JP2003201382A - Curable resin composition and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new curable resin composition capable of forming a cured product having excellent physical properties such as heat resistance, transparency, coating film strength, and to provide its use. <P>SOLUTION: The curable resin composition contains a polymer having a lacton ring prepared by lacton cyclization of a structural unit derived from 2-hydroxyalkyl acrylate and a compound having an active hydrogen group capable of reacting with the lacton ring. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel curable resin composition and its use. More specifically, the curable resin composition is capable of improving the physical properties of a cured product obtained by intermolecular crosslinking, and forms various members in color filters used in color liquid crystal display devices, color scanners, video cameras and the like. Is preferably used in.

[0002]

2. Description of the Related Art Up to now, many curable resin compositions have been proposed, but all have some problems.
It wasn't quite satisfactory. For example, a curable resin composition composed of a polymer having an alkoxysilyl group and a curing catalyst is known to crosslink in the presence of water and a curing catalyst. However, in principle, moisture is essential for crosslinking the curable resin composition, and it is difficult to cure under conditions where the moisture is low. Further, since the crosslinking reaction generates alcohol, there is a problem that bubbles are generated depending on the curing conditions.

A curable resin composition comprising a polymer having an active hydrogen group, a polyfunctional isocyanate, and a curing catalyst can be crosslinked by reacting a compound having an active hydrogen group with the polyfunctional isocyanate. However, the bond formed by the cross-linking, for example, the bond formed by the reaction of an active hydrogen group such as a hydroxyl group or a thiol group with an isocyanate group has a problem in that it is easily broken by heat and is easily colored. It was On the other hand, as the curable resin composition for a color filter, various photosensitive resin compositions and thermosetting resin compositions have been disclosed.
JP-A-152449 discloses a photosensitive resin composition for a color filter, which comprises a (meth) acrylic acid ester-based binder resin, a pigment, a dispersant, a photopolymerization initiator, and a photopolymerizable monomer. However, in this technique, since it is inferior in heat resistance and heat stability, deterioration or decomposition occurs in the subsequent heat treatment step, background stains, a decrease in the smoothness of the coating film, a decrease in the film thickness,
There was a problem of causing coloring. Further, in terms of coating film strength and exposure sensitivity, sufficiently satisfactory performance has not been obtained.

Further, Japanese Patent Application Laid-Open No. 6-27665 discloses that
(Meth) acrylic acid ester, (meth) acrylic acid, 2
There has been proposed a photosensitive resin composition for a dry film resist, which comprises a copolymer of-(hydroxymethyl) acrylic acid ester, a photopolymerization initiator and an ethylenically unsaturated compound. However, with this technique, the developability was insufficient, and the coating strength and exposure sensitivity were also insufficient.

[0005]

Therefore, an object of the present invention is to provide a novel curable resin composition capable of obtaining a cured product having excellent physical properties such as heat resistance, transparency and coating film strength and its use. The purpose is to provide.

[0006]

The curable resin composition of the present invention comprises a polymer having a lactone ring obtained by lactone cyclization of a structural unit derived from 2- (hydroxyalkyl) acrylic acid ester, and the lactone ring. And a compound having an active hydrogen group capable of reacting. The color filter of the present invention is characterized in that, in the color filter having a resin layer provided on a substrate, the resin layer is a resin layer obtained by curing the curable resin composition of the present invention. The display device of the present invention is a display device using a color filter in which a resin layer is provided on a substrate, wherein the resin layer is a resin layer obtained by curing the curable resin composition of the present invention. Is characterized by.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition of the present invention comprises 2
-A polymer having a lactone ring obtained by cyclizing a structural unit derived from (hydroxyalkyl) acrylic acid ester (hereinafter, also referred to as "lactone ring-containing polymer") and an activity capable of reacting with the lactone ring A compound having a hydrogen group (hereinafter sometimes referred to as “active hydrogen group-containing compound”) is contained as an essential component, and a lactone ring of a lactone ring-containing polymer and an active hydrogen group of an active hydrogen group-containing compound are contained. Is capable of forming a crosslinked structure by reacting between molecules to generate a new chemical bond. The crosslinked structure thus formed can improve physical properties such as transparency, heat resistance and coating film strength. Further, the lactone ring which remains without participating in the formation of the crosslinked structure not only does not adversely affect the heat resistance, transparency and coating film strength, but can also be improved.

The lactone ring-containing polymer, which is an essential component of the curable resin composition of the present invention, has a structure in which the structural unit derived from 2- (hydroxyalkyl) acrylic acid ester is lactone-cyclized to form a main skeleton of the polymer. It is a polymer having a lactone structure formed in 1. The lactone cyclization is
2 in the molecular chain formed by polymerizing a monomer component containing 2- (hydroxyalkyl) acrylic acid ester
The hydroxyl group of the structural unit derived from-(hydroxyalkyl) acrylic acid ester and the carboxyl group or ester group derived from the structural unit adjacent to the structural unit derived from 2- (hydroxyalkyl) acrylic acid ester are cyclocondensed to give a heavy polymer. This is a reaction for forming a lactone ring structure in the molecular chain of the coalescence (in the main skeleton of the polymer), and water and alcohol are by-produced by the lactone cyclization. In the lactone cyclization, it is not necessary that all the structural units derived from 2- (hydroxyalkyl) acrylic acid ester be lactone cyclized, and it is sufficient that a part thereof is lactone cyclized. Preferably, 40 mol% or more of the structural unit derived from 2- (hydroxyalkyl) acrylic acid ester is lactone cyclized, more preferably 60 mol% or more, most preferably 80 mol% or more lactone cyclized. Is good. Specific examples of the 2- (hydroxyalkyl) acrylic acid ester include compounds represented by the following general formula (1), and the structural unit derived from the 2- (hydroxyalkyl) acrylic acid ester is Examples of the lactone ring formed by lactone cyclization include a lactone ring structure represented by the following general formula (2).

[0009]

[Chemical 1]

(In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms.)

[0011]

[Chemical 2]

(In the formula (2), R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue contains an oxygen atom. Specific examples of the compound represented by the general formula (1) include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, and 2-
Isopropyl (hydroxymethyl) acrylate, 2-
Examples thereof include n-butyl (hydroxymethyl) acrylate, t-butyl 2- (hydroxymethyl) acrylate, and 2-ethylhexyl 2- (hydroxymethyl) acrylate. Among these, 2- (hydroxymethyl) acryl is particularly preferable. Methyl acid and ethyl 2- (hydroxymethyl) acrylate are preferred.

The lactone ring-containing polymer can be produced by polymerizing a monomer component containing 2- (hydroxyalkyl) acrylic acid ester and cyclizing the lactone at the same time as or after the polymerization. The conditions such as the polymerization method and the lactone cyclization method for producing the lactone ring-containing polymer are determined by the amount of 2- (hydroxyalkyl) acrylic acid ester in the monomer component used, the desired degree of lactone cyclization, and the desired lactone cyclization rate. It may be appropriately selected according to the molecular weight of the polymer, the amount of solvent, etc., and is not particularly limited. In particular, when polymerizing a monomer component containing a monomer having an acid group together with a 2- (hydroxyalkyl) acrylic acid ester, a solvent that sufficiently dissolves the monomer component and the resulting polymer is used.
By carrying out solution polymerization at ˜150 ° C., lactone cyclization can be performed almost quantitatively simultaneously with the polymerization. Therefore, the method is preferable as the method for producing the lactone ring-containing polymer, but the method is not limited to this method. In the above method, the monomer having an acid group or the resulting polymer acts as a catalyst in the cyclization, so that the lactone cyclization can be performed simultaneously with the copolymerization of the monomer components. At this time, the fact that the lactone cyclization is carried out at the same time as the polymerization is performed by using, for example, an IR device.
Reduction of absorption of vinyl group around 70 cm ^-1 and 5260c
It can be confirmed from the fact that the increase in absorption of the lactone ring near m ⁻¹ is observed at the same time. Note that, when performing polymerization and lactone cyclization at the same time, if necessary, a known ester exchange catalyst or esterification catalyst may be used as the lactone cyclization catalyst, but in the case of using the lactone cyclization catalyst,
Since the polymer may be markedly colored, it is preferable not to use a lactone cyclization catalyst. When a lactone cyclization catalyst is used, a tertiary amine such as triethylamine is preferable from the viewpoint of coloring.

A method for polymerizing a monomer component containing a monomer having an acid group together with a 2- (hydroxyalkyl) acrylic acid ester and simultaneously cyclizing the lactone will be described in detail below. Examples of the 2- (hydroxyalkyl) acrylic acid ester include compounds represented by the general formula (1), and these may be used alone or in combination of two or more. 2- in the monomer component
The ratio of (hydroxyalkyl) acrylic acid ester is
Although not particularly limited, 10 to 80% by weight, preferably 20 to 70% by weight, and more preferably 3% of the total monomer components.
It is preferably from 0 to 60% by weight. If the amount of the 2- (hydroxyalkyl) acrylic acid ester is too large, the solubility of the solvent and the viscosity are increased, and the polymer is precipitated during the polymerization or the workability is deteriorated. On the other hand, if the amount is too small, the ratio of the lactone ring structure is too small, so that sufficient crosslinkability and strength may not be obtained.

Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid, itaconic acid, maleic acid monoester and itaconic acid monoester, and acids such as maleic anhydride and itaconic anhydride. Examples thereof include a monomer having an anhydride group, a monomer having a phosphoric acid group, a monomer having a sulfonic acid group, a monomer having a phenol group, and the like, and (meth) acrylic acid is preferable. These may be used alone or in combination of two or more. The proportion of the monomer having an acid group in the monomer component is not particularly limited, but it is preferably 5 to 70% by weight, preferably 15 to 60% by weight based on the total monomer components. If the amount of the monomer having an acid group is too large,
This leads to a decrease in solvent solubility and an increase in viscosity, resulting in precipitation of a polymer during polymerization and a decrease in workability. On the other hand, if the amount is too small, quantitative lactone cyclization may not occur.

The monomer component preferably contains (meth) acrylic acid ester in addition to the 2- (hydroxyalkyl) acrylic acid ester and the monomer having an acid group, and may further contain other copolymers, if necessary. It may contain a polymerizable monomer. Examples of the (meth) acrylic acid ester include (meth) acrylic acid methyl ester,
Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (meth ) 2-Ethylhexyl acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and the like. Among these, methyl (meth) acrylate and (meth) acrylate are particularly preferable. Ethyl acrylate, (meth) acrylic acid n-
Those having a small number of carbon atoms in the ester group such as propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate are preferable. These may be used alone or in combination of two or more.

The proportion of the (meth) acrylic acid ester in the monomer component is not particularly limited, but the proportion of the 2- (hydroxyalkyl) acrylic acid ester and the monomer having an acid group in the total monomer component is the above. In order to obtain a preferable ratio, it is preferable that it is 0 to 80% by weight based on the total monomer components. Examples of other copolymerizable monomers used as necessary include, for example, styrene, vinyltoluene, α-methylstyrene, acrylonitrile, methyl vinyl ketone, ethylene, propylene, vinyl chloride, vinyl acetate and the like. Can be mentioned. Among these,
Styrene, α-methylstyrene, acrylonitrile,
It is preferable in that the heat resistance can be further improved.
These may be used alone or in combination of two or more.

The proportion of the copolymerizable monomer in the monomer component is not particularly limited, but is preferably 30% by weight or less. The method of adding the monomer components during the polymerization / lactone cyclization reaction is not particularly limited, and the whole amount may be charged all at once, or a part thereof may be charged all at once and the rest may be added dropwise, or the entire amount may be added dropwise. However, from the viewpoint of heat generation amount control, it is preferable to charge a part of them all at once and drop the rest, or drop the entire amount. The solvent used in the polymerization / lactone cyclization reaction is not particularly limited, but, for example, a solvent used in a usual radical polymerization reaction can be used, and examples thereof include tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. Ethers; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate; methanol, ethanol, isopropanol, n-butanol, ethylene Alcohols such as glycol monomethyl ether and propylene glycol monomethyl ether;
Aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform, dimethyl sulfoxide; and the like. In particular, when the boiling point of the solvent used is too high, the residual volatile content in the obtained curable resin composition increases, so that the polymer can be dissolved at the treatment temperature, and the boiling point is 50%.
It is preferably about 200 ° C. Among the ethers, ketones and esters, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are preferable from the viewpoint of solubility of the polymer. Further, the curable resin composition of the present invention can be preferably used for a curable resin composition for a color filter member, but in this case, diethylene glycol dimethyl ether, cyclohexanone, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc. The boiling point is 100 ~ 20
A solvent having a temperature of 0 ° C, preferably 120 to 180 ° C may be used. These solvents may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but is, for example, 5 to 90% by weight, preferably 10 to 80% by weight, and more preferably 30 to 75% by weight based on the total amount of the reaction solution.

At the time of the above-mentioned polymerization / lactone cyclization reaction, a polymerization initiator which is usually used may be added, if necessary. Specific examples of the initiator are not particularly limited, but for example, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate,
t-butylperoxy-2-ethylhexanoate, t
-Organic peroxides such as amylperoxy-2-ethylhexanoate; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis ( 2,4-dimethylvaleronitrile), azo compounds such as dimethyl 2,2′-azobis (2-methylpropionate); and the like. Among these, t-butylperoxy-2-ethylhexanoate and dimethyl 2,2′-azobis (2-methylpropionate) are preferred from the viewpoints of decomposition temperature, availability and handling. preferable. These may be used alone or in combination of two or more. The amount of the initiator used may be appropriately set according to the combination of monomers used, reaction conditions, etc., and is not particularly limited. The method of adding the initiator is not particularly limited, and the whole amount may be charged all at once,
One part may be charged all at once and the rest may be dropped, or the entire amount may be dropped. Further, it is preferable to add the monomer component together with the monomer component because the reaction can be easily controlled, and it is preferable to add the monomer component even after the monomer component is added, since the residual monomer can be reduced.

During the polymerization / lactone cyclization reaction, in order to adjust the molecular weight, a chain transfer agent which is usually used may be added, if necessary, within a range not impairing the effects of the present invention. Examples of the chain transfer agent include thiol chain transfer agents such as n-dodecanethiol and α-methylstyrene dimer, but preferably, the chain transfer effect is high, residual monomers can be reduced, and n is easily available. -Dodecanethiol is preferred. During the polymerization / lactone cyclization reaction, it is preferable to add the above-mentioned monomer components, a polymerization initiator, a chain transfer agent, etc., and then to perform aging if necessary. During the polymerization / lactone cyclization reaction, water and alcohol are by-produced by the lactone cyclization, so after the reaction and aging as necessary,
It is preferable to perform an operation for dehydration / dealcoholization. As a result, the lactone cyclization rate can be further improved, and at the same time, inhibition of crosslinking by water or alcohol can be prevented. Furthermore, when the curable resin composition of the present invention is used for a curable resin composition for a color filter member, the pigment dispersibility and curability are reduced in the presence of water or alcohol, and the color filter is produced using the resin composition. Although the color purity and the brightness may decrease when a liquid crystal display device is manufactured, this can be prevented by performing dehydration / dealcoholization. The method of dehydration / dealcoholization is not particularly limited, but for example, a method of distilling off under normal pressure or reduced pressure, a method of distilling off dry nitrogen or dry argon while bubbling under normal pressure or reduced pressure, normal pressure or reduced pressure And a method of azeotropically distilling with toluene or cyclohexane. The amount of water / alcohol remaining in the system after the dehydration / dealcoholization operation is 2% by weight or less, preferably 0.5% by weight or less, and most preferably 0.1% by weight or less based on the whole reaction solution. .

In the above polymerization / lactone cyclization reaction,
Structural units derived from 2- (hydroxyalkyl) acrylic acid ester can be quantified almost quantitatively with lactone, but it is not necessary that all structural units derived from 2- (hydroxyalkyl) acrylic acid ester are lactone cyclized. As described above, preferably 40 mol% or more, more preferably 60 mol% or more, most preferably 80 mol% or more of the structural unit derived from the 2- (hydroxyalkyl) acrylic acid ester is lactone-cyclized. . In addition,
The degree of lactone cyclization in the lactone ring-containing polymer can be measured by several methods described below.

<Lactone Cyclization Ratio> The degree of lactonization of the lactone ring-containing polymer can be determined by the lactone cyclization ratio in the above polymerization / lactone cyclization reaction. The lactone cyclization rate does not need to be 100 mol%, preferably 90 mol% or more, and more preferably 95 mol% or more. The lactone cyclization rate is defined by the following formula. Lactone cyclization rate (%) = Lactone cyclized 2- (human benzyloxyalkyl) acrylic acid ester unit amount (mol) / 2- (Hydroxyalkyl) acrylic acid ester unit total amount (mol) × 100 Specifically, the ratio of the monomer units in the polymer calculated from the charged amount and the residual monomer amount, the amount of the acid monomer units remaining without lactone cyclization in the polymer calculated from the acid value, and the generated alcohol amount or hydroxyl group. It can be calculated using the residual amount.
When calculating using the amount of generated alcohol, it is sufficient to sample from the reaction solution after the reaction and aging, and quantify the amount of alcohol present in the reaction solution by gas chromatography. Equal to the amount of 2- (hydroxyalkyl) acrylic acid ester units consumed. When calculating using the residual amount of hydroxyl group, benzoic anhydride and pyridine are added to the reaction solution sampled from the reaction solution after reaction and aging, and the unreacted hydroxyl group derived from 2- (hydroxyalkyl) acrylic acid ester is converted into benzoic acid. After acid esterification, water was added to hydrolyze excess benzoic acid anhydride, and after reprecipitation purification, ¹ H-NMR measurement was performed by drying under reduced pressure, and the amount of phenyl group derived from benzoic acid introduced was measured. The residual amount of the hydroxyl group may be calculated from the quantified amount of the obtained phenyl group, and the residual amount of the hydroxyl group is considered to be equal to the amount of the 2- (hydroxyalkyl) acrylic acid ester unit which is not lactone cyclized.

<Residual Hydroxyl Ratio> The degree of lactonization of the lactone ring-containing polymer can be determined by the hydroxylation residual ratio of the lactone ring-containing polymer. The hydroxyl group residual rate of the lactone ring-containing polymer is preferably 10 mol% or less, and more preferably the hydroxyl group residual rate is 5 mol% or less. The hydroxyl group residual rate is defined by the following formula. Hydroxyl group residual rate [mol%] = 2- (Hydroxyalkyl) in 1 g of polymer
Amount of residual hydroxyl group derived from acrylic acid ester unit [mol] / amount of 2- (human oxyalkyl) acrylic acid ester in 1 g of all monomer components [mol] × 100 The residual hydroxyl group is specifically defined by the above method ( The residual amount of the hydroxyl group measured by the method of quantifying the phenyl group by NMR after converting the hydroxyl group derived from the 2- (hydroxyalkyl) acrylic acid ester unit which is not lactone cyclized into benzoic acid ester, and It may be calculated from the amount of (hydroxyalkyl) acrylic acid ester and the amount of all monomer components.

The content ratio of the lactone ring in the lactone ring-containing polymer is such that the content of the lactone ring is 0.1 mm.
ol / g or more, more preferably 0.3 mmol / g or more, and most preferably 0.5 mmo.
It is preferably 1 / g or more. The content of lactone ring is 0.
If it is less than 1 mmol / g, sufficient crosslinkability tends not to be obtained. The amount of lactone ring means the amount [mmol] of lactone ring contained in 1 g of the polymer. The amount of lactone ring is the same as the above-mentioned lactone cyclization ratio, the ratio of monomer units in the polymer, the amount of acid monomer units remaining without lactone cyclization in the polymer calculated from the acid value, and the residual amount of hydroxyl groups. It can be calculated from
In addition, in the same manner as in the case of the residual amount of hydroxyl group described above, ¹ H-NM
It is also possible to perform R measurement to quantify the amount of lactone ring present from the methylene peak derived from the lactone ring.

The weight average molecular weight of the lactone ring-containing polymer may be appropriately set according to the use of the curable resin composition and is not particularly limited, but preferably 1,000 to.
1,000,000, more preferably 3,000-5
0,000, most preferably 5,000 to 200,0
It should be 00. If the weight average molecular weight is too small,
The strength after curing becomes insufficient, while if it is too large, the workability tends to deteriorate and it becomes difficult to handle. The lactone ring-containing polymer, if necessary, other than the lactone ring, for example, a hydroxyl group, a double bond group, a functional group such as an acid group,
You may have in the range which does not impair the effect of this invention. In particular, when the curable resin composition of the present invention is used as a negative photosensitive resin composition as described later, it is preferable to have an acid group. The acid group is not particularly limited,
Preferred examples include a carboxyl group and an acid anhydride group. For example, in order to introduce a carboxyl group, a monomer having a carboxyl group such as (meth) acrylic acid may be polymerized and lactone-cyclized together with the 2- (hydroxyalkyl) acrylic acid ester. On the other hand, in order to introduce an acid anhydride group, a monomer having an acid anhydride group such as maleic anhydride may be polymerized with the 2- (hydroxyalkyl) acrylic acid ester.

The active hydrogen group contained in the active hydrogen group-containing compound, which is an essential component of the curable resin composition of the present invention, is not particularly limited as long as it is an active hydrogen group capable of reacting with a lactone ring. , Amino groups, mercapto groups and the like. The mercapto group is preferable because it can react with a lactone ring to form a thioester bond and has high reactivity. The amino group is preferable because it has high reactivity and can form an amide bond having excellent heat resistance and strength. The hydroxyl group is most preferable because it can react with the lactone ring to form an ester bond having excellent heat resistance, strength and transparency, and the hydroxyl group-containing compound has low toxicity and is easy to handle and obtain.

When the lactone ring-containing polymer has no functional group other than the lactone ring, examples of the active hydrogen group-containing compound include the following compounds 1) or 2). When the lactone ring-containing polymer has a functional group X (for example, a carboxyl group or an acid anhydride group) in addition to the lactone ring, the following 3) may be mentioned. 1) A low molecular weight compound or polymer having two or more active hydrogen groups in the same molecule. However, two or more active hydrogen groups are
It may be the same or different. Specific examples thereof include, but are not limited to, low molecular weight polyhydric alcohols such as ethylene glycol, propylene glycol, glycerol, pentaerythritol, dipentaerythritol, and triethanolamine; methyl (meth) acrylate /
2-hydroxyethyl (meth) acrylate copolymer, 2
Functionally or higher functional polyethylene glycol, bifunctional or higher functional polypropylene glycol, methyl (meth) acrylate /
A polymer having two or more hydroxyl groups in one molecule such as a polymer obtained by adding an epoxy group-containing compound to a carboxyl group of a (meth) acrylic acid copolymer; ethylenediamine, 2,4
A low molecular weight polyamine such as diaminotoluene; a high molecular weight polyamine such as a polymer obtained by adding ethyleneimine to a methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer; trimethylolpropane Low molecular weight polyvalent mercaptans such as trithioglycolate and pentaerythritol tetrakisthioglycolate; low molecular weight compounds having hydroxyl groups and amino groups such as monoethanolamine and diethanolamine; trimethylolpropane dithioglycolate and pentaerythritol trithioglycolate A low molecular weight compound having a hydroxyl group and a mercapto group;

2) A low molecular weight compound or polymer having at least one active hydrogen group and at least one radically polymerizable double bond in the same molecule. Although not particularly limited, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methyl 2- (hydroxymethyl) acrylate, 2
Ethyl- (hydroxymethyl) acrylate, trimethylolpropane mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Low molecular weight compounds such as dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate At least one molecule such as a polymer obtained by adding glycidyl (meth) acrylate to a carboxyl group of a methyl (meth) acrylate / (meth) acrylic acid copolymer Polymer having one hydroxyl group and one radical polymerizable double bond; and the like.

3) having at least one functional group capable of reacting with the functional group X and at least one active hydrogen group,
Low molecular weight compound or polymer. When the functional group X is a carboxyl group, the functional group capable of reacting with the carboxyl group is not particularly limited, but for example, a distorted cyclic ether group such as an epoxy group or an oxetane group; an ethyleneimine group,
Examples include distorted cyclic imine groups such as azetidine groups; distorted cyclic thioether groups such as ethylene sulfide groups and trimethylene sulfide groups; and oxazoline groups. Specific examples of the compound having a functional group capable of reacting with these carboxyl groups and an active hydrogen group capable of reacting with the lactone ring include:
Although not particularly limited, examples thereof include glycidol and epoxy resin having a hydroxyl group. When the functional group X is an acid anhydride group, the functional group capable of reacting with the acid anhydride group is not particularly limited, and examples thereof include a hydroxyl group, an amino group,
Examples thereof include a mercapto group. Specific examples of the compound having a functional group capable of reacting with an acid anhydride group and an active hydrogen group capable of reacting with a lactone ring are not particularly limited,
For example, those exemplified in 1) above can be mentioned.

The content of active hydrogen groups in the active hydrogen group-containing compound is preferably 0.1 mmol / g or more. It is more preferably 0.3 mmol / g or more, and further preferably 0.5 mmol / g or more. When the content of the active hydrogen group is less than 0.1 mmol / g, sufficient crosslinkability may not be obtained. The amount of the active hydrogen group is, for example, a method in which the active hydrogen group is treated with benzoic anhydride to introduce a phenyl group and then the phenyl group is quantified by NMR, similarly to the measurement of the residual amount of the hydroxyl group described above. Can be measured at. In the curable resin composition of the present invention, the weight ratio of the lactone ring-containing polymer and the active hydrogen group-containing compound, the lactone ring amount and molecular weight of the lactone ring-containing polymer, the active hydrogen group of the active hydrogen group-containing compound It may be appropriately set according to the amount and the molecular weight, and is not particularly limited, but it is preferably lactone ring-containing polymer / active hydrogen group-containing compound = 20/80 to 99.9 / 0.1 (weight ratio), More preferably 30 / 70-9
It is preferably 9.5 / 0.5 (weight ratio). If the ratio of the lactone ring-containing polymer is too low, heat resistance, transparency, etc. will be reduced, while if it is too high, the amount of active hydrogen groups will be insufficient and crosslinking will be insufficient, and strength may be reduced. .

The content of the lactone ring-containing polymer and the active hydrogen group-containing compound in the curable resin composition of the present invention depends on the properties of the lactone ring-containing polymer and the active hydrogen group-containing compound and the use of the curable resin composition. It may be appropriately selected depending on the case, and is not particularly limited. The curable resin composition of the present invention may further contain a curing catalyst for promoting crosslinking, if necessary. As the curing catalyst, for example, known esterification catalysts, transesterification catalysts, etc. may be used and are not particularly limited.
It is preferable that the primary amine is less likely to be colored. The content of the curing catalyst may be appropriately selected depending on the crosslinking temperature and time, the type of active hydrogen group, the amount of lactone ring and active hydrogen group, the type of catalyst, the thickness of the layer to be crosslinked, and is not particularly limited. The amount is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the lactone ring-containing polymer and the active hydrogen group-containing compound. If the amount of the curing catalyst is too small, the crosslinking may not sufficiently occur, while if it is too large, not only is it uneconomical, but coloring tends to occur.

The curable resin composition of the present invention can also contain a radically polymerizable compound and can be cured by a photopolymerization reaction or a thermal polymerization reaction. In particular, when a negative photosensitive resin composition described below is used, curing by a photopolymerization reaction is preferable. As the radically polymerizable compound,
There are oligomers and monomers, and examples of radically polymerizable oligomers include unsaturated polyesters, epoxy acrylates, urethane acrylates, polyester acrylates, and acrylic polymers having a double bond in the side chain. Examples of radically polymerizable monomers include aromatic vinyl-based monomers, vinyl ester monomers, (meth) acrylate-based monomers, and polyfunctional (meth)
Acrylate etc. are mentioned. Of these, polyfunctional (meth) acrylates are particularly preferable in view of the polymerizability and developability of the resulting resin composition, and the physical properties of the coating film after post-baking, and specifically, pentaerythritol tri (meth) acrylate, diester. Pentaerythritol hexa (meth) acrylate and the like are preferable. These radically polymerizable compounds may be used either individually or in combination of two or more.

The content of the radical-polymerizable compound is 5 to 500 parts by weight, preferably 20 to 300 parts by weight, and more preferably 100 parts by weight of the lactone ring-containing polymer and the active hydrogen group-containing compound. Is 10 to 200
It is preferably part by weight. When the curable resin composition of the present invention is cured by a polymerization reaction, the curable resin composition of the present invention should also contain a polymerization initiator necessary for the polymerization reaction together with the radically polymerizable compound. You can As the polymerization initiator, a photopolymerizable initiator and / or a thermal polymerizable initiator can be used, and either one of them may be used alone, or they may be used in combination.

As the photopolymerization initiator, known ones can be used. Specifically, benzoin and its alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1- Acetophenones such as dichloroacetophenone; 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, anthraquinones such as 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4
-Thioxanthones such as diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal;
Benzophenones such as benzophenone; 2-methyl-1
-[4- (methylthio) phenyl] -2-morpholino-propan-1-one or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; acylphosphine oxides; xanthones; Etc. These photopolymerization initiators may be used alone or in combination of two or more.

As the thermal polymerization initiator, known ones can be used, and specifically, cumene hydroperoxide, diisopropylbenzene peroxide,
Organic peroxides such as di-t-butyl peroxide; 2,
Azo compounds such as 2′-azobis (isobutyronitrile); and the like. These thermal polymerization initiators may be used alone or in combination of two or more. The content of the polymerization initiator is 0.1 to 50 parts by weight, preferably 0.5 to 40 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the radically polymerizable compound. preferable. If the amount of the polymerization initiator is too small, it may take a long time to cure or it may be difficult to carry out sufficient polymerization, so that sufficient strength may not be obtained. On the other hand, if the polymerization initiator is blended in an amount exceeding the above range, not only it becomes uneconomical, but the coating film may be colored and the strength may be lowered.

The curable resin composition of the present invention may be diluted with a diluent, if necessary. As the diluent, the radically polymerizable compound or a suitable solvent can be used. The amount of the diluent used may be appropriately set according to the optimum viscosity when the resin composition is used, but for example, it is preferably 5 to 500 parts by weight with respect to 100 parts by weight of the resin composition. The curable resin composition of the present invention,
A colorant may be included. As the colorant, known dyes and pigments can be used, and among them, pigments are preferable. As the pigment, specifically, the color index C
I (The Society of Dyers and
Pigments (Pigment) by Colorists
organic pigments such as organic compounds classified as "ment";
Inorganic pigments such as metal oxides or composite oxides; and the like. You may use these colorants individually or in mixture of 2 or more types. The amount of the colorant used is usually 0.1 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 10 to 120 parts by weight, and most preferably 100 parts by weight of the solid content in the curable resin composition. Is preferably 30 to 110 parts by weight.

The curable resin composition of the present invention may contain a dispersant. In particular, the dispersant is preferably used in combination with the colorant. Examples of the dispersant include a surfactant, a pigment intermediate, a dye intermediate, and a polymer dispersant. Examples of intermediates of pigments and intermediates of dyes include, for example, a base organic dye, a hydroxyl group, a carboxyl group,
A derivative of an organic dye having a substituent such as a sulfonic acid group introduced therein is preferable. The amount of these dispersants used is usually 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, and more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the colorant.
It is desirable that the amount is 1 part by weight, most preferably 1 to 10 parts by weight.

The curable resin composition of the present invention may further contain, if necessary, fillers such as aluminum hydroxide, talc, clay and barium sulfate, defoaming agents, coupling agents, leveling agents, sensitizers, Known additives such as a release agent, a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, a polymerization inhibitor and a thickener may be added. Further, a novolac type epoxy resin, a bisphenol type epoxy resin, an alicyclic epoxy resin, an epoxy resin such as triglycidyl isocyanurate, an epoxy curing agent such as dicyandiamide or an imidazole compound, or a dioxazoline compound may be contained. The content of these may be appropriately set within a range that does not impair the effects of the present invention.

The curable resin composition of the present invention can form a crosslinked product by intermolecularly crosslinking a lactone ring and an active hydrogen group. The crosslinking can be easily performed by heating. it can. The temperature and time required for crosslinking are
Type of active hydrogen group, amount of lactone ring and active hydrogen group,
It may be appropriately selected depending on the amount and type of the catalyst to be described later, the thickness of the layer to be crosslinked, and the like, and the temperature is not particularly limited,
When the curing catalyst described below is not used, 100 ° C or higher,
It is preferably 150 ° C or higher, and when a curing catalyst is used,
50 ° C or higher, preferably 100 ° C or higher,
The time is 1 minute to 3 hours, preferably 5 minutes to 2 hours.

The crosslinked product obtained from the curable resin composition of the present invention is excellent in heat resistance, transparency and strength.
It can be suitably used for applications requiring heat resistance, transparency and strength such as paints, coating materials, transparent substrates and display materials. In particular, the crosslinked product obtained from the curable resin composition of the present invention is excellent in heat resistance, transparency and strength even in a thin film state, and the curable resin composition of the present invention is used for a protective layer of various electronic elements, It is suitable for color filter members. In particular, the curable resin composition of the present invention is suitable as a curable resin composition for color filter members. Microfabrication is required to manufacture color filters,
The curable resin composition of the present invention is further blended with a necessary compound to form a negative photosensitive resin composition (negative resist),
You may directly perform fine processing by photolithography process,
When the curable resin composition of the present invention is non-photosensitive,
After curing, fine processing may be performed by a photolithography-etching process using a positive resist. Since the number of steps is small, it is preferable to use a negative photosensitive resin composition. When the curable resin composition for a color filter member is used, the total content of the lactone ring-containing polymer and the active hydrogen group-containing compound is 0.1 in the resin composition.
Is preferably 50 to 50% by weight, more preferably 0.5 to 40% by weight, still more preferably 1 to 30% by weight.
It should be If it is out of this range, workability and coating film strength may decrease.

The color filter of the present invention has a resin layer formed by curing the curable resin composition of the present invention provided on a substrate. A color filter is an optical filter that is necessary for colorization of pixels and has a fine pixel of at least three primary colors on a transparent substrate and a black matrix that separates the pixels from each other. Generally, the three primary colors are red (R) and green ( G) and blue (B) are used. Specifically, the color filter member includes three primary color (RGB) pixels, a resin black matrix, a protective film, and a columnar spacer. In the color filter of the present invention, at least one of the members constituting the filter may be formed by curing the curable resin composition, but at least R
A preferred embodiment is a color filter in which GB pixels, preferably all members are formed of the curable resin composition of the present invention.

The curable resin composition for a color filter member is preferably a photosensitive resin composition containing the radically polymerizable compound and the photopolymerization initiator.
Specifically, the curable resin composition for color filter members,
When used for RGB pixels, 3 for each of red, green, and blue
When it is used as a resin black matrix, it further contains a primary color pigment, and when it is used as a protective film member or columnar spacer, it further contains a black pigment.
The pigment may not be included. When it contains a pigment,
It may also contain a dispersant. Specifically, the color filter of the present invention is preferably prepared, for example, as follows by using the curable resin composition of the present invention as a photosensitive resin composition.

1) A photosensitive resin composition containing a pigment is coated on a transparent substrate such as glass, preferably alkali-free glass or transparent plastic, by a known method such as a spin coating method or a spray method, and then dried. Make a coating film. A spin coating method is preferably used as the coating method. Drying conditions include room temperature to 120 ° C, preferably 60 ° C to 1
A method of heating and drying at a temperature of 00 ° C. for 10 seconds to 60 minutes, preferably 30 seconds to 10 minutes under normal pressure or vacuum is preferable. 2) After that, a photomask (patterning film) provided with openings corresponding to a desired pattern shape is placed on the coating film in a contact state or a non-contact state, and light is irradiated to cure the photomask. In the present invention, light means not only visible light but also radiation such as ultraviolet rays, X-rays and electron beams, and ultraviolet rays are most preferable. Generally, a high pressure mercury lamp is preferably used as the ultraviolet ray source.

3) After irradiation with light, development is carried out with a solvent, water, an alkaline aqueous solution or the like. Of these, an alkaline aqueous solution is preferable because it has a low environmental load and enables high-sensitive development. As the alkaline component, potassium hydroxide, sodium hydroxide, sodium carbonate and the like are preferable. The concentration of alkali is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight. If the alkali concentration is lower than the above range, the dissolving power is too low, and conversely, if the alkali concentration is high, the dissolving power is too high and the developability may be poor. Further, a surfactant may be added to the alkaline aqueous solution. The coating film formed from the curable resin composition of the present invention is excellent in tack-free property even before exposure, so that it can be easily peeled off even when a photomask is placed in a contact state. Therefore, the pattern can be reproduced accurately.

First, the above steps 1) to 3) are performed using a photosensitive resin composition containing a black pigment to form a resin black matrix, and then the pigments are red (R), green (G),
The above steps 1) to 3) are repeated sequentially changing to blue (B) to form R, G, and B pixels on the substrate to produce RGB pixels. Next, in order to protect the RGB pixels formed on the substrate and to improve the smoothness of the surface, a protective film may be formed. As the color filter protective film, a known thermosetting resin or photocurable resin can be used,
It is preferable to use the curable resin composition of the present invention in terms of coating film strength, smoothness, and low colorability of the resulting color filter protective film.

Further, when the color filter is a color filter for a liquid crystal display device, it is preferable to form a columnar spacer. The columnar spacer can be produced by coating the photosensitive resin composition on the surface on which the spacer is to be formed to a thickness such that the desired spacer height is obtained, and through the above steps 1) to 3). When producing a color filter, it is preferable to heat after development (post-baking) to further accelerate curing and completely remove the remaining solvent when producing each member. Here, the curing means either of the following cases or both. That is, by curing the radical-polymerizable double bond that has not been cured by exposure of the radical-polymerizable compound that is added to have photosensitivity, and reacting the lactone ring with the active hydrogen group, the radical-polymerizable double bond is reacted. The formation of a chemical bond different from the carbon-carbon covalent bond by curing the bond to form a crosslink. Therefore, the curable resin composition of the present invention containing the lactone ring-containing polymer and the active hydrogen group-containing compound becomes a very strong crosslinked product by post-baking and is most preferable. The curing temperature is 1
20-300 degreeC is preferable, 150-250 degreeC is more preferable, 180-230 degreeC is the most preferable. If the post-baking temperature is higher than the above, there is a risk of coloring or impairing the smoothness of the coating film due to thermal decomposition. On the other hand, if it is lower than the above, the progress of curing is low and the coating film strength may decrease. . Post-baking may be performed after development in forming each member, or after forming all members.

The display device of the present invention uses the color filter. Specifically, a liquid crystal display device is preferably mentioned, but the present invention is not limited to this, and a display device using an organic EL or the like may be used. The case of a liquid crystal display device will be described below. In the liquid crystal display device, between the color filter and a color filter substrate provided with an ITO electrode and an alignment film as necessary, and a counter substrate provided with an alignment film, an ITO electrode and a drive element as necessary,
A liquid crystal display device incorporating a liquid crystal display panel, in which a liquid crystal spacer is kept at a constant interval, a liquid crystal substance is sealed in the interval, the orientation of the liquid crystal is changed by an electric signal, and the light transmittance is changed to perform color display. is there. LCD operating mode,
As a driving method, a known driving method can be used. Among them, the TFT method is preferable in terms of display quality, response speed and the like.

As the liquid crystal spacer, a well-known fine particle spacer, a columnar spacer made of a photosensitive resin or the like can be used. Among them, a columnar spacer formed by using the curable resin composition of the present invention as a photosensitive resin composition. Is preferred. The color filter substrate and the counter substrate are provided with an alignment film having an alignment according to the operation mode of each liquid crystal and a driving method, and if necessary, fine protrusions (ribs), a polyimide alignment film is preferably used. To be In addition to polyimide, the curable resin composition of the present invention may be used as the photosensitive resin composition for the rib. Further, it is necessary to dispose a deflection plate and an optical compensation film according to the operation mode and driving method of each liquid crystal on the outer side of the color filter substrate and the counter substrate.

[0049]

EXAMPLES Each example of the present invention is described below as an example and a comparative example. Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition,
In the following Examples and Comparative Examples, the description of "part" indicates "part by weight", and the description of "%" indicates "% by weight". [Production Example 1] A separable flask equipped with a cooling tube was prepared as a reaction tank, 426 parts of diethylene glycol dimethyl ether (hereinafter abbreviated as "DMDG") were charged, and after nitrogen substitution, the temperature was raised to 90 ° C by heating in an oil bath. Warmed.

On the other hand, as a monomer dropping tank, ethyl 2- (hydroxymethyl) acrylate (hereinafter referred to as "E") was placed in a beaker.
60 parts of methacrylic acid (hereinafter abbreviated as “MA”)
66 parts, methyl methacrylate (hereinafter referred to as "MM")
A)), t-butylperoxy-2-ethylhexanoate (NOF "Perbutyl O"; hereinafter abbreviated as "PBO") 3 parts, and thoroughly stirred and mixed to prepare, As a chain transfer agent dropping tank, n-
6 parts of dodecanethiol (hereinafter abbreviated as "n-DM"), D
24 parts of MDG was added, and a well-mixed mixture was prepared. After the temperature of the reaction tank became stable at 90 ° C., the dropping was started from the monomer dropping tank and the chain transfer agent dropping tank to start the polymerization. 18 drops each while keeping the temperature at 90 ℃
It took 0 minutes. 60 minutes after the dropping is completed, PBO
0.3 part was added. After that, PBO was reduced to 0 every 60 minutes.
A total of 5 times (1.5 parts) of 3 parts each was added. Meanwhile, the temperature of the reaction vessel was maintained at 90 ° C. After the last PBO was added, the mixture was aged for 60 minutes, cooled to room temperature, sampled, and the amount of residual monomer and generated alcohol in the system and the amount of residual hydroxyl group were measured by the methods described below.

Next, a distillation tool and a nitrogen gas introduction pipe were attached to the reaction tank, and bubbling of nitrogen gas and temperature increase of the oil bath were started. The temperature of the oil bath was raised to 150 ° C. while distilling water and alcohol in the system out of the system. When the amount of distillate decreases, sampling is performed and the residual water content is measured by the Karl Fischer type automatic water content measuring device.
After confirming that the water content in the system became 1000 ppm or less, the system was cooled to room temperature to obtain a lactone ring-containing polymer as a polymer solution. [Production Example 2] As a monomer dropping tank, 120 parts of EHMA,
A lactone ring-containing polymer was obtained as a polymer solution in the same manner as in Production Example 1 except that 81 parts of MAA, 99 parts of MMA, and 3 parts of PBO were thoroughly stirred and mixed.

[Production Example 3] EHM was used as a monomer dropping tank.
A180, MAA105, MMA15, PBO3
A lactone ring-containing polymer was obtained as a polymer solution in the same manner as in Production Example 1, except that the well mixed parts were used. [Comparative Production Example 1] A separable flask equipped with a cooling tube was prepared as a reaction tank, 426 parts of DMDG was charged, the atmosphere was replaced with nitrogen, and then heated in an oil bath to raise the temperature to 90 ° C.
On the other hand, as a monomer dropping tank, 2-hydroxyethylmethacrylate (hereinafter abbreviated as "HEMA") 9 in a beaker.
0 part, 54 parts of MAA, 156 parts of MMA, and 3 parts of PBO were added and well stirred and prepared. As a chain transfer agent dropping tank, 6 parts of n-DM and 24 parts of DMDG were put into a beaker, and well stirred and prepared. .

After the temperature of the reaction tank became stable at 90 ° C., the dropping was started from the monomer dropping tank and the chain transfer agent dropping tank to start the polymerization. The dropping was performed for 180 minutes while maintaining the temperature at 90 ° C. 60 minutes after the dropping was completed, 0.3 part of PBO was added. After that, PB every 60 minutes
0.3 part of O was added three times in total (0.9 parts). Meanwhile, the temperature of the reaction vessel was maintained at 90 ° C. After the last PBO was added, the mixture was aged for 60 minutes and then cooled to room temperature to obtain a polymer solution for comparison. [Comparative Production Example 2] 90 parts of benzyl methacrylate (hereinafter abbreviated as “BzMA”) and MAA5 as a monomer dropping tank
4 parts, MMA 156 parts, and PBO 3 parts were well mixed with stirring in the same manner as in Comparative Production Example 1, except that
A polymer solution for comparison was obtained.

Each analysis of the polymer solutions of the lactone ring-containing polymers obtained in the above Production Examples 1 to 3 and the polymer solutions obtained in Comparative Production Examples 1 and 2 was carried out as follows. The results are shown in Table 1. (Weight average molecular weight) GPC device (Showa Denko KK "S
Hodex GPC System-21H ") was used for measurement in terms of polystyrene. (Acid Value) Polymer solution 0.5 to 1 g, acetone 80 m
1 and 10 ml of water were added and stirred to dissolve uniformly,
Using 0.1 mol / LKOH aqueous solution as a titration solution, titration was performed using an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., COM-555) to measure the acid value of the solution.

On the other hand, acetone 2 was added to 0.3 g of the polymer solution.
After adding and dissolving ml, the solution is naturally dried at room temperature,
After vacuum drying (140 ° C / 5mmHg) for 3 hours,
The sample was allowed to cool in a desiccator and weighed. Then, again in the same manner as above, acetone is added to dissolve it, and it is naturally dried,
The operation of drying under reduced pressure and measuring the weight was repeated until the weight became constant, and the nonvolatile content of the polymer solution was calculated from the weight loss. Then, the acid value of the polymer was calculated from the acid value of the solution and the nonvolatile content of the solution. (Amount of residual monomer) Regarding the reaction solution (polymer solution in the comparative example) sampled after the completion of the polymerization reaction and aging, a gas chromatograph (manufactured by Shimadzu Corporation "GC-") was used.
14A ", carrier gas: helium) and quantified by a calibration curve of each monomer.

(Residual Amount of Hydroxyl Group) First, the following procedure is performed.
The hydroxyl group derived from the 2- (hydroxyalkyl) acrylic acid ester unit which was not lactone cyclized was converted into a benzoic acid ester, and further purified. That is, the polymerization reaction
After the aging was completed, 2.5 g of the reaction solution sampled, 1.5 to 2 g of benzoic anhydride and 5.0 g of pyridine were weighed in a flask and stirred to dissolve uniformly, and then the flask was adjusted to 100 ° C. It was immersed in an oil bath and stirred for 1 hour. Next, 1.0 g of distilled water was added, and the mixture was further stirred for 1 hour. After that, the flask was removed from the oil bath and purified by reprecipitation by using hexane / toluene = 1/1 (v / v) as a reprecipitation solvent, and the obtained powder was dried under reduced pressure for 3 hours (70 ° C. /
5 mmHg).

Sample 200 obtained as described above
mg, chloroform as an internal standard substance 30-40 m
g, about 3 dimethyl sulfoxide-d6 as an NMR solvent
g in a screw tube, shaken and mixed to dissolve well, and an NMR apparatus ("GEMINI 200" manufactured by Varian Co., Ltd.) is used.
0 ") was used for ¹ H-NMR measurement. The amount of phenyl groups was calculated from the integral ratio of the phenyl group peak (δ7.4 to 8.2, 5H) and the chloroform peak (δ8.3, 1H) in the obtained NMR chart, and the polymer weight and chloroform weight.
Then, from the amount of phenyl groups to the residual amount of hydroxyl groups (mmol /
g) was calculated. (Hydroxyl group residual rate) From the residual hydroxyl group amount measured by the above method, the hydroxyl group residual rate was calculated according to the following formula. Hydroxyl group residual rate [mol%] = residual hydroxyl group amount [mmol / g] / (preparation 2-
(Hydroxyalkyl) acrylic acid ester amount [mmol] / total amount of charged monomers
[g]) × 100 (Calculation from lactone ring content-residual amount of hydroxyl group) Calculate the molar ratio of polymerized monomer (monomer unit ratio in polymer) from the amount of residual monomer and the amount of charged monomer measured by the above method. Then, the amount of the acid monomer unit remaining in the polymer without lactone cyclization was calculated from the acid value of the polymer measured by the above method. Then, lactone cyclization was carried out based on three values, that is, the residual amount of the hydroxyl group per 1 g of the polymer measured by the above method, the molar ratio of the polymerized monomers, and the amount of the acid monomer unit remaining without lactone cyclization in the polymer. The amount of (hydroxyalkyl) acrylate unit was calculated, and the amount of lactone ring (mmol / g) per 1 g of the polymer was calculated. The amount of the lactone-cyclized 2- (hydroxyalkyl) acrylic acid ester unit is equal to the amount of lactone ring.

(Lactone cyclization rate) Calculation from residual amount of hydroxyl group The lactone cyclization rate (mol%) was calculated from the amount of lactone cyclized 2- (hydroxyalkyl) acrylate unit calculated by the above method. . Calculation from the amount of alcohol generated Using the same gas chromatograph for the sample used to measure the amount of residual monomer, the amount of alcohol generated was quantified from the calibration curve of methanol and ethanol, and the lactone cyclization rate (mol%) ) Was calculated. The amount of the generated alcohol was consumed for lactone cyclization 2
Equal to the amount of-(hydroxyalkyl) acrylic acid ester units.

[0059]

[Table 1]

[Examples 1-1 to 1-3] Using each of the polymer solutions obtained in Production Examples 1 to 3, 100 parts of each polymer solution diluted with DMDG to 20% and 1,3-
2.5 parts of propanediol and 0.15 parts of triethylamine (hereinafter abbreviated as “TEA”) are added at 30 ° C. to 30 parts.
A curable resin composition was obtained by mixing well for a minute to form a uniform solution. The obtained curable resin composition is 5 cm × 5 c
m was coated on the glass substrate by spin coating to form a uniform coating film having a thickness of 2 μm, which was then heated at 180 ° C. for 1 hour to be cured. After curing, a heating test of heating at 250 ° C. for 1 hour was performed, and the coloring after the heating test was visually confirmed. Further, the surface condition after the heating test was measured using a surface roughness meter. The results are shown in Table 2.

[Comparative Example 1-1] The polymer solution obtained in Comparative Production Example 1 was diluted to 20% with DMDG to obtain 100%.
Parts, 4.0 parts of tolylene 2,4-diisocyanate, and 0.1 parts of TEA are stirred at 0 ° C. to form a uniform solution,
A resin composition for comparison was obtained. Immediately after obtaining the resin composition for comparison, it was applied on a 5 cm × 5 cm glass substrate by spin coating to form a uniform coating film with a thickness of 2 μm, and then heated at 70 ° C. for 1 hour to cure. Let 25 after curing
A heating test of heating at 0 ° C. for 1 hour was performed, and the coloring after the heating test was visually confirmed. Further, the surface condition after the heating test was measured using a surface roughness meter. The results are shown in Table 2.

[0062]

[Table 2]

Example 2-1 100 parts of the polymer solution obtained in Production Example 2 diluted with DMDG to 10%,
And 0.05 part of TEA were heated to 100 ° C. and mixed with stirring to form a uniform solution. Then, after cooling to room temperature,
10 parts of dipentaerythritol tetraacrylate as a radically polymerizable compound having an active hydrogen group, 0.9 part of benzophenone as a photopolymerization initiator, 0.02 part of p, p'-diethylaminobenzophenone, and 2,2-bis (o- Chlorophenyl) -4,5,4'5'-tetraphenyl-1,2-biimidazole (0.08 part) was well mixed with stirring to obtain a photosensitive resin composition.

The following performance test was conducted using the obtained photosensitive resin composition. The results are shown in Table 3. (Developability) After coating the photosensitive resin composition on a 5 cm × 5 cm glass substrate by spin coating, the temperature is 100 ° C.
And dried for 5 minutes to form a uniform coating film having a thickness of 2 μm.
The light quantity was changed on the coating film through a photomask having a predetermined pattern with an ultra-high pressure mercury lamp (light quantity [mJ / cm ² ] = 50, 10).
(0, 200) UV irradiation was performed to cure the coating film. Then, it was developed using a 0.1% KOH aqueous solution at 25 ° C. as a developing solution to form a line and space having a width of 20 μm.
After the development, the sample was washed with pure water and post-baked at 190 ° C. for 40 minutes to obtain a completely cured sample. The following samples were evaluated for the obtained samples. Exposure sensitivity; minimum light intensity [m when a good pattern is formed
J / cm ² ] is ∘: 50, ∘: 100, and Δ: 200. Pattern shape: a sample developed by exposure with a light amount of 200 [mJ / cm ² ] is ∘: No defects are found and the corners are not rounded.

◯: There is a very small portion of the exposed portion or a portion with rounded corners. Δ: The line and space was developed, but some defects were observed and the corners were slightly rounded as a whole. Background stain: A sample exposed and developed with a light amount of 200 [mJ / cm ² ] is ⊚: undeveloped portion has no development residue. ◯: There is a small amount of undeveloped residue on the unexposed area. Δ: A part of the development residue is seen in the unexposed area. X: The undeveloped portion has a noticeable development residue. Development time: When developing a sample exposed with a light amount of 200 [mJ / cm ² ], it can be developed in 20 seconds or less.

Good: Development is possible in 40 seconds or less. Δ: Development is possible in 60 seconds or less. (Heat-resistant transparency) The photosensitive resin composition was applied onto a glass substrate by a spin coating method and then dried at 100 ° C for 5 minutes to form a uniform coating film having a thickness of 2 µm. The coating film was irradiated with ultraviolet rays at a light amount of 200 [mJ / cm ² ] using an ultrahigh pressure mercury lamp without passing through a photomask to cure the coating film. Then, post-baking was performed at 190 ° C. for 40 minutes to obtain a sample whose curing was completed. About the obtained sample, 250 ° C for 1 hour
Visually observe the state after performing a heating test to heat with,
Evaluation was performed according to the following criteria. ⊚: colorless and transparent, ◯: slightly yellow, Δ: yellow, ×: dark yellow (heat-resistant film reduction property), using a surface roughness meter to measure the surface roughness of the sample obtained in the same manner as the heat-resistant transparency evaluation. The surface roughness was measured using a surface roughness meter again after performing a heating test of heating the surface at 250 ° C. for 1 hour. The surface condition before and after the heating test was evaluated according to the following criteria.

⊚: Almost no change after heating after heating. ◯: After heating, it is slightly rougher than before heating, but flat. Δ: After heating, the surface is tentatively flat, but the rough part is noticeable. X: It is uneven after heating. (Fracture Strength) The photosensitive resin composition was applied on a glass substrate by a spin coating method and then dried at 100 ° C. for 5 minutes to form a uniform coating film having a thickness of 5 μm. The coating film is irradiated with ultraviolet rays through a photomask having a predetermined pattern with a light amount of 200 [mJ / cm ² ] using an ultrahigh pressure mercury lamp,
The coating was cured. Then, using a 0.1% KOH aqueous solution at 25 ° C. as a developing solution, the cross section is 15 μm square and the height is 5
A columnar spacer of μm was formed. After the development, the sample was washed with pure water and post-baked at 190 ° C. for 40 minutes to obtain a completely cured sample. With respect to the obtained sample, the load [gf] at the time of breaking the columnar spacer was measured using a micro compression tester at room temperature, and the load value [gf] at the time of breaking
It was evaluated according to the following criteria. ◎: 15 or more, ◯: 10 or more and less than 15, Δ: 5 or more and 10
Less, x: less than 5 (adhesiveness) A photosensitive resin composition is applied onto a glass substrate by a spin coating method, and then dried at 100 ° C. for 5 minutes,
A uniform coating film having a thickness of 2 μm was formed. To the coating film, 100 [mJ /
cm ² ], and the coating film was cured by irradiation with ultraviolet rays. Then, post-baking is performed at 190 ° C. for 40 minutes,
A sample of which curing was completed was obtained. The adhesion of the obtained sample was measured by a cross-cut test method (JIS-K5400), and scored according to JIS-K5400, and evaluated according to the following criteria. ◎: 9 points or more, ○: 7 points or more and less than 9 points, △: 5 points or more 7
Less than, x: less than 5 [Example 2-2] DM was added to the polymer solution obtained in Production Example 2.
100 parts diluted with DG to 10%, and TEA
0.05 part was heated to 100 ° C. and mixed with stirring to form a uniform solution. Then, after cooling to room temperature, 1 part of 1,3-propanediol, 10 parts of pentaerythritol tetraacrylate as a radical polymerizable compound, 0.9 part of benzophenone as a photopolymerization initiator, and 0.02 of p, p′-diethylaminobenzophenone. Parts and 0.08 parts of 2,2-bis (o-chlorophenyl) -4,5,4'5'-tetraphenyl-1,2-biimidazole were thoroughly stirred and mixed to obtain a photosensitive resin composition. .

A performance test was conducted in the same manner as in Example 2-1 using the obtained photosensitive resin composition. The results are shown in Table 3. [Comparative Example 2-1] 100 parts of the polymer solution obtained in Comparative Production Example 1 diluted with DMDG to 10%, pentaerythritol tetraacrylate as a radically polymerizable compound 10 parts, and benzophenone as a photopolymerization initiator.
9 parts, p, p'-diethylaminobenzophenone 0.0
2 parts, and 2,2-bis (o-chlorophenyl)-
0.08 part of 4,5,4'5'-tetraphenyl-1,2-biimidazole was well stirred and mixed to obtain a photosensitive resin composition.

A performance test was conducted in the same manner as in Example 2-1 using the obtained photosensitive resin composition. The results are shown in Table 3.

[0070]

[Table 3]

Example 3-1 A black photosensitive resin composition obtained by adding 5 parts of a black pigment and 0.5 part of a surfactant to 100 parts of the photosensitive resin composition obtained in Example 2-2. A red photosensitive resin composition containing 5 parts of a red pigment and 0.5 part of a surfactant, 5 parts of a green pigment and 0.5 part of a surfactant
A green photosensitive resin composition containing 5 parts of a blue pigment and a blue photosensitive resin composition containing 5 parts of a blue pigment and 0.5 part of a surfactant were prepared. The black photosensitive resin composition was spin-coated on a thoroughly washed alkali-free glass substrate and dried at 100 ° C. for 5 minutes to obtain a uniform coating film having a thickness of 0.5 μm. 500 [mJ / c] is applied to this coating film through a photomask having a predetermined pattern using an ultra-high pressure mercury lamp.
m ² ], and the coating film was cured by irradiating ultraviolet rays. After that, it was developed with a 0.1% KOH aqueous solution at 30 ° C., washed with pure water, and post-baked at 210 ° C. for 30 minutes to form a black matrix. When observed with an optical microscope, no defect was found in the black matrix and the shape was good, and no background stain was found in the unexposed portion.

Further, the red photosensitive resin composition was spin-coated on the black matrix to form 10
After drying at 0 ° C. for 5 minutes, a uniform coating film having a thickness of 2 μm was obtained. This coating film was irradiated with ultraviolet rays through a predetermined photomask with an ultrahigh pressure mercury lamp at a light amount of 200 [mJ / cm ² ] to cure the coating film. Then 0.1% of 30 ℃
After development with KOH aqueous solution and washing with pure water, 210
Post-baking was performed at 30 ° C. for 30 minutes to form red pixels.
Then, in the same procedure, a green pixel was formed using the green photosensitive resin composition and a blue pixel was formed using the blue photosensitive resin composition. Observation with an optical microscope revealed that no defect was found in each pixel and that the pixel had a good shape, and that unexposed areas did not show scumming and the surface had good smoothness.

Further, the photosensitive resin composition obtained in Example 2-2 was spin-coated and dried at 100 ° C. for 5 minutes to obtain a uniform coating film having a thickness of 2 μm. This coating film is passed through a predetermined photomask, and the ultrahigh pressure mercury lamp is used for 200
Ultraviolet irradiation was performed with a light amount of [mJ / cm ² ] to cure the coating film. After that, it was developed with a 0.1% KOH aqueous solution at 30 ° C., washed with pure water, and then post-baked at 210 ° C. for 30 minutes to form a protective film, thereby manufacturing a color filter. When 100 color filters were manufactured by the above procedure, only two defective products were generated due to the black matrix and missing pixels.

Next, a TFT type liquid crystal display panel was produced by a known method using the obtained color filter. The obtained liquid crystal display panel had high color purity, a clear image, and high brightness. [Comparative Example 3-1] The procedure of Example 3-1 was repeated except that the photosensitive resin composition obtained in Comparative Example 2-1 was used.
A color filter was produced. At that time, in the formed black matrix and each pixel, some defects were found and the surface was considerably roughened.

When 100 color filters were produced in the same manner as in Example 3-1, eight defective products were caused by the black matrix and the lack of pixels. Next, a TFT type liquid crystal display panel was produced by a known method using the obtained color filter. The obtained liquid crystal display panel had low color purity, lacked in vividness, and had low brightness.

[0076]

According to the present invention, it is possible to provide a novel curable resin composition capable of obtaining a cured product having excellent physical properties such as heat resistance, transparency and coating film strength. In addition, when the curable resin composition of the present invention is used as a photosensitive resin composition, a uniform coating film can be obtained without causing background stains, deterioration of smoothness, reduction of film thickness, and coloring due to decomposition in a heat treatment in a subsequent step. Since it can be formed with a coating film strength and at the same time can exhibit good exposure sensitivity, an excellent color filter and display device can be provided using the curable resin composition.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/032 G03F 7/032 (72) Inventor Tomomi Makino 5-8 Nishimitabicho Suita City Osaka Prefecture Stock Company Nippon catalyst F-term (reference) 2H025 AA02 AA04 AA10 AA13 AB13 AC01 AD01 BC13 BC42 CA00 CB13 CB14 CB41 CB42 CC17 FA17 2H048 BA02 BA45 BA48 BB02 BB42 BB46 2H091 FA02Y FA0Y FA35Y060X0X0X0X0X0X0 EH106 FD206 GP00

Claims (3)

[Claims] 1. A cured product comprising a polymer having a lactone ring obtained by cyclizing a structural unit derived from 2- (hydroxyalkyl) acrylic acid ester and a compound having an active hydrogen group capable of reacting with the lactone ring. Resin composition. 2. A color filter having a resin layer provided on a substrate, wherein the resin layer is a resin layer obtained by curing the curable resin composition according to claim 1. filter. 3. A display device using a color filter in which a resin layer is provided on a substrate, wherein the resin layer is a resin layer obtained by curing the curable resin composition according to claim 1. A display device characterized by.