JP2001089623A - Curble resin composition and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition having excellent reactivity, and its cured product. SOLUTION: This curable resin composition comprises (A) a fluorine- containing copolymer having a hydroxy group and an epoxy group or either of them, (B) a compound having at least two alkoxyalkylamino groups or hydroxyalkylamino groups in the molecule, and (c) an acid generator of a disulfonylmethane derivative and a tri(alokoxyphenyl)sulfonyl sulfonate derivative or either of them. The cured product is obtained by curing the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable resin composition and a cured product obtained by photocuring the same. More specifically, the present invention relates to a curable resin composition having excellent reactivity and a cured product obtained by curing the same, which is suitable as an antireflection film.

[0002]

2. Description of the Related Art Conventionally, a photocurable resin composition has been used as an antireflection film because it can be quickly formed. Such a photocurable resin composition is disclosed in, for example, JP-A-10-25388, and comprises a fluorinated copolymer having a hydroxyl group and an epoxy group, and a hydroxyalkylamino group or an alkoxyalkylamino group. An alkoxyalkylmelamine compound or a photoacid generator is added as a crosslinking agent to a curable fluorinated copolymer obtained by reacting with a compound having the compound. Such a photocurable resin composition is usually one which is cured by post-curing heating after photocuring, has a low refractive index, and has an antireflection film made of a cured product excellent in hardness and weather resistance. It was intended to obtain.

[0003]

However, the curable resin composition disclosed in Japanese Patent Application Laid-Open No. H10-25388 discloses that a photoacid generator such as a sulfonyl salt or an onium salt is used. At a post-cure temperature of less than 100 ° C., there was a problem that the obtained cured product had poor scratch resistance. On the other hand, if post-curing is performed at a temperature of 100 ° C. or higher in order to sufficiently promote the curing, there may be a case in which a substrate or the like on which a cured product is formed is deformed or deteriorated by heat.

On the other hand, JP-A-10-339947 and JP-A-11-30856 disclose disulfonylmethane derivatives and tri (alkoxyphenyl) sulfonylsulfonate derivatives as acid generators for resist materials. However, when used in combination with a compound having at least two or more alkoxyalkylamino groups or hydroxyalkylamino groups in one molecule,
There is no disclosure, and in applications such as antireflection films,
There was no example used in the reaction of the fluorine-containing copolymer. Thus, the present inventors have conducted intensive studies and as a result, in a use such as an anti-reflection film, among sulfonyl salts and onium salts, a disulfonylmethane derivative or a tri (alkoxyphenyl) sulfonylsulfonate derivative is used as an acid generator. In addition, by using an amino compound having a specific functional group in combination, the fluorine-containing copolymer can be sufficiently cured, and the obtained cured product is post-treated at a low temperature of less than 100 ° C. for a short time, for example. It has been found that even when cured, excellent scratch resistance and the like can be obtained. That is, the present invention is excellent in reactivity and eliminates the need for post-curing, or a cured product having excellent scratch resistance and the like, even under low-temperature, short-time post-curing conditions. It is an object of the present invention to provide a curable resin composition and to provide a cured product suitable for an antireflection film or the like made of such a curable resin composition.

[0005]

Means for Solving the Problems The present invention provides the following (A) to
The present invention relates to a curable resin composition containing the component (C). (A) a fluorine-containing copolymer having a hydroxyl group and / or an epoxy group, or one of the functional groups (B) a compound having at least two alkoxyalkylamino groups or hydroxyalkylamino groups in one molecule (C) disulfonyl Methane derivative and tri (alkoxyphenyl) sulfonylsulfonate derivative, or one of the acid generators

According to this structure, the fluorine-containing copolymer of the component (A) is reacted with the compound of the component (B) using the alkoxyalkyl group or the hydroxyalkyl group of the component (B). In addition, a cross-linking reaction can be highly generated by self-condensing these reactive groups with the acid generator (C). Therefore, even when post-cured under low-temperature and short-time conditions, excellent scratch resistance and the like can be obtained. In order to cause a crosslinking reaction, at least two alkoxyalkylamino groups or hydroxyalkylamino groups are required in one molecule.

[0007] In constituting the curable resin composition of the present invention, the disulfonylmethane derivative is preferably a compound represented by the following general formula (1).

[0008]

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[In the general formula (1), R ¹ and R ² represent a monovalent organic group which may be the same or different from each other;
X and Y each represent a monovalent organic group which may be the same as or different from each other, or a monocyclic or polycyclic structure in which X and Y are connected to each other. ]

In constituting the curable resin composition of the present invention, the tri (alkoxyphenyl) sulfonylsulfonate derivative is preferably a compound represented by the following general formula (2).

[0011]

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[In the general formula (2), R ³ is a group having 1 to 1 carbon atoms.
R ⁴ is an alkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a carbon atom having 7 carbon atoms.
It is an aralkyl group having 10 to 10 or a group having an alicyclic skeleton having 4 to 12 carbon atoms. ]

In constituting the curable resin composition of the present invention, the component (B) is preferably a methylolated melamine compound. When such a melamine-based compound is used, the fluorine-containing copolymer can be efficiently cured, and when the curable resin composition is cured to form a cured product, the composition is excellent for a substrate. Adhesion can be obtained.

In constituting the curable resin composition of the present invention, it is preferable that the component (A) and the component (B) have reacted. By reacting in advance in this manner, the hardness of the obtained cured product can be increased, and phase separation between component (A) and component (B) can be prevented,
Excellent solvent resistance and chemical resistance can be obtained.

[0015] Another embodiment of the present invention relates to a cured product obtained by photocuring the curable resin composition described above. When the cured product is constituted as described above, the fluorine-containing copolymer of the component (A) is strongly cured by the amino compound of the component (B), and the alkoxyalkyl group or the hydroxyalkyl group of the component (B) is used. And, because it has a high molecular weight (cross-linked), while having excellent scratch resistance, etc.,
Excellent adhesion to the substrate can be obtained.

In constituting the cured product of the present invention, it is preferable that the cured product is post-cured. By performing post-curing in this way, not only can the curing proceed further, but also the curing conditions before post-curing can be relaxed. Note that by post-curing at a low temperature for a short period of time, even when a base material or the like is used to support a cured product, it is necessary to effectively prevent thermal deterioration or thermal deformation of the base material or the like. Can be. That is, the curable resin composition of the present invention is characterized in that excellent scratch resistance and the like can be obtained even when post-cured under low-temperature and short-time conditions after photocuring.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The embodiment relating to the curable resin composition of the present invention (first embodiment) and the embodiment relating to an antireflection film which is a cured product thereof (second embodiment) will be specifically described. explain.

[First Embodiment] The first embodiment relates to a curable resin composition containing the following components (A) to (C). (A) a fluorine-containing copolymer having a hydroxyl group and / or an epoxy group, or one of the functional groups (B) a compound having at least two alkoxyalkylamino groups or hydroxyalkylamino groups in one molecule (C) disulfonyl Methane derivative and tri (alkoxyphenyl) sulfonylsulfonate derivative, or one of the acid generators

(1) Component (A) The component (A) is a fluorine-containing copolymer having a hydroxyl group and an epoxy group, or one of the functional groups. Such a fluorine-containing copolymer is, for example, a fluorine-containing monomer, a hydroxyl group-containing monomer, an epoxy group-containing monomer, and, if necessary, another radical polymerizable monomer. It can be obtained by polymerization.

Fluorinated monomers Examples of the fluorinated monomers include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3,3,3-trifluoropropylene, chlorotrifluoroethylene; alkyl perfluorovinyl ethers and the like. Perfluoro (methyl vinyl ether), perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (alkyl vinyl ether) such as perfluoro (isobutyl vinyl ether); perfluoro (propoxypropyl vinyl ether) ) And the like; trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acryl Rate, octafluoropentyl (meth) acrylate, fluorine-containing (meth) acrylates such as heptadecafluorodecyl (meth) acrylate, etc., alone or in combination of two or more.

Of the above-mentioned fluorine-containing monomers, fluoroolefins, perfluoro (alkyl vinyl ether) s, or perfluoro (alkoxyalkyl vinyl ether) s are particularly easy to adjust the fluorine content and have excellent reactivity. Is more preferable. Examples of such a fluorine-containing monomer include hexafluoropropylene, perfluoropropyl vinyl ether and perfluoropropoxypropyl vinyl ether.

The amount of the structural unit derived from the fluorine-containing monomer is preferably in the range of 20 to 70% by mole, when the total amount of the fluorine-containing copolymer is 100% by mole. . The reason for this is that if the amount of the structural unit derived from the fluorine-containing monomer is less than 20 mol%, the fluorine content in the fluorine-based copolymer decreases, and the refractive index of the cured product may not be sufficiently low. That's why. On the other hand, if the amount of the structural unit exceeds 70 mol%, the solubility and transparency of the fluoropolymer in an organic solvent, or the adhesion to a substrate may decrease. Therefore, since the balance between the refractive index of the cured product and the solubility in an organic solvent and the like becomes better, the amount of the structural unit derived from the fluorine-containing monomer is in the range of 25 to 65 mol%. Is more preferable, and the value is more preferably in the range of 30 to 60 mol%.

Hydroxyl-containing monomer Examples of the hydroxyl-containing monomer include 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether,
3-hydroxypropyl vinyl ether, 3-hydroxybutyl vinyl ether, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6
-Hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, etc., alone or in combination of two or more.

The amount of the structural unit derived from the hydroxyl group-containing monomer is preferably in the range of 2 to 70 mol%, when the total amount of the fluorocopolymer is 100 mol%. , More preferably within a range of 5 to 60 mol%, and even more preferably within a range of 10 to 50 mol%. The reason for this is that if the amount of the structural unit derived from the hydroxyl group-containing monomer is less than 2 mol%, the reactivity with the amino compound of the component (B) and the adhesion to the substrate may be significantly reduced. It is. On the other hand, if the amount of the structural unit exceeds 70 mol%, the transparency of the obtained cured product may be reduced, or the value of the refractive index may be increased.

Epoxy Group-Containing Monomers Epoxy group-containing monomers include vinyl glycidyl ether, allyl glycidyl ether, glycidyl (meth)
One type of acrylate, glycidyl crotonate, methyl glycidyl maleate and the like may be used alone or in combination of two or more types.

The amount of the structural unit derived from the epoxy group-containing monomer is defined as 100 mol% based on the total amount of the fluorocopolymer.
In this case, the value is preferably in the range of 2 to 70 mol%, more preferably in the range of 5 to 60 mol%, and more preferably in the range of 10 to 50 mol%. Is more preferable. The reason for this is that when the amount of structural units derived from the epoxy group-containing monomer is less than 2 mol%,
This is because the reactivity with the amino compound of the component (B) and the adhesion to the substrate may be significantly reduced. on the other hand,
If the amount of the structural unit exceeds 70 mol%, the resulting cured product may have reduced transparency or a high refractive index.

Weight Average Molecular Weight The molecular weight of the fluorine-containing copolymer is not particularly limited either. For example, the weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) is 3,000 to 3,000. 2,000,
Preferably, the value is in the range of 000. The reason is that if the weight average molecular weight is smaller than 3,000,
This is because the mechanical strength and viscosity of the obtained fluorinated copolymer may be reduced and handling may be difficult.
If it exceeds 2,000,000, the viscosity becomes excessively high, and conversely, handling may be difficult.
Therefore, the weight average molecular weight of the fluorinated copolymer is 1
The value is more preferably in the range of 000 to 1,000,000, and more preferably in the range of 20,000 to 500,000.

Fluorine content The fluorine content in the fluorine-containing copolymer is not particularly limited, but is preferably, for example, at least 40% by weight, more preferably at least 45% by weight. Is more preferable. If the fluorine content is less than 40% by weight, the refractive index increases, and the properties as an antireflection film or the like may not be exhibited. The fluorine content in the fluorine-containing hydroxy compound polymer can be measured by using the alizarin complexon method. The same applies to the determination of the fluorine content.

Production Method The method for producing the fluorine-containing copolymer as the component (A) is not particularly limited, either. For example, an emulsion polymerization method, a suspension polymerization method, It can be obtained by a bulk polymerization method or a solution polymerization method. Also, these polymerization operations can be appropriately selected from a batch operation, a semi-continuous operation, a continuous operation, or the like.
Further, the polymerization conditions of the fluorinated copolymer are not particularly limited. For example, it is preferable to perform the polymerization at a temperature of 50 to 200 ° C. for 1 to 100 hours.

Further, in producing the fluorine-containing copolymer of the component (A), it is preferable to use an organic solvent because it can be reacted uniformly. Examples of such an organic solvent include esters such as ethyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; cyclic ethers such as tetrahydrofuran;
Amides such as dimethylformamide; and aromatic hydrocarbons such as toluene.

Further, after polymerization of the fluorine-containing copolymer of the component (A), a compound having at least two alkoxyalkylamino groups or hydroxyalkylamino groups in one molecule, which is the component (B) described below, is added. And (A)
It is also preferred to react with the components in advance. The reason for this is that, as described above in part, by pre-reacting the component (A) and the component (B) in this way, phase separation between the component (A) and the component (B) is effectively prevented. Thus, the hardness of the obtained cured product can be increased, and the solvent resistance, chemical resistance, and the like can be improved.

The conditions for preliminarily reacting the component (A) and the component (B) are not particularly limited. For example, the reaction ratio between the component (A) and the component (B) may be changed. The molar ratio is preferably in the range of 1: 100 to 1: 1. However, the final addition amount of the component (B) is, as described later, a value in which the addition amount of the component (B) is within a range of 1 to 100 parts by weight with respect to 100 parts by weight of the component (A). It is preferable to adjust so as to include the amount reacted in advance.

It is also preferable to use an azo initiator in which azo groups are linked by polydimethylsiloxane as a radical generator when polymerizing the fluorine-containing copolymer of the component (A). For example, when VPS1001 or VPS0501 (manufactured by Wako Pure Chemical Industries, Ltd.) is used, a polydimethylsiloxane structural unit can be contained in a fluorine-based copolymer. That is, by including the polydimethylsiloxane structural unit in the molecule, the surface of the cured product obtained can be made smooth and smooth. It is also preferable to use, as another radical generator, an azo initiator in which an azo group is linked by polyethylene glycol. For example, when VPE0201 (manufactured by Wako Pure Chemical Industries, Ltd.) is used, the structural unit of polyethylene glycol can be contained in the fluorine-based copolymer.

(2) Component (B) Kind In the curable resin composition of the first embodiment,
As the component (B), a compound having at least two or more alkoxyalkylamino groups or hydroxyalkylamino groups in one molecule (hereinafter sometimes simply referred to as an amino compound) is contained. By containing the amino compound of the component (B) in this way, it reacts with the hydroxyl group or epoxy group contained in the fluorinated copolymer of the component (A) and the alkoxyalkyl group of the amino compound of the component (B) Alternatively, crosslinking can be performed by reacting a hydroxyalkyl group. Therefore, a cured product having excellent heat resistance and the like can be obtained.

The type of the component (B) is not particularly limited, either. For example, an alkoxyalkylmelamine compound, a hydroxyalkylmelamine compound, an alkoxyalkylurea compound, a hydroxyalkylurea compound, an alkoxyalkylguanamine Compounds, hydroxyalkyl guanamine compounds, glycoluril compounds and the like may be used alone or in combination of two or more.

As the component (B), an alkoxyalkylmelamine compound or a hydroxyalkylmelamine compound is more preferable because of its excellent reactivity and heat resistance. The melamine compound represented by the following general formula (3) is preferably introduced. In addition, in the case of an alkoxyalkylmelamine compound, it becomes possible to react after hydrolyzing an alkoxy group to obtain a hydroxyalkylmelamine compound.

[0037]

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[In the general formula (3), R is a group represented by CH ₂ OCH ₃ . ]

Addition Amount The addition amount of the amine compound as the component (B) is not particularly limited.
It is preferable that the addition amount of the component (B) is within a range of 1 to 100 parts by weight based on 0 parts by weight. The reason for this is
When the addition amount of the component (B) is less than 1 part by weight, (A)
This is because the reaction of the fluorine-containing copolymer as a component becomes insufficient, and the heat resistance and the like of the obtained cured product may decrease.
On the other hand, when the addition amount of the component (B) exceeds 100 parts by weight, the reaction of the fluorine-containing copolymer of the component (A) becomes excessive, and the obtained cured product becomes brittle or has a high refractive index. Because there is. Therefore, the balance between the reactivity and the refractive index of the fluorinated copolymer is better, so that the addition amount of the component (B) is in the range of 10 to 80 parts by weight based on 100 parts by weight of the component (A). And more preferably within a range of 20 to 70 parts by weight.

(3) Component (C) Type In the curable resin composition of the first embodiment,
As the component (C), a disulfonylmethane derivative and a tri (alkoxyphenyl) sulfonylsulfonate derivative, or any one of the acid generators is contained. By including the component (C) in this way, the self-condensation reaction of the methylol group or the like of the amine compound of the component (B) is promoted, and the fluorine-containing copolymer as the component (A) is so-called. Melamine crosslinking and the like can be performed. Therefore, a cured product excellent in heat resistance, adhesion, and the like can be obtained.

Of the component (C), the disulfonylmethane derivative is preferably a compound represented by the general formula (1) as described above. Here, in the general formula (1), R ¹ and R ² are monovalent organic groups which may be the same or different from each other, and more specifically, a hydrogen atom, a carbon atom having 1 to 10 carbon atoms. Alkyl group, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an organic group having 1 to 20 carbon atoms having a hetero atom. Among these R ¹ and R ² , a phenyl group is particularly preferable because of high light absorption.

It is also preferred that X and Y have a monocyclic or polycyclic structure linked to each other. More specifically, it is preferable that X and Y are mutually connected to form a carbon monocyclic structure or a carbon polycyclic structure having 3 to 10 carbon atoms. Further, the carbon single ring structure or the carbon polycyclic structure may be an aliphatic ring or a ring structure having an unsaturated bond. For example, examples of the carbon monocyclic structure having 3 to 10 carbon atoms include cyclobutane, cyclopentane, and cyclohexane. In the general formula (1), the methane moiety to which the X and Y groups are bonded is
A plurality is linked linearly, for example, the number of repetitions is 2
It is also preferable to set the value in the range of 10.

Further, preferred structural examples of the disulfonylmethane derivative are shown in the following formulas (4) to (14). In particular, X and Y
Are linked to each other to form an aliphatic ring, 1,1-bis (phenylsulfonyl) cyclobutane represented by the following formula (4), and 1,1-bis (phenylsulfonyl) represented by the following formula (5) ) Cyclopentane and 1,1-bis (phenylsulfonyl) cyclohexane represented by the following formula (6) are preferred.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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Further, among the component (C), tri (alkoxyphenyl) sulfonylsulfonate derivatives include:
As described above, the compound represented by the general formula (2) is preferable, but more preferably tri (p-methoxyphenyl) sulfonyltrifluoromethanesulfonate and tri (p-methoxyphenyl) sulfonylnonafluorobutanesulfonate , Tri (p-methoxyphenyl) sulfonyl p-toluenesulfonate, tri (p-methoxyphenyl) sulfonyl
(Methoxyphenyl) sulfonylnaphthalenesulfonate, tri (p-methoxyphenyl) sulfonylcamphorsulfonate, tri (p-methoxyphenyl) sulfonylcyclohexylsulfonate, tri (p-ethoxyphenyl) sulfonyltrifluoromethanesulfonate, tri (p-ethoxyphenyl) sulfonylnona One or a combination of two or more of fluorobutanesulfonate, tri (p-ethoxyphenyl) sulfonylcamphorsulfonate, tri (p-phenoxyphenyl) sulfonylnonafluorobutanesulfonate and the like can be mentioned.

It is preferable to use a thermal acid generator together with the above-mentioned acid generator. Examples of such a thermal acid generator include aliphatic sulfonic acid, aliphatic sulfonic acid salt, aliphatic carboxylic acid, aliphatic carboxylic acid salt, aromatic carboxylic acid, aromatic carboxylic acid salt, alkylbenzenesulfonic acid, and alkylbenzenesulfonic acid. One type or a combination of two or more types such as ammonium salts, phosphates, and metal salts may be used. By using such a thermal acid generator in combination, when post-cured after photo-curing,
The reaction between the component (A) and the component (B) can proceed more effectively.

Addition Amount The addition amount of the acid generator as the component (C) is not particularly limited, either. For example, (100 parts by weight of the fluorine-containing copolymer as the component (A) It is preferable that the added amount of the component (C) be a value within the range of 0.1 to 30 parts by weight. The reason for this is that if the amount of the component (C) is less than 0.1 part by weight, the sensitivity decreases, and the component (A)
This is because the reaction with the component (B) becomes insufficient, and the heat resistance and the like of the obtained cured product may decrease. on the other hand,
If the amount of component (C) exceeds 30 parts by weight, (A)
This is because the reaction between the component and the component (B) becomes excessive, and the resulting cured product may become brittle or have a high refractive index. Therefore, the balance between the reactivity and the refractive index of the fluorinated copolymer is better, so that (A)
Component (C) is added in an amount of 0.1 to 100 parts by weight of component.
The value is more preferably in the range of 5 to 20 parts by weight, and even more preferably in the range of 1 to 15 parts by weight.

(4) Additives In the curable resin composition, additives such as a polymer additive, a reactive diluent, a radical photopolymerization initiator, a photosensitizer, a polymerization inhibitor, and a polymerization initiator Auxiliaries, leveling agents, wettability improvers, surfactants, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, inorganic fillers, fungicides, humectants, dye dissolving agents, buffer solutions, chelates It is also preferable to include one kind of agents or a combination of two or more kinds.

[Second Embodiment] The second embodiment is a cured product obtained by curing the curable resin composition containing the components (A) to (C) of the first embodiment (anti-reflection material). This is an embodiment used for the antireflection film 12 in the antireflection film laminate 10 as shown in FIG. Hereinafter, the antireflection film 12 will be described with reference to the antireflection film stack 10 as shown in FIG.

(1) Structure of Composite Antireflection Film As shown in FIG. 1, the antireflection film 12, which is a cured product of the present invention, has a hard coat layer 14 formed on a transparent substrate 16, It can be formed by applying the curable resin composition of the present invention thereon, followed by curing.

Antireflection Film Although the lower the refractive index value of the antireflection film, the more excellent the antireflection effect can be obtained, specifically, a value of 1.7 (−) or less is preferable, and more preferably 1.3 (−). ~ 1.6 (-)
And more preferably in the range of 1.3 to 1.5 (-). The reason for this is that if the refractive index is less than 1.3 (-), the types of usable materials may be excessively limited, while if the refractive index exceeds 1.7 (-). This is because the antireflection effect may be significantly reduced. In addition, it is also preferable that the antireflection film is composed of a high refractive index film and a low refractive index film from the transparent substrate side. With this configuration, a more excellent antireflection effect can be obtained. In this case, it is preferable that the refractive index of the high refractive index film is, for example, a value of 1.5 or more, and the refractive index of the low refractive index film is, for example, a value less than 1.5.

The thickness of the antireflection film is not particularly limited, but is preferably, for example, a value within the range of 50 to 1,000 nm. This is because the thickness is 50
When the thickness is less than nm, the antireflection effect and the adhesion to the substrate may be reduced.
If it exceeds 000 nm, light interference may occur and the antireflection effect may be reduced. Therefore, the thickness of the antireflection film is more preferably set to a value within the range of 50 to 500 nm, and even more preferably set to a value within the range of 60 to 200 nm. When the antireflection film has a multilayer structure, the thickness is preferably a value obtained by multiplying the preferable thickness when the antireflection film has one layer by the number of layers. For example, when two layers of antireflection films are provided, the total thickness should be 100 to
Preferably, the value is in the range of 2,000 nm.

Transparent substrate As the transparent substrate, for example, an inorganic transparent substrate such as soda glass or quartz glass, or a polyester resin, a polycarbonate resin, an acrylic resin, a styryl resin, an arylate resin, a norbornane resin, a triacetyl cellulose resin, or the like. Organic transparent substrates can be mentioned. Particularly, in the application of the anti-reflection film, the transparent base material is more preferably a polyester resin or a polycarbonate resin, because a light weight and a large screen can be obtained.

Hard coat layer The hard coat layer is made of melamine resin, phenol resin, guanamine resin, urea resin, polyacetal resin, polyvinyl acetate resin, epoxy resin, urethane resin, acrylic resin. It is preferable to use a single resin such as a silicone resin or two or more resins. Also,
The thickness of the hard coat layer is not particularly limited, but is preferably, for example, in the range of 1 to 50 μm. The reason is that when the thickness is less than 1 μm,
On the other hand, when the thickness exceeds 50 μm, light interference may occur and the antireflection effect in the antireflection film laminate may be reduced. Therefore, the thickness of the hard coat layer is 2 to 40 μm
Is more preferably set in the range of 3 to 30 μm.

(2) Curing Method Coating Method When applying the curable resin composition of the present invention, it is preferable to use an organic solvent since a coated film having a uniform thickness can be obtained. Preferred organic solvents include the organic solvents used when radically polymerizing the component (A), for example,
Examples thereof include ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, N, N-dimethylformamide, and toluene. Then, by adjusting the amount of the organic solvent added, the viscosity of the curable resin composition,
The value is preferably in the range of 1 to 10,000 cps (25 ° C.), and more preferably in the range of 1 to 1,000 cps (25 ° C.). The reason is that if the viscosity exceeds this range, it may be difficult to form a coating film having a uniform thickness.

The coating method is not particularly limited, and a known coating method can be used. For example, a method such as a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, or an inkjet method can be used. In addition, in order to adjust the rheological properties suitable for various coating methods, it is also preferable to mix various leveling agents, thixotropes, fillers, organic solvents, surfactants, and the like, as necessary.

Light Curing Method When the curable resin composition of the present invention is cured, it is preferable to carry out light curing as described above. For example, as a condition for photocuring, an exposure amount is set to 100
Is preferably within a range of ~3,000mJ / cm ^2, more preferably to a value within the range of 200~2,000mJ / cm ^2, 300~1,000mJ / cm
More preferably, the value is in the range of ² .

Post Cure After the curable resin composition of the present invention is light-cured, it is preferable to perform post cure heating. Specifically, it is preferable to perform post-curing heating at a heating temperature of less than 100 ° C. for 1 minute to 24 hours. By post-curing under such conditions, productivity is improved and the influence of heating on the substrate and the like is reduced. Therefore, it is more preferable to perform post-curing heating at a heating temperature of 90 ° C. or lower for 1 minute to 12 hours.
Post-curing heating is performed at a heating temperature of 80 ° C. or lower for 1 minute to 10 hours.

[0069]

The present invention will be described in more detail with reference to the following examples. Parts and% in Examples are parts by weight and% by weight unless otherwise specified.

[Synthesis Example 1 of Fluorine-Containing Copolymer] A nitrogen autoclave having an internal volume of 1.5 L and equipped with a magnetic stirrer was sufficiently replaced with nitrogen gas. Next, the following raw materials were accommodated in an autoclave. Ethyl acetate: 500 g Perfluoro (propyl vinyl ether): 53.2 g (abbreviated as FPVE) Ethyl vinyl ether (abbreviated as EVE): 50.5 g Hydroxyethyl vinyl ether: 26.4 g (abbreviated as HEVE) Peroxidation Lauroyl: 1.25g

Next, the temperature inside the autoclave was cooled to -50 ° C. using dry ice and methanol. Thereafter, oxygen in the autoclave was removed using nitrogen gas again. Next, 120.0 g of hexafluoropropylene (abbreviated as HFP) was charged, and the temperature was raised. The pressure when the temperature in the autoclave reached 60 ° C. was 5.4 kgf / cm ² . The reaction was continued at 70 ° C. for 20 hours while stirring as it was.
Then, when the pressure dropped to 1.7 kgf / cm ² , the autoclave was cooled with water to stop the reaction. The mixture was left as it was, and after reaching room temperature, the autoclave was opened and unreacted monomers were released to obtain a polymer solution having a solid concentration of 26.4%. The obtained polymer solution was poured into methanol to precipitate a polymer. Thereafter, the resultant was washed with methanol and further dried in a vacuum at 50 ° C. to obtain 220 g of a fluorine-containing copolymer.

The obtained fluorinated copolymer was subjected to GPC
Weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene, glass transition temperature (Tg) according to DSC, and fluorine content according to the alizarin complexon method. Further, the proportion of each monomer component constituting the fluorine-containing copolymer was determined from ¹ H-NMR analysis, ¹³ C-NMR analysis, FT-IR elemental analysis, and the measured fluorine content. Table 1 shows the results.

[Synthesis Example 2 of Fluorinated Copolymer] HEVE
Was replaced with glycidyl vinyl ether (abbreviated as GVE), and a fluorine-containing copolymer was synthesized in the same manner as in Synthesis Example 1 except that the charged amounts of the respective monomers were changed as shown in Table 1. And evaluated. Table 1 shows the obtained results.

[Synthesis Example 3 of Fluorine-Containing Copolymer] As shown in Table 1, as a nonionic reactive emulsifier, Adecaria Soap NE-30 (manufactured by Asahi Denka Kogyo KK) and azo group-containing polydimethyl VPS-1001 as siloxane
(Wako Pure Chemical Industries, Ltd.)
In the same manner as in Synthesis Example 1, a fluorinated copolymer having a polysiloxane segment was synthesized and evaluated. Table 1 shows the obtained results.

[Synthesis Example 4 of Fluorine-Containing Copolymer] As shown in Table 1, as a nonionic reactive emulsifier, Adecaria Soap NE-30 (manufactured by Asahi Denka Kogyo KK) and azo group-containing polydimethyl VPS-1001 as siloxane
(Wako Pure Chemical Industries, Ltd.)
A fluorinated copolymer having a polysiloxane segment was synthesized and evaluated in the same manner as in Synthesis Example 2. Table 1 shows the obtained results.

Example 1 100 g obtained in Synthesis Example 1
And 10 g of an alkoxymethylated melamine compound (trade name MX30, manufactured by Sanwa Chemical Co., Ltd.)
3) and 3 g of 1,1-bis (phenylsulfonyl) cyclohexane (abbreviated as C1) as a photoacid generator.
With a mixed solvent of methyl isobutyl ketone and tert-butanol (mixing ratio = 60/40% by weight) 365
4 g was stirred until it was uniformly dissolved to obtain a curable resin composition solution having a solid content of 3% by weight.

(1) Measurement of reflectivity The obtained curable resin composition solution was coated with a dip coater with a thickness of 3 mm at a pulling rate of 250 mm / min.
It was applied on an acrylic plate having a thickness of 1 mm and dried in an oven at 80 ° C. for 1 minute. Thereafter, ultraviolet rays were irradiated using an exposure machine so that the exposure amount was 300 mJ / cm ² . Further, using an oven, 80 ℃,
Post cure heating was performed for 15 minutes to obtain an antireflection film. It was 115 nm when the film thickness of the obtained antireflection film was measured using an ellipsometer. Then
The acrylic plate on which the antireflection film was formed was attached to a spectrophotometer with a 60 mmφ integrating sphere (U-3410, manufactured by Hitachi, Ltd.), and the reflectance of the antireflection film was measured. Table 2 shows the results. If the reflectance is 2% or less, it can be generally said that the film has a practical antireflection property. If the reflectance is 1.5% or less, it can be generally said that the film has an excellent antireflection property. If it is 1.0% or less, it can be generally said that the composition has extremely excellent antireflection properties.

(2) Evaluation of Scratch Resistance Scratch resistance test was performed on each of the acrylic plates on which the antireflection film was formed for the reflectance measurement.
That is, the surface of each anti-reflection film was adjusted to about 1 kg / c using Kimwipe paper manufactured by Jujo Kimberly Co., Ltd.
The surface of the anti-reflection film was scratched by rubbing 25 times repeatedly under a load of m ² , and the scratches were visually determined based on the following criteria. Table 2 shows the results. It has been found that the lower the adhesion of the coating film to the substrate, the lower the evaluation of the scratch resistance. 〇: No change in the coating film. Δ: slight change in coating film. X: The coating film has remarkable scratches and disappears due to abrasion.

[Examples 2 to 4] An antireflection film was prepared and evaluated in the same manner as in Example 1 except that the fluorinated copolymer synthesized in Synthesis Examples 2 to 4 was used. Table 2 shows the obtained results.

[Examples 5 to 8] In Example 5, 1,1-bis (phenylsulfonyl) cyclopentane (abbreviated as C2) was used as the acid generator of the component (C), and in Example 6, And tri (p-methoxyphenyl) sulfonyltrifluoromethanesulfonate (abbreviated as C3). In Example 7, triphenylsulfonyltrifluoromethanesulfonate (abbreviated as C4) was used.
In Example 8, an antireflection film was formed and evaluated in the same manner as in Example 1 except that 1-naphthyldimethylsulfonyltrifluoromethanesulfonate (abbreviated as C5) was used. Table 2 shows the obtained results.
Shown in

Comparative Examples 1 to 3 In Comparative Example 1, 2,4,6-tris (trichloromethyl) -s was used as a photoacid generator.
-Triazine (abbreviated as C6) was used, and in Comparative Example 2, tris (methanesulfonyloxy) benzene (C7
Abbreviated. In Comparative Example 3, bis (cyclohexylsulfonyl) diazomethane (abbreviated as C8) was used.
And an antireflection film was formed and evaluated in the same manner as in Example 1 except that the respective compositions shown in Table 2 were used. Table 2 shows the obtained results. As is clear from these results, in all of Comparative Examples 1 to 3, since no disulfonylmethane derivative or tri (alkoxyphenyl) sulfonylsulfonate derivative was used as the acid generator, post-curing was performed at 80 ° C. for 15 minutes. When the conditions were adopted, it was found that the scratch resistance was poor.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

According to the curable resin composition of the present invention, a disulfonylmethane derivative or a tri (alkoxyphenyl) sulfonylsulfonate derivative can be used as a component (C) among general sulfonyl salts and onium salts. Since the acid generator consisting of (A) and (B) is selected and used, the component (A) and the component (B) can be rapidly cured. Therefore, even when post-curing is performed at a low temperature for a short time, a cured product having excellent antireflection properties, scratch resistance and the like can be obtained.

Further, according to the cured product of the present invention, it is possible to obtain a low refractive index and excellent scratch resistance without performing post-curing under high temperature and long time conditions. became. Therefore, since the thermal deformation of the substrate can be effectively prevented, the cured product of the present invention can be suitably applied to applications such as an antireflection film and an antifouling film.

[Detailed description of drawings]

FIG. 1 is a view showing an anti-reflection film.

[Explanation of symbols]

 Reference Signs List 10 antireflection film laminate 12 antireflection film 14 hard coat layer 16 transparent substrate

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 317/24 C07C 317/24 C08G 59/34 C08G 59/34 59/68 59/68 C08J 3/24 CEW C08J 3/24 CEW C08K 5/3477 C08K 5/3477 5/41 5/41 5/42 5/42 (72) Inventor Takashi Ukaji 2-11-11 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. Terms (reference) 4F070 AA23 AB02 AB09 AC45 AC46 AC49 AC50 AE08 GA10 GC09 4H006 AA01 AB49 TA02 TB33 TB74 4J002 BD121 BD151 BD161 BE041 BG081 CD191 ET016 EU186 EV217 EV297 FD146 FD157 GH00 4J036 AK09 AK10 DC14 DC14

Claims (6)

[Claims] 1. A curable resin composition comprising the following components (A) to (C). (A) a fluorine-containing copolymer having a hydroxyl group and / or an epoxy group, or one of the functional groups (B) a compound having at least two alkoxyalkylamino groups or hydroxyalkylamino groups in one molecule (C) disulfonyl Methane derivative and tri (alkoxyphenyl) sulfonylsulfonate derivative, or one of the acid generators 2. The curable resin composition according to claim 1, wherein the disulfonylmethane derivative is a compound represented by the following general formula (1). Embedded image [In the general formula (1), even if R ¹ and R ² are the same as each other,
X represents a monovalent organic group which may be different,
Is a monovalent organic group which may be the same or different from each other,
Alternatively, it is a monocyclic or polycyclic structure in which X and Y are connected to each other. ] 3. The curable resin composition according to claim 1, wherein the tri (alkoxyphenyl) sulfonylsulfonate derivative is a compound represented by the following general formula (2). Embedded image [In the general formula (2), R ³ is an alkyl group having 1 to 10 carbon atoms or a phenyl group, R ⁴ is an alkyl group having 1 to 10 carbon atoms, a perfluoroalkyl group having 1 to 10 carbon atoms, An aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or a group having an alicyclic skeleton having 4 to 12 carbon atoms. ] 4. The curable resin composition according to claim 1, wherein the component (B) is a methylolated melamine-based compound. 5. The curable resin composition according to claim 1, wherein the component (A) is reacted with the component (B). 6. A cured product obtained by curing the curable resin composition according to claim 1.