechanical properties of the cured product formed by the curable composition of the present embodiment may not be obtained. is there.
As the ethylenically unsaturated group-containing carbonyloxy group which may have a substituent represented by R ¹² , a group represented by the following general formula (A-II) is more preferable.

[In formula (A-II), R ¹⁵ , R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group, and Q represents an absent or arbitrary divalent group. ]

  In the formula (A-II), Q is preferably absent, an alkylene group which may have a substituent and / or an arylene group which may have a substituent, and a carbonyloxy group. And a divalent group containing More preferably, Q is absent or has 1 to 10 carbon atoms which may have a C1-C10 alkylene group or / and optionally has 1 to 10 carbon atoms. A divalent group containing an arylene group and a carbonyloxy group is shown.

In formula (AI), R ¹³ preferably represents a hydrogen atom, a substituent represented by the following general formula (A-IIIa), or a substituent represented by the following general formula (A-IIIb). .

[In the formulas (A-IIIa) and (A-IIIb), R ²¹ and R ²² have an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. A cycloalkyl group that may be substituted, a cycloalkenyl group that may have a substituent, or an aryl group that may have a substituent. ]

Here, as an alkyl group of R <^21> , R < ²² >, a C1-C20 thing is preferable. Moreover, as an alkenyl group, a C2-C20 thing is preferable. Moreover, as a cycloalkyl group, what is C3-C20 is preferable. Further, as the cycloalkenyl group, those having 3 to 20 carbon atoms are preferable. The aryl group is preferably one having 6 to 20 carbon atoms.

Examples of the substituent that R ²¹ and R ²² may have include, for example, a halogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and a phenyl group. , Carboxyl group, carbonyl group, sulfanyl group, phosphino group, amino group, nitro group and the like. Among these, R ²¹ preferably has a carboxyl group as a substituent.

Examples of the substituent represented by R ¹⁴ in the compound represented by the aforementioned general formula (A-I), is not particularly limited, for example, there are substituents represented by the following formula (A-IV) .

[In the formula (A-IV), R ¹¹ , R ¹² , R ¹³ and n have the same meanings as in the general formula (AI). ]

  X in the compound represented by the general formula (AI) described above represents an arbitrary organic group which may have a substituent. This X has a basic function of bonding a double bond-containing group, and serves as a site for bonding an appropriate molecular weight and an appropriate number of substituents so as not to increase the double bond equivalent of the entire compound. There is a function to provide a functional group.

  The molecular weight of X in the compound represented by formula (AI) is usually 14 or more, preferably 28 or more, and usually 3000 or less, preferably 2000 or less.

In the present embodiment, specific examples of the organic group that can be used as X include a linear or cyclic organic group.
Examples of the linear organic group include organic groups derived from alkanes and alkenes; (meth) acrylic acid, (meth) acrylic ester, (meth) acrylonitrile, (meth) acrylamide, maleic acid, styrene, vinyl acetate , Organic groups derived from homo- or copolymers such as vinylidene chloride and maleimide; derived from acid-modified epoxy acrylate, polyolefin, polyamide, polyester, polyether, polyurethane, polyvinyl butyral, polyvinyl alcohol, polyvinyl pyrrolidone, acetyl cellulose, etc. An organic group is mentioned.

In addition, as the cyclic organic group, an alicyclic ring, an aromatic ring, an alicyclic heterocyclic ring, a heterocyclic ring or the like, or an organic group derived from a condensed ring thereof, and these rings via a linking group are used. Organic groups derived from those bonded to each other.
Among these, examples of the alicyclic ring include a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, and a tricyclodecane ring.
Examples of the aromatic ring include a benzene ring, biphenyl ring, naphthalene ring, anthracene ring, phenanthrene ring, azulene ring, fluorene ring, acenaphthylene ring, biphenylene ring, and indene ring.
As the alicyclic heterocycle or heterocycle, furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine Ring, pyridazine ring, pyrimidine ring, pyrazine ring and the like.

  Examples of the linking group via the bond of the cyclic organic group include a direct bond or a divalent or higher valent linking group. As the divalent or higher linking group, known ones can be used. For example, alkylene, polyoxyalkylene, amine, O atom, S atom, ketone group, thioketone group, -C (= O) O-, amide , Se, Te, P, As, Sb, Bi, Si, B, and other metals, heterocycles, aromatic rings, heteroaromatic rings, and any combination thereof.

  Examples of the organic group represented by X include an alkylene group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms; an arylene group having 6 to 10 carbon atoms; and 2 to 50 carbon atoms. , Preferably a polyether having 2 to 30 carbon atoms; bisphenol such as bisphenol A and bisphenol F shown below: trisphenol; residues obtained by removing a hydroxyl group of a polyol compound such as novolak ((X-1 ) To (X-21)).

  In the exemplary formula of the organic group represented by X, z represents an integer of 0 or more. In the exemplified (X-13), (X-15), (X-18), (X-19), and (X-20), * represents a bond. In these exemplary structures, when there are three or more bonds *, the number of bonds as the linking group X covers at least two of these bonds. In this case, the substituent linked to the remaining one or more bonds is not particularly limited and is preferably a group represented by the general formula (A-IV).

  In addition, when the compound represented with the said general formula (AI) has a benzene ring, as a substituent which the benzene ring may have, for example, a C1-C15 alkyl group, carbon C1-C15 alkoxy group, C2-C15 acyl group, C6-C14 aryl group, carboxyl group, hydroxyl group, C1-C16 alkoxycarbonyl group, carboxyl Group, halogen atom and the like. Among these, a C1-C5 alkyl group, a phenyl group, and a halogen atom are still more preferable.

  Although it does not specifically limit as a manufacturing method of the compound represented by the said general formula (AI), if it is a manufacturing method with which the compound which has a structure represented by general formula (AI) is obtained, the following general The production method using the epoxy group-containing compound represented by the formula (A-V) will be described as an example. That is, a compound obtained by using a compound represented by the following general formula (A-V) as a raw material, forming an ethylenically unsaturated group-containing carbonyloxy group thereon, and then forming this ethylenically unsaturated group-containing carbonyloxy group And a compound represented by the general formula (AI) by reacting with one or more compounds selected from the group consisting of a compound having a polyvalent carboxylic acid and its anhydride and an isocyanate group. it can.

[In the formula (A-V), R ¹¹ , X and n have the same meanings as in the general formula (AI). R ¹⁸ has the same meaning as R ¹¹ in formula (AI). ]

  Examples of the epoxy group-containing compound represented by the general formula (A-V) include (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, ( Poly) pentamethylene glycol polyglycidyl ether, (poly) neopentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) Aliphatic polyepoxy compounds such as sorbitol polyglycidyl ether;

Phenol novolac polyepoxy compound, brominated phenol novolak polyepoxy compound, (o-, m-, p-) cresol novolac polyepoxy compound, bisphenol A polyepoxy compound, bisphenol F polyepoxy compound, bis (hydroxyphenyl) fluorene type poly Aromatic polyepoxy compounds such as epoxy compounds; polyepoxy compounds such as heterocyclic polyepoxy compounds such as sorbitan polyglycidyl ether, triglycidyl isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, and the like.
The epoxy group-containing compound represented by the general formula (A-V) may be used alone or in combination of two or more.

  In addition, the lower limit of the carbon number of the ethylenically unsaturated group-containing carbonyloxy group formed in the epoxy group-containing compound represented by the general formula (A-V) is usually 3, preferably 5, and more preferably 10. . The upper limit is not particularly limited, but is preferably 50, more preferably 40, and particularly preferably 35. When the number of carbon atoms is less than the above range, when the curable composition is used as a cured product, flexibility tends to be insufficient and adhesion to the substrate tends to be poor. On the other hand, when the carbon number is excessively large, the heat resistance tends to decrease.

  These ethylenically unsaturated group-containing carbonyloxy groups are preferably groups represented by the general formula (A-II).

  Here, as a formation method of the ethylenically unsaturated group containing carbonyloxy group represented by the said general formula (A-II), as a result of the reaction which uses the compound represented by the said general formula (AV) as a raw material The method is not particularly limited as long as an ethylenically unsaturated group-containing carbonyloxy group is formed. For example, the compound represented by the general formula (A-V) and the ethylenically unsaturated group-containing carboxyl Examples thereof include a method of reacting with an acid (A-2-a).

  Examples of the ethylenically unsaturated group-containing carboxylic acid (A-2-a) include: (meth) acrylic acid; reaction product of (meth) acrylic acid and lactone or polylactone; saturated or unsaturated dicarboxylic acid anhydride And a half ester obtained by reacting a (meth) acrylate derivative having one or more hydroxyl groups in one molecule; a saturated or unsaturated dicarboxylic acid anhydride and an unsaturated group-containing glycidyl compound The half ester obtained is mentioned.

  Examples of the saturated or unsaturated dicarboxylic acid anhydride include succinic anhydride, adipic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride. Examples include acid, methylendomethylenetetrahydrophthalic anhydride, and phthalic anhydride.

  Examples of (meth) acrylate derivatives having one or more hydroxyl groups in one molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and polyethylene glycol mono (meth) acrylate. Glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like.

  Examples of the unsaturated group-containing glycidyl compound include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 8,9-epoxy [bicyclo [4.3.0] non-3-yl] ( And (meth) acrylate, 8,9-epoxy [bicyclo [4.3.0] non-3-yl] oxymethyl (meth) acrylate, and the like.

In the present embodiment, as “ethylenically unsaturated group-containing carboxylic acid (A-2-a)”, among these, (meth) acrylic acid or saturated or unsaturated dicarboxylic acid anhydride is included in one molecule. A half ester obtained by reacting with a (meth) acrylate derivative having one or more hydroxyl groups is preferred.
In this case, the saturated or unsaturated dicarboxylic acid anhydride is preferably succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or phthalic anhydride. In addition, (meth) acrylate derivatives having one or more hydroxyl groups in one molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentaerythritol tri (meth) acrylate. Dipentaerythritol penta (meth) acrylate is preferred.

These ethylenically unsaturated group-containing carboxylic acids (A-2-a) may be used alone or in combination of two or more.
In addition, the ethylenically unsaturated group-containing carboxylic acid (A-2-a) is usually 0.8 chemical equivalent to 1.5 chemical equivalents relative to 1 chemical equivalent of the epoxy group of the epoxy group-containing compound as a raw material, Preferably, an amount of 0.9 chemical equivalent to 1.1 chemical equivalent is added.

In addition, as an epoxy group-containing compound represented by the general formula (A-V) as a raw material, an ethylenically unsaturated group-containing carbonyloxy group is formed thereon, and then further reacted as a polyvalent carboxylic acid or an anhydride thereof. Include the following compounds.
For example, saturated or unsaturated dicarboxylic acids such as succinic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, phthalic acid, chlorendic acid, etc. Acids and their acid anhydrides; trimellitic acid and its anhydrides; pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, etc. Examples thereof include tetracarboxylic acids and acid anhydrides thereof.

Among these, as a curable composition, dicarboxylic acids such as oxalic acid, tetrahydrophthalic acid, and phthalic acid, and acid anhydrides thereof, trimellitic acid and acids thereof from the viewpoint of dissolution and removal of non-image areas during alkali development. Preference is given to tetracarboxylic acids such as anhydrides, pyromellitic acid, biphenyltetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, and acid dianhydrides thereof.
Further, among these, acid anhydrides of polyvalent carboxylic acids having an acid dissociation constant (first dissociation constant) of 3.5 or more are preferable. The acid dissociation constant is preferably 3.8 or more, and particularly preferably 4.0 or more. Examples of acid anhydrides of polycarboxylic acids having an acid dissociation constant (first dissociation constant) of 3.5 or more include oxalic acid anhydride, tetrahydrophthalic acid anhydride, 1, 2, An acid dianhydride of 3,4-butanetetracarboxylic acid may be mentioned. Of these, succinic acid anhydride and tetrahydrophthalic acid anhydride are particularly preferred.

Here, as for the acid dissociation constant, Reference can be made of Determination of Organic Structures by Physical Methods, Academic Press, New York, 1955 (Brown, HC, etc.).
Further, from the viewpoint of the storage stability of the curable composition, it is preferable to use dicarboxylic acids such as succinic acid, tetrahydrophthalic acid, and phthalic acid, their acid anhydrides, trimellitic acid, and their acid anhydrides.
The selection of the carboxylic acid and its anhydride is appropriately adjusted according to the required properties of the curable composition.
In the present embodiment, these polyvalent carboxylic acids and acid anhydrides thereof may be used alone or in combination of two or more.
In addition, the polyvalent carboxylic acid or its anhydride is usually 0.05 chemical equivalents to 1. .1 chemical equivalent to 1 chemical equivalent of the hydroxyl group produced by the addition reaction between the epoxy group-containing compound and the ethylenically unsaturated group-containing carboxylic acid. 0 chemical equivalents, preferably 0.1 to 0.9 chemical equivalents are added.

Moreover, the following compounds are mentioned as a compound which has the isocyanate group made to react after forming an ethylenically unsaturated group containing carbonyloxy group in the epoxy group containing compound represented by the said general formula (AV). It is done.
For example, organic monoisocyanates such as butane isocyanate, 3-chlorobenzene isocyanate, cyclohexane isocyanate, 3-isopropenoyl-α, α-dimethylbenzyl isocyanate; paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, Aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate;

Aliphatic diisocyanates such as hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate; alicyclic rings such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), ω, ω′-diisocyanate dimethylcyclohexane Aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate; lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8 Diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate Enirumetan), tris (isocyanate phenyl) thiophosphate, etc. triisocyanate; and, trimer of isocyanate compound as mentioned above, water adducts, and the like of these polyol adducts.

Among these, dimers and trimers of organic diisocyanate are preferable, and a trimethylolpropane adduct of tolylene diisocyanate, a trimer of tolylene diisocyanate, and a trimer of isophorone diisocyanate are most preferable. The said compound may be used individually by 1 type, or may use 2 or more types together.
In addition, these compounds having an isocyanate group are usually 0.05 chemical equivalents to 1.0 chemical equivalent to 1 chemical equivalent of a hydroxyl group produced by an addition reaction between an epoxy group-containing compound and an ethylenically unsaturated group-containing carboxylic acid. It is added in an amount equivalent to an equivalent amount, preferably 0.1 chemical equivalent to 0.5 chemical equivalent.

  In addition, the acid value of the compound represented by the general formula (AI) in the present embodiment is preferably 30 mg-KOH / g to 150 mg-KOH / g, and more preferably 40 mg-KOH / g. g to 100 mg-KOH / g. Moreover, the weight average molecular weight (Mw) of the standard polystyrene conversion by GPC of the compound represented by general formula (AI) becomes like this. Preferably it is 1,000-100,000, More preferably, it is 1,500- 10,000, particularly preferably 2,000 to 10,000.

  An example of a specific method for synthesizing the compound represented by formula (AI) used in the present embodiment is described in, for example, JP-A-4-355450.

  In the present embodiment, the compound represented by the general formula (AI) synthesized in this way includes the influence of the mixture contained in the raw materials and thermal polymerization during the reaction of double bonds. , Compounds other than the compound represented by formula (AI) may be included.

[A-2] Acid-modified epoxy (meth) acrylate In the present embodiment, as [A-2] acid-modified epoxy (meth) acrylate, in addition to the compound represented by the above general formula (AI) For example, the compound represented by the following general formula (A-VI) is mentioned.

[In formula (A-VI), R ¹² , R ¹³ and R ¹⁴ have the same meanings as in formula (AI). ]

  Although it will not specifically limit as a manufacturing method of the compound represented by general formula (A-VI) if it is a method by which the compound which has a structure represented by general formula (A-VI) is obtained, For example, it mentioned above As in the case of the method for producing the compound represented by the general formula (AI), diglycidyl ether is used as a raw material to form an ethylenically unsaturated group-containing carbonyloxy group, and a polyvalent carboxylic acid and its anhydride are further formed. And a production method in which one or more compounds selected from compounds having an isocyanate group are reacted.

  In the curable composition to which the present embodiment is applied, (A) the ethylenically unsaturated compound can be used alone or as a mixture of two or more.

(B) Photopolymerization initiator and / or thermal polymerization initiator The photopolymerization initiator and / or thermal polymerization initiator used in the present embodiment is a compound that polymerizes an ethylenically unsaturated group by actinic rays and / or heat. If it is, it will not specifically limit, A well-known photoinitiator and / or a thermal-polymerization initiator polymerization initiator can be used.
Specific examples of the photopolymerization initiator include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Halomethylated triazine derivatives such as trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine; 2-trichloromethyl-5- (2′-benzofuryl) ) Halomethylated oxadiazole derivatives such as 1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxadiazole;

Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; benzophenone and Michler's ketone Benzophenone derivatives such as 4,4′-bis (diethylamino) benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;

2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl- [ Acetophenone derivatives such as 4- (methylthio) phenyl] -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone;

Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; ethyl p-dimethylaminobenzoate, Benzoic acid ester derivatives such as ethyl p-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; Phenazine derivatives such as 9,10-dimethylbenzphenazine; Anthrone derivatives such as benzanthrone ;

Dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-2,6-di-fluoro-3- (pyru-1-yl ) -Titanocene derivatives such as phenyl-1-yl;

Acetophenone oxime-o-acetate and 1,2-octanedione-1- [4- described in JP-A No. 2000-80068, JP-A No. 2006-036750 (Japanese Patent Application No. 2004-183593) and the like. Oximes such as (phenylthio) -2- (o-benzoyloxime)], 1- [9-ethyl-6- (2-benzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime) Examples include ester compounds. These can be used alone or in combination of two or more.

  In addition, for example, Fine Chemical, March 1, 1991, Vol. 20, no. 4, p. 16-p. 26, JP-A-59-152396, JP-A-61-151197, JP-B-45-37377, JP-A-58-40302, JP-A-10-39503, and the like. Initiators.

  In addition to these photopolymerization initiators, a hydrogen donating compound as a polymerization accelerator may be used in combination. Examples of the hydrogen donating compound include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline. , Β-mercaptonaphthalene, ethylene glycol dithiopropionate, trimethylolpropane tristhiopropionate, mercapto group-containing compounds such as pentaerythritol tetrakisthiopropionate; hexanedithiol, trimethylolpropane tristhioglyconate, pentaerythritol tetrakis Polyfunctional thiol compounds such as thiopropionate; N, N-dialkylaminobenzoic acid ester, N-phenylglycine, ammonium salt or sodium salt of N-phenylglycine, etc. Derivatives; phenylalanine, derivatives of such ammonium and sodium salts of phenylalanine; such derivatives, such as esters of phenylalanine. These can be used alone or in combination of two or more.

  Among these, from the viewpoint of the sensitivity of the curable composition, the hydrogen donating compound is preferably a mercapto group-containing heterocyclic compound such as 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole.

  Next, specific examples of the thermal polymerization initiator include azo compounds, organic peroxides, hydrogen peroxide, and the like. These can be used alone or in combination of two or more.

As the azo compounds, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexene-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyronitrile), 2,2-azobis [2-Methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide], 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2 , 2′-azobis [N- (2-propenyl) -2-ethylpropionamide], 2,2′-azobis [N-butyl-2-methylpropionamide], 2,2′-azobis (N-cydo (Rohexyl-2-methylpropionamide), 2,2′-azobis (dimethyl-2-methylpropionamide), 2,2′-azobis (dimethyl-2-methylpropionate), 2,2′-azobis (2 , 4,4-trimethylpentene).
Of these, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and the like are preferable.

  Examples of the organic peroxide include benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, and the like. Specifically, diisobutyryl peroxide, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3, 3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di (2-ethoxyethyl) peroxy Dicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t -Butyl peroxypivale Door,

Di (3,5,5-trimethylhexanoyl) peroxide, di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethyl Hexanoate, disuccinic acid peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4- Methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, dibenzoyl peroxide, t-butylperoxyisobutyrate,

1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylper) Oxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di- (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate , T-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di- (3-methyl Benzoylperoxy) hexane,

t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-di-methyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxyacetate, 2,2-di- (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl 4,4-di- (t-butylperoxy) valerate, di (2 -T-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane,

Di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3 -Tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyltrimethylsilyl peroxide, 2,3-dimethyl-2,3-diphenylbutane, di (3-methylbenzoyl) peroxide and benzoyl And a mixture of (3-methylbenzoyl) peroxide and dibenzoyl peroxide.

  In the curable composition to which the present embodiment is applied, (B) a photopolymerization initiator and / or a thermal polymerization initiator (when used in combination with two or more polymerization accelerators, The total content thereof) is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.5% by weight or more based on the total solid content of the curable composition. However, it is usually 30% by weight or less, preferably 20% by weight or less. If the content of the photopolymerization initiator and / or the thermal polymerization initiator is excessively large, the adhesion to the substrate may be lowered. On the other hand, if it is too small, curability may be lowered.

  The blending ratio of (B) photopolymerization initiator and / or thermal polymerization initiator to (A) ethylenically unsaturated compound is (ethylenically unsaturated compound) / (photopolymerization initiator and / or thermal polymerization start). The value of (agent) (weight ratio) is usually (1/1) to (100/1), preferably (2/1) to (50/1). If the blending ratio deviates from the above range, adhesion and curability may be lowered.

(C) Polymerizable monomer The polymerizable monomer used in the curable composition to which the present embodiment is applied means a concept that is opposed to a so-called polymer substance, and in addition to a narrowly-defined “monomer”. It means a concept including “dimer”, “trimer” and “oligomer”. (Hereinafter, these may be collectively referred to as ethylenic monomers)

  Examples of the polymerizable monomer include compounds having at least one ethylenically unsaturated group in the molecule. Specific examples of the compound having an ethylenically unsaturated group in the molecule include, for example, (meth) acrylic acid, alkyl ester of (meth) acrylic acid, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond, and Examples include monoesters of poly (mono) hydric alcohols.

  In the present embodiment, it is desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. Examples of the polyfunctional ethylenic monomer include, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound, an aromatic Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol tetraacrylate. Acrylic acid esters of aliphatic polyhydroxy compounds such as dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate; methacrylic acid esters in which the acrylates of these exemplary compounds are replaced with methacrylates; itaconic acid esters in which itaconate is similarly substituted; Examples include crotonic acid esters that are substituted; maleic acid esters that are substituted for maleates.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, and the like. And methacrylic acid esters.

  The ester obtained by the esterification reaction of a polyvalent hydroxy compound with a polybasic carboxylic acid and an unsaturated carboxylic acid is not necessarily a single substance, but representative examples include acrylic acid, Condensates of phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin .

  In addition, as an example of a polyfunctional ethylenic monomer, for example, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester or a polyisocyanate compound, a polyol and a hydroxyl group-containing (meth) acrylic acid ester are obtained. Useful are urethane (meth) acrylates; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate.

The content of the polymerizable monomer (C) in the curable composition to which the present embodiment is applied is usually less than 80% by weight, preferably less than 70% by weight, preferably with respect to the total solid content. Is 10% by weight or more. When the content of the polymerizable monomer is out of the above range, it is difficult to obtain an image with a good pattern.
The blending ratio of the polymerizable monomer (C) to the ethylenically unsaturated compound (A) is usually (10/1) as the value of (ethylenically unsaturated compound) / (polymerizable monomer) (weight ratio). ) To (1/10), preferably (5/1) to (1/5).

The polymerizable monomer used in the curable composition to which this embodiment is applied will be described in further detail.
Examples of the compound having one ethylenically unsaturated bond in the molecule include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, itaconic acid, citraconic acid and other unsaturated carboxylic acids, and alkyl esters thereof, (Meth) acrylonitrile, (meth) acrylamide, styrene and the like can be mentioned.

Examples of the compound having two or more ethylenically unsaturated bonds in the molecule include:
(A) an ester of an unsaturated carboxylic acid and a polyhydroxy compound (hereinafter sometimes referred to as “ester (meth) acrylate”),
(B) (meth) acryloyloxy group-containing phosphate,
(C) urethane (meth) acrylate of a hydroxy (meth) acrylate compound and a polyisocyanate compound,
(D) (Meth) acrylic acid or an epoxy (meth) acrylate of a hydroxy (meth) acrylate compound and a polyepoxy compound can be used. These can be used alone or in combination of two or more.

  Among them, a compound having two or more ethylenically unsaturated bonds in the molecule from the viewpoints of, for example, the ability to expand the difference in developer solubility between the exposed portion and the unexposed portion due to polymerizability, crosslinkability, and the like. An acrylate compound in which the unsaturated bond is derived from a (meth) acryloyloxy group is particularly preferable.

  Examples of the above-mentioned (a) ester (meth) acrylate include unsaturated carboxylic acid, ethylene glycol, polyethylene glycol (addition number 2 to addition number 14), propylene glycol, polypropylene glycol (addition number 2 to addition number 14). , Trimethylene glycol, tetramethylene glycol, hexamethylene glycol, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, and their ethylene oxide adducts, propylene oxide adducts, diethanolamine, triethanolamine, and other aliphatic polyhydroxys A reaction product with a compound is mentioned.

  More specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri Methylolpropane ethylene oxide addition tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, glycerol propylene oxide addition tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Sa (meth) acrylate, and the like crotonate, isobutyl crotonate, maleate, itaconate, citraconate, and the like.

  In addition, (a) ester (meth) acrylate includes a reaction product of an unsaturated carboxylic acid and an aromatic polyhydroxy compound such as hydroquinone, resorcin, pyrogallol, bisphenol F, bisphenol A, or an ethylene oxide adduct thereof. Can be mentioned.

  More specifically, for example, bisphenol A di (meth) acrylate, bisphenol A bis [oxyethylene (meth) acrylate], bisphenol A bis [glycidyl ether (meth) acrylate], etc .; tris (2-hydroxyethyl) isocyanurate A reaction product of an unsaturated carboxylic acid and a heterocyclic polyhydroxy compound such as tris (2-hydroxyethyl) isocyanurate, such as di (meth) acrylate and tri (meth) acrylate of (meth) acrylic acid Condensates of phthalic acid and ethylene glycol, condensates of (meth) acrylic acid with maleic acid and diethylene glycol, condensates of (meth) acrylic acid with terephthalic acid and pentaerythritol, (meth) acrylic acid and adipic acid And butanediol and glycerin As the condensates, the reaction product of an unsaturated carboxylic acid and a polycarboxylic acid and polyhydroxy compounds.

  (B) The (meth) acryloyloxy group-containing phosphate is not particularly limited as long as it is a phosphate compound containing a (meth) acryloyloxy group, but those represented by the following general formulas (Ia) to (Ic) are preferable. .

(In Formulas (Ia), (Ib), and (Ic), R ¹⁰ represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 25, and q is 1, 2, or 3.)

  Here, it is preferable that p and p ′ are 1 to 10, particularly 1 to 4. Specific examples of such compounds include, for example, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) acryloyloxyethylene glycol phosphate, and these are used alone. Or may be used as a mixture.

  (C) As urethane (meth) acrylate, the reaction material of a hydroxy (meth) acrylate compound and a polyisocyanate compound is mentioned, for example.

  Examples of the hydroxy (meth) acrylate compound include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, tetramethylolethane tri (meth) acrylate, and the like.

  Examples of the polyisocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate and 1,8-diisocyanate-4-isocyanate methyloctane; cyclohexane diisocyanate, dimethylcyclohexane diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone. Polyisocyanate compounds such as alicyclic polyisocyanates such as diisocyanate and bicycloheptane triisocyanate; aromatic polyisocyanates such as 4,4-diphenylmethane diisocyanate and tris (isocyanatephenyl) thiophosphate; and heterocyclic polyisocyanates such as isocyanurate Can be mentioned.

  (C) As urethane (meth) acrylate, 4 or more (preferably 6 or more, more preferably 8 or more) urethane bonds [—NH—CO—O—] in a molecule and 4 or more ( Preferably, it is a compound having 6 or more, more preferably 8 or more (meth) acryloyloxy groups. Such a compound can be obtained, for example, by reacting the following compound (i) with the following compound (ii).

(I) Compound having four or more isocyanate groups in one molecule For example, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate is added to a compound having four or more hydroxyl groups in one molecule such as pentaerythritol and polyglycerol. Compound (i-1) obtained by reacting a diisocyanate compound such as tolylene diisocyanate; a compound having two or more hydroxyl groups in one molecule such as ethylene glycol, “Duranate 24A-100” manufactured by Asahi Kasei Kogyo Co., Ltd. "Duranate 22A-75PX", "Duranate 21S-75E", "Duranate 18H-70B" and other biuret types, "Duranate P-301-75E", "Duranate E-402-90T", "Dulane Compound (i-2) obtained by reacting a compound having three or more isocyanate groups in one molecule, such as adduct type such as "Eat E-405-80T"; polymerizing isocyanate ethyl (meth) acrylate, etc. Or the compound (i-3) obtained by making it copolymerize etc. are mentioned.
A commercial item can be used as such a compound, for example, "Duranate ME20-100" (i) by Asahi Kasei Kogyo Co., Ltd. is mentioned.

(Ii) a compound having one or more hydroxyl groups and two or more (meth) acryloyloxy groups in one molecule. For example, pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra ( Examples thereof include compounds having one or more hydroxyl groups and two or more, preferably three or more (meth) acryloyloxy groups in one molecule, such as (meth) acrylate and dipentaerythritol penta (meth) acrylate.

  Here, the molecular weight of the above-mentioned compound (i) is 500 to 200,000 as the weight average molecular weight (Mw) in terms of standard polystyrene measured using a gel permeation chromatography method (GPC method). Is preferable, and 1,000 to 150,000 is particularly preferable. Moreover, as a weight average molecular weight (Mw) of urethane (meth) acrylate of standard polystyrene conversion, it is preferable that it is 600-150,000.

  In addition, such urethane (meth) acrylate is, for example, the above compound (i) and the above compound (ii) in an organic solvent such as toluene and ethyl acetate at 10 ° C. to 150 ° C. for 5 minutes to It can be produced by a method of reacting for about 3 hours. In this case, it is preferable that the molar ratio of the former isocyanate group and the latter hydroxyl group is a ratio of (1/10) to (10/1), and a catalyst such as n-butyltin dilaurate is used if necessary. is there.

  In the present embodiment, among the urethane (meth) acrylates, those represented by the following general formula (II) are particularly preferably used.

[In the formula (II), Ra represents a group having an alkyleneoxy group or an aryleneoxy group repeating structure and 4 to 20 oxy groups capable of binding to Rb. Rb and Rc each independently represent an alkylene group having 1 to 10 carbon atoms, and Rd represents an organic residue having 1 to 10 (meth) acryloyloxy groups. Ra, Rb, Rc, and Rd may have a substituent. x is an integer of 4 to 20, y is an integer of 0 to 15, and z is an integer of 1 to 15. ]

  Here, examples of the repeating structure of the alkyleneoxy group of Ra in the formula (II) include those derived from propylene triol, glycerin, pentaerythritol and the like. In addition, examples of the repeating structure of the aryleneoxy group of Ra include those derived from pyrogallol, 1,3,5-benzenetriol, and the like.

  Moreover, it is preferable that carbon number of the alkylene group of Rb and Rc is 1-5 each independently. The number of (meth) acryloyloxy groups in Rd is preferably 1-7. It is preferable that x is 4 to 15, y is 1 to 10, and z is 1 to 10.

  Further, as Ra, the following formula [wherein, k is an integer of 2 to 10. It is preferable that Rb and Rc are preferably each independently a dimethylene group, a monomethyldimethylene group, or a trimethylene group. Further, Rd is preferably the following formula.

  Examples of the (d) epoxy (meth) acrylate include a reaction product of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound.

  Examples of the polyepoxy compound include (poly) ethylene glycol polyglycidyl ether, (poly) propylene glycol polyglycidyl ether, (poly) tetramethylene glycol polyglycidyl ether, (poly) pentamethylene glycol polyglycidyl ether, and (poly) neo. Aliphatic polyepoxy compounds such as pentyl glycol polyglycidyl ether, (poly) hexamethylene glycol polyglycidyl ether, (poly) trimethylolpropane polyglycidyl ether, (poly) glycerol polyglycidyl ether, (poly) sorbitol polyglycidyl ether;

Aromatic polyepoxy compounds such as phenol novolac polyepoxy compounds, brominated phenol novolac polyepoxy compounds, (o-, m-, p-) cresol novolac polyepoxy compounds, bisphenol A polyepoxy compounds, bisphenol F polyepoxy compounds; sorbitan Examples thereof include polyepoxy compounds such as heterocyclic polyepoxy compounds such as polyglycidyl ether, triglycidyl isocyanurate, and triglycidyl tris (2-hydroxyethyl) isocyanurate.

  As an epoxy (meth) acrylate of a (meth) acrylic acid or hydroxy (meth) acrylate compound and a polyepoxy compound, such a polyepoxy compound and the above (meth) acrylic acid or the above hydroxy (meth) acrylate compound And the like.

  Other ethylenically unsaturated compounds include, for example, (meth) acrylamides such as ethylenebis (meth) acrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinyl phthalate, ether bond-containing ethylenically unsaturated compounds And thioether bond-containing compounds in which the crosslinking rate is improved by sulfidizing the ether bond with phosphorus pentasulfide to change it to a thioether bond.

  Further, for example, polyfunctional (meth) acrylate compounds described in Japanese Patent No. 3164407 and JP-A-9-100111 and silica sol having a particle diameter of 5 to 30 nm [for example, isopropanol-dispersed organosilica sol (manufactured by Nissan Chemical Co., Ltd.) "IPA-ST"), methyl ethyl ketone-dispersed organosilica sol ("MEK-ST" manufactured by Nissan Chemical Co., Ltd.), methyl isobutyl ketone-dispersed organosilica sol ("MIBK-ST" manufactured by Nissan Chemical Co., Ltd.), isocyanate group or mercapto Compound bonded using a group-containing silane coupling agent (compound with improved strength and heat resistance as a cured product by reacting and bonding an ethylenically unsaturated compound with silica sol via a silane coupling agent) Is mentioned.

In the present embodiment, from the viewpoint of the mechanical strength of the cured product, (a) ester (meth) acrylate, (b) (meth) acryloyloxy group-containing phosphate, or (c) urethane (meth) acrylate. It is preferable that it is (a) an ester (meth) acrylate.
Further, among (a) ester (meth) acrylates, esters (meth) containing polyoxyalkylene groups such as polyethylene glycol adducts of polyethylene glycol, polypropylene glycol, and bisphenol A, and containing two or more (meth) acryloyloxy groups. Acrylate is particularly preferred.

(D) Solvent The solvent used in the curable composition to which the present embodiment is applied is not particularly limited. For example, water, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, apco # 18 solvent , Diisobutylene, amyl acetate, butyl butyrate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane,

Social solvent No. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, butyl acetate (n, sec, t), hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone,

Propyl acetate, amyl acetate, amyl formate, cyclohexyl acetate, bicyclohexyl, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether acetate (viscosity 3.1 mPa · sec, 25 ° C.), diethylene glycol monobutyl ether (viscosity 4. 9 mPa · sec, 25 ° C.), dipentene, methoxymethylpentanol, methyl amyl ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, Cyclohexanone,

Ethyl acetate, propylene glycol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether (viscosity 1.7 mPa · sec, 25 ° C), propylene glycol monomethyl ether acetate (viscosity 1.1 mPa · sec, 25 ° C), propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate,

3-methoxypropionic acid, 3-ethoxypropionic acid, ethyl 3-ethoxypropionate (viscosity 1.2 mPa · sec, 25 ° C.), methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate , Butyl 3-methoxypropionate, diglyme (viscosity 0.98 mPa · sec, 25 ° C.), diethyl carbitol (viscosity 1.4 mPa · sec, 25 ° C.), diethylene glycol methyl ethyl ether (viscosity 1.2 mPa · sec, 20 ° C.) ), Dipropylene glycol monomethyl ether, ethylene glycol acetate, methyl carbitol (viscosity 3.5 mPa · sec, 25 ° C.), ethyl carbitol (viscosity 3.9 mPa · sec, 25 ° C.), butyl carbitol (viscosity 4.9 mPa)・ Sec, 5 ° C), ethylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methoxybutanol (viscosity 2.9 mPa · sec, 25 ° C), 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl Specific examples include solvents such as -3-methoxybutyl acetate and 3-methoxybutyl acetate (viscosity 1.2 mPa · sec, 25 ° C.).

  A solvent will not be specifically limited if each component can be melt | dissolved or disperse | distributed, According to the usage method of a curable composition, it selects suitably. Especially, it is preferable to select the solvent whose boiling point is the range of 60 to 280 degreeC. More preferably, it has a boiling point of 70 ° C to 260 ° C. These solvents can be used alone or in combination. These solvents are used in such an amount that the ratio of the total solid content in the curable composition of the present embodiment is usually 2% by weight or more and 50% by weight or less.

  In the curable composition to which this embodiment is applied, other components ((E) epoxy compound, (F) amino compound, (G) surfactant) can be blended as necessary. Hereinafter, other components will be described.

(E) Epoxy compound As an epoxy compound, a polyglycidyl ether compound obtained by reacting a polyhydroxy compound and epichlorohydrin constituting a repeating unit of an epoxy resin; a polyglycidyl ester obtained by reacting a polycarboxylic acid compound and epichlorohydrin Compound: Examples include compounds ranging from low molecular weight substances to high molecular weight substances such as polyglycidylamine compounds obtained by reacting polyamine compounds with epichlorohydrin.

  Examples of the polyglycidyl ether compound include polyethylene glycol diglycidyl ether type epoxy; bis (4-hydroxyphenyl) diglycidyl ether type epoxy; bis (3,5-dimethyl-4-hydroxyphenyl) diglycidyl ether type. Epoxy; Diglycidyl ether type epoxy of bisphenol F; Diglycidyl ether type epoxy of bisphenol A; Diglycidyl ether type epoxy of tetramethylbisphenol A; Diglycidyl ether type epoxy of ethylene oxide-added bisphenol A; Diglycidyl ether type of fluorene type bisphenol Epoxy; phenol novolac type epoxy; cresol novolac type epoxy and the like. These polyglycidyl ether compounds may be those obtained by reacting a remaining hydroxyl group with an acid anhydride or a divalent acid compound to introduce a carboxyl group.

  Examples of the polyglycidyl ester compound include diglycidyl ester type epoxy of hexahydrophthalic acid; diglycidyl ester type epoxy of phthalic acid and the like. Examples of the polyglycidylamine compound include diglycidylamine type epoxy of bis (4-aminophenyl) methane; triglycidylamine type epoxy of isocyanuric acid.

  The content of the epoxy compound is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content. When there is too much content, the storage stability of a curable composition may deteriorate.

(F) Amino compound It is preferable that the curable composition to which this Embodiment is applied contains an amino compound from a viewpoint of suppressing the thermal contraction in a thermosetting process. By adding an amino compound, thermosetting is promoted, and height fluctuation during thermosetting can be suppressed.

  The content of the amino compound is usually 40% by weight or less, preferably 30% by weight or less, based on the total solid content. Moreover, it is 0.5 weight% or more normally, Preferably it is 1 weight% or more. When content is too large, the storage stability of a curable composition may deteriorate. Moreover, when there is too little content, the heat shrinkage | contraction suppression effect in said thermosetting may become low.

Examples of the amino compound include an amino compound having at least two methylol groups as functional groups and alkoxymethyl groups obtained by subjecting the methylol group to alcohol condensation modification having 1 to 8 carbon atoms.
Specifically, for example, melamine resin obtained by polycondensation of melamine and formaldehyde; benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensation of glycoluril and formaldehyde; urea and formaldehyde Polycondensed urea resins; resins obtained by copolycondensation of two or more of melamine, benzoguanamine, glycoluril, or urea and formaldehyde; or modified resins obtained by alcohol condensation modification of methylol groups of these resins . These can be used alone or in combination of two or more.

Among them, melamine resins and modified resins thereof are preferable, modified resins having a methylol group modification ratio of 70% or more are more preferable, and modified resins of 80% or more are particularly preferable.
As specific examples of amino compounds, melamine resins and modified resins thereof include, for example, “Cymel” (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327 manufactured by Mitsui Cytec Co., Ltd. , 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158; "Nikarak" (registered trademark) MW-390, MW-100LM of Sanwa Chemical Co., Ltd. MX-750LM, MW-30M, MX-45, MX-302, etc. are mentioned.

Examples of the benzoguanamine resin and its modified resin include “Cymel” (registered trademark) 1123, 1125, 1128, and the like.
Examples of the glycoluril resin and its modified resin include “Cymel” (registered trademark) 1170, 1171, 1174, 1172, “Nicarak” (registered trademark) MX-270, and the like.
Examples of the urea resin and its modified resin include “UFR” (registered trademark) 65, 300, “Nicarak” (registered trademark) MX-290, etc., manufactured by Mitsui Cytec.

  Among them, from the viewpoint of reducing the heat shrinkage rate and improving the heat curing rate, “Nikarak” (registered trademark) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45 of Sanwa Chemical Co., Ltd. MX-302 is particularly preferably used.

(G) Surfactant Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, monoglyceride alkyl ester; Anionic surfactants such as acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids.

(H) Resin not having an ethylenically unsaturated group In the curable composition to which the present embodiment is applied, for the purpose of adjusting the viscosity of the curable composition solution and improving the mechanical properties of the cured product, (H) A resin having no ethylenically unsaturated group can be blended.
Examples of the resin having no ethylenically unsaturated group (H) include the carboxyl group-containing vinyl resins described in [A-1-1] above.
Moreover, the copolymer etc. which contain the carboxyl group and epoxy group which were described in Unexamined-Japanese-Patent No. 11-133600 can be mentioned.

In addition, a colorant, a coating property improver, a development improver, an ultraviolet absorber, a polymerization inhibitor, an antioxidant, a silane coupling agent, and the like are appropriately blended in the curable composition to which the present embodiment is applied. be able to.
As the colorant, known colorants such as pigments and dyes can be used. For example, when using a pigment, a known dispersant or dispersion aid may be used in combination so that the pigment can be stably present in the curable composition without agglomeration.

  As the coatability improver or the development improver, for example, a known cationic, anionic, nonionic, fluorine-based or silicon-based surfactant can be used. Further, as the development improver, known ones such as organic carboxylic acids or anhydrides thereof can be used. The content thereof is usually 20% by weight or less, preferably 10% by weight or less, based on the total solid content.

  Examples of the polymerization inhibitor include hydroquinone and methoxyphenol. Examples of the antioxidant include 2,6-di-tert-butyl-4-cresol (BHT). The content thereof is usually in the range of 5 ppm to 1000 ppm, preferably 10 ppm to 600 ppm, based on the total solid content. If the content is too small, the stability tends to deteriorate. On the other hand, if the amount is excessively large, for example, the curing may be insufficient at the time of curing by heat and / or light. In particular, when used in a normal photolithography method, it is necessary to set the optimum amount in view of both storage stability and sensitivity of the curable composition.

  Various types of silane coupling agents such as epoxy, methacrylic, and amino can be used, and epoxy silane coupling agents are particularly preferable. The content thereof is usually 20% by weight or less, preferably 15% by weight or less, based on the total solid content.

[4] Method of using curable composition The curable composition to which the present embodiment is applied is used in the same manner as known curable compositions for color filters, but is hereinafter used as a spacer. The case will be described.
Usually, a curable composition dissolved or dispersed in a solvent is supplied into a film or pattern by a method such as coating on a substrate on which a spacer is to be provided, and the solvent is dried. After the film is supplied, pattern formation may be performed by a method such as photolithography in which exposure and development are performed if necessary. Then, a spacer is formed on a board | substrate by performing additional exposure and a thermosetting process as needed.

[4-1] Method of Supplying to Substrate The curable composition to which the present embodiment is applied is usually supplied onto the substrate in a state of being dissolved or dispersed in a solvent. As the supply method, a conventionally known method such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method or the like can be used. In particular, the die coating method significantly reduces the amount of coating solution used, has no influence of mist adhering to the spin coating method, and suppresses the generation of foreign matter. From the viewpoint, the curable composition to which the present embodiment is applied is particularly suitable for a coating method by a die coating method.

The coating amount varies depending on the application. For example, in the case of a spacer, the dry film thickness is usually in the range of 0.5 μm to 10 μm, preferably 1 μm to 9 μm, particularly preferably 1 μm to 7 μm. In addition, it is important that the dry film thickness or the height of the finally formed spacer is uniform over the entire area of the substrate. When the variation is large, a nonuniformity defect occurs in the liquid crystal panel. Further, it may be supplied in a pattern by an inkjet method, a printing method, or the like.
A known substrate such as a glass substrate can be used as the substrate. The substrate surface is preferably a flat surface.

[4-2] Drying method Drying after supplying the curable composition onto the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. Moreover, you may combine the reduced pressure drying method of drying in a decompression chamber, without raising temperature.
The drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably 50 ° C. to 110 ° C., depending on the type of solvent component, the performance of the dryer used, and the like. The temperature is selected in the range of 30 seconds to 3 minutes.

[4-3] Exposure Method Exposure is performed by superimposing a negative mask pattern on the coating film of the curable composition and irradiating an ultraviolet light source or a visible light source through the mask pattern. Further, a scanning exposure method using a laser beam without using a mask pattern may be used. At this time, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure is performed after deoxygenation or after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. Or you may.

  The light source used for said exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples thereof include laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, blue-violet semiconductor laser, and near infrared semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

  The optical filter may be, for example, a thin film type that can control the light transmittance at the exposure wavelength. In this case, examples of the material used for the optical filter include Cr compounds (Cr oxide, nitride, oxynitride, fluoride, and the like), MoSi, Si, W, Al, and the like. When a mask in which such an optical filter is arbitrarily arranged in the opening (translucent portion) of the mask pattern (that is, a mask in which an opening provided with an optical filter and an opening provided without an optical filter are appropriately arranged) is used. It is possible to form patterns having different photopolymerization rates in accordance with the light transmittance of the openings by the multiple exposure steps. In addition, for example, it is possible to simultaneously form patterns having different heights in a single exposure process.

Energy of exposure generally, 1 mJ / cm ² or more, preferably 5 mJ / cm ² or more, more preferably 10 mJ / cm ² or more, usually 1000 mJ / cm ² or less, preferably 800 mJ / cm ² or less, more preferably 500 mJ / cm ² or less.
The distance between the exposure object and the mask pattern is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less.

[4-4] Development Method After performing the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. This aqueous solution may further contain a surfactant, an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or triethanolamine, mono-di- or trimethylamine, Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline Organic alkali compound may be mentioned. These alkaline compounds may be a mixture of two or more.

Examples of the surfactant include the same ones as described above.
Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or in combination with an aqueous solution.

[4-5] Additional exposure and thermosetting treatment The substrate after development may be subjected to additional exposure by a method similar to the above exposure method, if necessary, or may be subjected to thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature ranges from 100 ° C. to 280 ° C., preferably from 150 ° C. to 250 ° C., and the time ranges from 5 minutes to 60 minutes.

[4-6] Total deformation, elastic recovery rate, recovery rate When the curable composition in the present embodiment is used for a spacer, in the load-unloading test with a microhardness meter, the following (1) It is the characteristic that the hardened | cured material which satisfy | fills and satisfy | fills (2) and / or (3) can be formed.
(1) The total deformation is 1.35 μm or more. (2) The elastic recovery rate is 50% or more. (3) The recovery rate is 80% or more. In the following, the spacer used in the panel or the like is likely to be loaded in the manufacturing process of the panel, and the total amount of deformation of the spacer tends to increase. In particular, in a large screen panel, the load tends to be uneven in each part. Even in such a case, the curable composition of the present invention is significant in that the cured product (spacer) has a high elastic recovery rate and / or high recovery rate.

Here, the load-unloading test by the micro altimeter is performed as follows.
Among the spacer patterns formed by the above method [4], one pattern having a height of 4 μm and an upper cross-sectional area of 80 ± 10 μm ² is measured using a microhardness meter.
The upper cross-sectional area of the spacer pattern means the following area. First, a vertical cross section passing through the central axis of the spacer pattern is profiled for one spacer pattern using an ultra-deep color 3D shape measurement microscope (manufactured by Keyence Corporation: VK-9500). The profile position is shown in FIG. Next, a straight line AA ′ parallel to the substrate surface in the spacer pattern graphic at a height of 90% of the height from the substrate surface of the profiled graphic (schematic diagram shown in FIG. 3) to the point Q at the highest position. Measure the length. The area of a circle whose diameter is the straight line AA ′ is the upper cross-sectional area of the spacer pattern.

The hardness measurement is performed using a dynamic ultra micro hardness meter (manufactured by Shimadzu Corporation: Shimadzu dynamic ultra micro hardness meter DUH-W201S).
The test conditions were as follows: a flat indenter with a measurement temperature of 23 ° C. and a diameter of 50 μm, a load was applied to the spacer at a constant speed (0.22 gf / sec), and when a predetermined maximum load of 5 gf was reached, the load was held for 5 seconds. Unload at the same speed. The maximum displacement H [max] and the final displacement H [last] are measured from the load-displacement curve obtained from this test (schematic diagram shown in FIG. 4). The maximum displacement H [max] is defined as the total deformation amount.

The total deformation amount is preferably 1.4 μm or more, more preferably 1.5 μm or more, preferably 5 μm or less, more preferably 3 μm or less.
If the total deformation amount is too large, the elastic recovery rate and / or the recovery rate deteriorates. On the other hand, if the total amount of deformation is too small, the cured product cannot cope with load unevenness during panel manufacture.

The elastic recovery rate and recovery rate are calculated as follows based on the values measured by the load-unloading test using the micro hardness tester.
Recovery rate (%) = {(pattern height before test) −H [last]} / (pattern height before test) × 100
Elastic recovery rate (%) = (H [max] −H [last]) / H [max] × 100
The recovery rate is preferably 85% or more, more preferably 90% or more.

The elastic recovery rate is preferably 60% or more, more preferably 80% or more.
If the recovery rate and / or elastic recovery rate is too small, the cured product cannot cope with load unevenness during panel manufacture.

  The curable composition to which the present embodiment is applied is a curable composition that provides a cured product having excellent height uniformity in application by a die coating method. Moreover, according to the present embodiment, a curable composition that balances such height uniformity with various performances conventionally required for curable compositions used for color filters and the like is realized. Is done.

  The curable composition to which this embodiment is applied is a curable resin composition that is suitably used when forming a black matrix, overcoat, ribs, spacers, and the like in a color filter such as a liquid crystal display. According to this embodiment, it is possible to provide a high-quality color filter, a liquid crystal display device, and the like.

[5] Color Filter Next, the color filter will be described.
FIG. 5 is a schematic diagram illustrating an example of a color filter. As shown in FIG. 5, in the color filter 20, a black matrix 22, a pixel coloring layer 23, and an overcoat layer 24 are laminated on a glass substrate 21 as a transparent substrate.
The black matrix 22 blocks external light and improves black display quality and contrast. The pixel coloring layer 23 is formed by applying pigments or dyes for displaying three colors of RGB (Red, Green, Blue). The overcoat layer 24 fills the level difference of the pixel coloring layer 23 and flattens it.

Examples of the material having properties equivalent to the glass substrate 21 as the transparent substrate include polyester resins such as polyethylene terephthalate; polyolefin resins such as polypropylene and polyethylene; sheets made of thermoplastic resin such as polycarbonate, polymethyl methacrylate, and polysulfone; Examples thereof include thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly (meth) acrylic resins.
If necessary, the glass substrate 21 as a transparent substrate is subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins, etc. to improve surface properties such as adhesion. May be. The thickness of the glass substrate 21 is generally 0.05 mm to 10 mm, preferably 0.1 mm to 7 mm.

The black matrix 22 is formed on the glass substrate 21 using a light shielding metal thin film or a black matrix pigment dispersion.
When the light shielding metal thin film for the black matrix 22 is used, as the light shielding metal thin film material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloy, etc. are used, and these are laminated in a plurality of layers. It may be made.
These light-shielding metal thin film materials are usually formed on the glass substrate 21 by a vapor deposition method or a sputtering method, and then a desired pattern is formed in a film shape by a positive photoresist. Etching solution mixed with ceric ammonium and perchloric acid is used, and other materials are etched using the etching solution according to the material. Finally, the positive photoresist is stripped with a special stripper. By doing so, the black matrix 22 can be formed.

  When utilizing the pigment dispersion liquid for the black matrix 22, the black matrix 22 is formed using the curable composition containing a black coloring material. For example, black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or a single color material, or a red, green, blue, or the like appropriately selected from inorganic or organic pigments and dyes The black matrix 22 can be formed in the same manner as the method of forming the red, green, and blue pixel coloring layers 23 using a curable composition containing a black color material by mixing.

Next, a pixel coloring layer 23 of RGB (Red, Green, Blue) three colors is formed on the glass substrate 21 provided with the black matrix 22 by using a cured product of the curable composition to which the present embodiment is applied. Further, the color filter 20 is manufactured by forming the overcoat layer 24 to fill the level difference of the pixel coloring layer 23 and flattening.
The curable composition used for forming the pixel coloring layer 23 is used as at least one resist forming coating solution of red, green, and blue. For red, green, and blue, a resist-forming coating solution is formed on a resin black matrix forming surface formed on the glass substrate 21 or on a metal black matrix forming surface formed using a chromium compound or other light shielding metal material. After coating and drying, a photomask is layered on the coating film, and image coloring through this photomask, development, and pixel coloring consisting of a cured product of a curable composition by thermal curing or photocuring as necessary Layer 23 is formed. By performing this operation for each of the three colors red, green, and blue, a color filter image can be formed.

The method for supplying the resist-forming coating solution onto the glass substrate 21, the drying method, the exposure method, the development method, the additional exposure, and the thermosetting treatment are the same as the operations and conditions described in the spacer formation method described above. I do.
Here, as described above, the curable composition in the present embodiment is excellent in rheological characteristics and excellent in the coating property by the die coating method. Therefore, the color filter 20 to which the present embodiment is applied has the curable composition described above. It is preferable that a product is manufactured through a coating process by a die coating method in terms of manufacturing yield and product quality.

[6] Liquid Crystal Display Device Next, a liquid crystal display device will be described.
FIG. 6 is a schematic diagram showing an example of a layer structure of a liquid crystal display (panel) LCD. As shown in FIG. 6, the liquid crystal display (panel) LCD has a liquid crystal cell 40 formed by providing a spacer 28 between a color filter 20 provided with a transparent electrode 25 and a TFT (Thin Film Transistor) array substrate 30. The liquid crystal 29 is filled.

  In the color filter 20, a black matrix 22, a pixel coloring layer 23, and an overcoat layer 24 are laminated on a glass substrate 21. On the overcoat layer 24, a transparent electrode 25 made of ITO (indium tin oxide) is disposed. On the transparent electrode 25, a liquid crystal alignment control protrusion (rib) 27 and a spacer 28 are disposed, and an alignment film 26 is laminated thereon. The transparent electrode 25 applies a voltage to the liquid crystal 29 to control the direction of liquid crystal molecules. The alignment film 26 is provided to twist the molecules of the liquid crystal 29 into a special shape.

The TFT array substrate 30 is provided on a glass substrate 31 with a TFT 32 for controlling the display of a liquid crystal display device (panel) LCD, an insulating film 33, a transparent electrode 34 made of ITO, a liquid crystal alignment control protrusion (rib) 37, The alignment film 35 is sequentially arranged.
A polarizing plate (not shown) is attached to the outside of each of the glass substrates 21 and 31. Further, an illumination device (BL) is provided outside the TFT array substrate 30.

As described above, in the color filter 20 of the liquid crystal display device (panel) LCD, the pixel coloring layer 23 displays RGB (Red, Green, Blue) color using the curable composition in the present embodiment. It is formed as a pixel image. Further, the liquid crystal alignment control protrusions (ribs) 27 and 37 and the spacer 28 of the liquid crystal display device (panel) LCD are also formed using the curable composition in the present embodiment.
The alignment films 26 and 35 are preferably resin films such as polyimide. As a method for forming the alignment films 26 and 35, a gravure printing method, a flexographic printing method, or the like is usually employed, and a curing process is performed by thermal baking. The thickness of the alignment films 26 and 35 is usually several tens of nm.

The liquid crystal display device (panel) LCD is manufactured, for example, by the following operation.
The color filter 20 forms a black matrix 22 and a pixel coloring layer 23 on a glass substrate 21. Next, the pixel coloring layer 23 is covered with an overcoat layer 24 as necessary, and a transparent electrode 25 is applied. Next, liquid crystal alignment control protrusions (ribs) 27 and spacers 28 are formed. Further, an alignment film 26 is formed on the liquid crystal alignment control protrusions (ribs) 27 and the spacers 28.
In the TFT array substrate 30, a TFT 32, an insulating film 33, a transparent electrode 34, a liquid crystal alignment control protrusion (rib) 37 and an alignment film 35 are formed on a glass substrate 31. Next, the color filter 20 and the TFT array substrate 30 are bonded together with the alignment film 26 of the color filter 20 and the alignment film 35 of the TFT array substrate 30 facing each other to form the liquid crystal cell 40. Then, liquid crystal 29 is injected into the formed liquid crystal cell 40 and connected to a counter electrode (not shown) to manufacture a liquid crystal display (panel) LCD.

  Hereinafter, based on an Example, this invention is demonstrated more concretely. In addition, this invention is not limited to a following example, unless the summary is exceeded.

(1) Compound synthesis example (Synthesis example 1: ethylenically unsaturated compound (A1))
A reaction vessel was charged with 180 parts of propylene glycol monomethyl ether (viscosity 1.7 mPa · sec, 25 ° C.) and 7.3 parts of an azo polymerization initiator (“V-59” manufactured by Wako Pure Chemical Industries, Ltd.). The temperature was raised to 80 ° C., 4 parts of methyl methacrylate, 70 parts of methacrylic acid and 31 parts of isobornyl methacrylate were added dropwise, and the mixture was further stirred for 4 hours.
Next, the inside of the reaction vessel was purged with air, and 0.1 part of paramethoxyphenol, 103.8 parts of glycidyl methacrylate and 4.2 parts of tetraethylammonium chloride were added, and the reaction was continued at 85 ° C. for 10 hours.
Propylene glycol monomethyl ether was added to the resulting reaction solution to obtain a solution having a solid concentration of 50% by weight.
The obtained ethylenically unsaturated compound (A1) had a solid content acid value of 22 mgKOH / g and a weight average molecular weight (Mw) of 16,000. (Double bond equivalent 286)

(Synthesis Example 2: Ethylenically unsaturated compound (A2))
90 parts of propylene glycol monomethyl ether acetate and 6.1 parts of an azo polymerization initiator (“V-59” manufactured by Wako Pure Chemical Industries, Ltd.) were charged into a reaction vessel, heated to 80 ° C. in a nitrogen atmosphere, and 15 parts of styrene. Then, 42 parts of glycidyl methacrylate and 30 parts of monomethacrylate ("FA-513M" manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise, followed by further stirring for 4 hours.

Next, the inside of the reaction vessel was purged with air, 0.05 part of paramethoxyphenol, 21.3 parts of acrylic acid and 2.1 parts of tetraethylammonium chloride were added, and the reaction was continued at 80 ° C. for 8 hours.
Thereafter, 12.5 parts of tetrahydrophthalic anhydride was added and reacted at 85 ° C. for 4 hours.
Propylene glycol monomethyl ether acetate was added to the obtained reaction solution to obtain a solution having a solid content concentration of 50% by weight.
The obtained ethylenically unsaturated compound (A2) had a solid content acid value of 38 mgKOH / g and a weight average molecular weight (Mw) of 10,000. (Double bond equivalent is 409)

(Compound (H): Compound obtained by the following production example (acrylic resin described in Synthesis Example 3 (paragraph 0043) in JP-A-11-133600)
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol dimethyl ether.
Subsequently, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 45 parts by weight of glycidyl methacrylate, and 25 parts by weight of dicyclopentanyl methacrylate were charged and nitrogen was stirred.
The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (H). The obtained polymer solution had a solid content concentration of 33%, a solid content acid value of 110 mgKOH / g, and a weight average molecular weight (Mw) of 18,000.

(Synthesis Example 3: Ethylenically unsaturated compound (A4))
118 parts by weight of succinic anhydride and 596 parts by weight of commercially available pentaerythritol triacrylate were reacted at 85 ° C. for 5 hours in the presence of 2.5 parts by weight of triethylamine and 0.25 parts by weight of hydroquinone. After the reaction, a polyfunctional acrylate mixture composed of 66% polyfunctional acrylate having one carboxyl group and two or more acryloyl groups in one molecule and 34% pentaerythritol tetraacrylate (ethylenically unsaturated group-containing carboxylic acid) A mixture AA1) was obtained. The acid value of this polyfunctional acrylate mixture is 92.7.

  Next, in a 1000 ml four-necked flask, 231 g of 9,9-bis (4′-hydroxyphenyl) fluorene diglycidyl etherified product (epoxy equivalent 231) and the ethylenically unsaturated group-containing carboxylic acid mixture (AA1) 605 g, triethylbenzylammonium chloride 6.06 g, p-methoxyphenol 0.15 g, and propylene glycol monomethyl ether acetate 170 g were charged. Then, these were heated and dissolved at 70 ° C. to 80 ° C., and further heated to 85 ° C. gradually in a state where the solution became cloudy to be completely dissolved. Subsequently, the solution which became transparent and viscous was continuously heated and stirred for 8 hours until the acid value reached 3.0 KOH mg / g, and a colorless and transparent reaction product was obtained. Further, propylene glycol monomethyl ether acetate was added to the obtained reaction product to prepare a solid content of 50%.

  Subsequently, 8.7 g of 1,2,3,6-tetrahydrophthalic anhydride was added to 100 g of the obtained 50% solid solution, and the temperature was gradually raised and reacted at 80 to 85 ° C. for 3 hours. A solution of (A4) was obtained. (The solid concentration of this solution is 54%) The compound (A4) obtained has a solid content acid value of 55 KOH mg / g and a weight average molecular weight (Mw) of 2,500.

(2) Evaluation of curable composition (i) Viscosity In the blending ratio shown in Table 2, the ethylenically unsaturated compounds (A1) to (A4) ((A) component) and the photopolymerization initiator ((B) Component), polymerizable monomer (component (C)), solvent (component (D)), surfactant (component (G)) and resin having no ethylenically unsaturated group (component (H)) at room temperature The coating solution was prepared by stirring and measured at a temperature of 23 ° C. using a viscometer (E-type viscometer manufactured by Tokyo Keiki Co., Ltd.).

(Ii) Leveling resistance value, sagging resistance value Based on the solid content concentration and viscosity value of the curable composition prepared at the blending ratio shown in Table 2, the leveling resistance value (RL) represented by the formula (1) described above. And the sagging resistance value (RS) represented by Formula (2) was calculated.

(Iii) Leveling characteristics and sagging characteristics evaluation A curable composition (color resist 4) prepared at a blending ratio shown in Table 2 is a shim 1 having a protrusion 1a shown in FIG. 1 (a) in FIG. 1 (b). As shown, it was discharged from the discharge port 2a of the slit die 2 having a width of 550 mm and coated on the glass substrate 3 under the conditions of a coating speed of 100 mm / s, a coating gap of 100 μm, and a dry film thickness of 4.5 μm.

Regarding the “height uniformity” in the leveling characteristics, after the application, after processing for 0.5 Torr × 120 seconds in a reduced pressure drying apparatus, it was processed in a convection oven at 230 ° C. for 30 minutes. The film thickness distribution in the width direction was measured, and the height distribution (standard deviation) was evaluated. Further, the occurrence of streak unevenness 5 on the coated substrate was macro-observed with a Na lamp and evaluated according to the following criteria.
○: There is no interference fringe on the entire surface except the range of 1 cm to 2 cm from the coating end.
X: A strong interference fringe is seen over the whole substrate surface.

For the sagging property “dripping”, the coated substrate immediately after coating is held at an inclination of 30 degrees for 10 seconds, then treated with a vacuum dryer for 0.5 Torr × 120 seconds, and then treated at 230 ° C. for 30 minutes in a convection oven. Then, the film thickness distribution in the tilt direction of the obtained coated substrate was measured, and the film thickness fluctuation due to sagging was evaluated according to the following criteria.
○: The film thickness difference at a point of 2 cm from both end portions in the inclined direction of the coated substrate is 0.4 mm or less.
(Triangle | delta): The film thickness difference of a 2 cm point from the both ends of the inclination direction of a coating substrate exceeds 0.4 mm.

(Iv) Evaluation of total deformation, recovery rate, elastic recovery rate (iv-1) Formation of spacer pattern The blending ratio shown in Table 2 using a spinner on the ITO film of the glass substrate on which the ITO film was formed on the surface After applying the curable composition prepared in (1), the coating film was formed by heating and drying on a hot plate at 80 ° C. for 3 minutes. The obtained coating film was exposed to an exposure amount of 100 mJ / cm ² using ultraviolet rays having an intensity at 365 nm of 32 mW / cm ² using a predetermined pattern mask. The ultraviolet irradiation at this time was performed under air. Subsequently, spray development was carried out with a 0.1 wt% potassium hydroxide aqueous solution at 23 ° C. for twice the minimum development time, followed by rinsing with pure water for 1 minute. Here, the minimum development time means a time during which the unexposed area is completely dissolved under the same development conditions. By these operations, the glass substrate on which the unnecessary portion was removed and the spacer pattern was formed was cured by heating in an oven at 230 ° C. for 30 minutes to obtain a cylindrical spacer pattern having a height of 4 μm.

(Iv-2) Shape measurement of spacer pattern About the pattern obtained in the above (iv-1), using an ultra-deep color 3D shape measurement microscope (manufactured by Keyence Corporation: VK-9500), as shown in FIG. A longitudinal section passing through the central axis of the spacer pattern was profiled, and the upper sectional area and height were measured. The height of 90% of the height from the substrate surface of the profiled figure (schematic diagram shown in FIG. 3) to the point Q at the highest position is the height of the spacer. The length of the straight line AA ′ parallel to the substrate surface was measured, and the area of the circle having the diameter of the straight line AA ′ was taken as the upper cross-sectional area of the spacer pattern.

(Iv-3) Evaluation of the mechanical properties of the spacer Among the spacer patterns obtained in the above (iv-1), the mechanical properties of one pattern having a height of 4 μm and an upper cross-sectional area of 80 ± 10 μm ² were obtained. Was evaluated by a load-unloading test using a Shimadzu dynamic microhardness meter (manufactured by Shimadzu Corporation: DUH-W201S).
A load L is applied to the spacer pattern at a constant speed (0.22 gf / sec) with a flat indenter with a diameter of 50 μm at a measurement temperature of 23 ° C., and when the predetermined maximum load of 5 gf is reached, the load is held for 5 seconds. Unloaded at
The maximum displacement (total deformation amount) H [max] and final displacement H [last] are measured from the load-displacement curve (schematic diagram shown in FIG. 4) obtained from this test, and the recovery rate (%), elasticity The restoration rate (%) was calculated as follows based on the measured values, and the results are shown in Table 2.
Recovery rate (%) = {(pattern height before test) −H [last]} / (pattern height before test) × 100
Elastic recovery rate (%) = (H [max] −H [last]) / H [max] × 100

(Examples 1-6, Comparative Examples 1-3)
Ethylenically unsaturated compounds (A1) to (A4) (component (A)), photopolymerization initiator (component (B)), polymerizable monomer (component (C)), solvent (component (D)), surface activity Viscosity (μ) and leveling resistance of the curable composition prepared at the blending ratio shown in Table 2 using the agent (component (G)) and the resin having no ethylenically unsaturated group (component (H)) A value (RL) and a sag resistance value (RS) were obtained, and height uniformity and sag characteristics were evaluated. The results are shown in Table 2.

Here, in Table 2, (B) component (photopolymerization initiator), (C) component (polysynthetic monomer), (D) component (solvent), and (G) component (surfactant) are as follows. It is.
(B) Photopolymerization initiator: “Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd.
(C1) Dipentaerythritol hexaacrylate: “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd. (viscosity 5500-8000 mPa · sec, 25 ° C.)
(C2) Pentaerythritol triacrylate hexamethylene diisocyanate Urethane prepolymer: “UA-306H” manufactured by Kyoeisha Chemical Co., Ltd. (viscosity 10000-40000 mPa · sec, 25 ° C.)
(D1) Propylene glycol monomethyl ether acetate (viscosity 1.1 mPa · sec, 25 ° C.)
(D2) 3-methoxybutanol (viscosity 2.9 mPa · sec, 25 ° C.)
(G) Surfactant: “Megafac F475” manufactured by Dainippon Ink & Chemicals, Inc.

From the results in Table 2, the ethylenically unsaturated compounds (A1) to (A4) (component (A)), photopolymerization initiator (component (B)), polymerizable monomer (component (C)), solvent ((D ) Component) and a curable composition prepared using a surfactant (component (G)), the leveling resistance value (RL) is in the range of 0.01 to 0.05, and the sag resistance value (RS) ) Is 0.1 or more (Examples 1 to 6), it can be seen that the height uniformity in the die coat is good, the leveling characteristics are excellent, and the sagging characteristics are good.
On the other hand, when the leveling resistance value (RL) exceeds 0.05 (Comparative Examples 1 and 2) or less than 0.01 (Comparative Example 3), the height uniformity in the die coat is poor and the leveling characteristics are low. It turns out that it is damaged.

FIG. 1A is a plan view showing a shim used in an evaluation test, and FIG. 1B is a perspective view showing a coating state by a slit die attached with the shim. It is a schematic diagram which shows the position to profile when a spacer pattern is seen from the top. It is a schematic diagram which shows the profile of the longitudinal cross-section of a spacer pattern. It is a schematic diagram which shows the load-displacement curve in the load-unloading test of a spacer. It is the schematic which shows an example of a color filter. It is the schematic which shows an example of the laminated constitution of a liquid crystal display device (panel).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Shim, 2 ... Slit die, 3, 21, 31 ... Glass substrate, 4 ... Color resist, 5 ... Stripe irregularity, 11 ... Spacer pattern, 12 ... Center axis of spacer pattern, 13 ... Profile position, 14 ... Spacer pattern Profile of longitudinal section, 15: height from substrate surface to highest position, 16: height of 90% of height from substrate surface to highest position, 17: straight line AA ′ of circle in upper section, 20: color filter , 22 ... Black matrix, 23 ... Pixel coloring layer, 24 ... Overcoat, 25, 34 ... Transparent electrode, 26, 35 ... Alignment film, 27, 37 ... Liquid crystal alignment control protrusion (rib), 28 ... Spacer, 29 ... Liquid crystal 30 ... TFT array substrate, 32 ... TFT, 33 ... insulating film, 40 ... liquid crystal cell

Claims (6)

A curable composition satisfying the following (a) and (b).
(A) The leveling resistance value (RL) represented by the following formula (1) using the viscosity (μ) and solid content concentration (C) of the coating solution is in the range of 0.01 to 0.05.
RL = μ × C ³ (1)
(In formula (1), RL is the leveling resistance value, μ is the viscosity of the coating solution (unit: mPa · s), and C is the solid content concentration (unit: kg / kg).)
(B) The sagging resistance value (RS) represented by the following formula (2) is 0.1 or more.
RS = μ × C ² (2)
(In Formula (2), RS is a sag resistance value, μ is the viscosity of the coating solution (unit: mPa · s), and C is the solid content concentration (unit: kg / kg).)   The curable composition according to claim 1, wherein the curable composition is used for die coating.   The curable composition according to claim 1, wherein the curable composition is used for forming a color filter.   A cured product obtained by curing the curable composition according to claim 1.   A color filter comprising the cured product according to claim 4.   A liquid crystal display device comprising the color filter according to claim 5.

Images