KR100977962B1 - Curable Resin Composition, Protective Film and Process for Forming the Same - Google Patents

Curable Resin Composition, Protective Film and Process for Forming the Same Download PDF

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KR100977962B1
KR100977962B1 KR20040046480A KR20040046480A KR100977962B1 KR 100977962 B1 KR100977962 B1 KR 100977962B1 KR 20040046480 A KR20040046480 A KR 20040046480A KR 20040046480 A KR20040046480 A KR 20040046480A KR 100977962 B1 KR100977962 B1 KR 100977962B1
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component
curable resin
resin composition
protective film
copolymer
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KR20040046480A
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KR20050000331A (en
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미찌노리 니시까와
아쯔시 바바
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제이에스알 가부시끼가이샤
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Abstract

The present invention satisfies the desired transparency, heat resistance, surface hardness, and adhesion, and at the same time, curable resin capable of forming a protective film for an optical device that is excellent in load resistance even under heating and excellent in flattening a step of a filter formed on a base substrate. The composition, the protective film formed from this composition, and the formation method of this protective film are provided.
The curable resin composition is one selected from the group consisting of polymers having two or more epoxy groups, cationically polymerizable compounds, and thiazoles, thiazolins, sulfenamides, dithiocarbamate, and thiurams in the molecule. It contains the above compound.
Curable resin composition, hardening | curing agent, protective film, the formation method of a protective film, a cationically polymerizable compound, an epoxy group, an acetal structure, a ketal structure, t-butoxycarbonyl structure

Description

Curable Resin Composition, Protective Film and Forming Method thereof {Curable Resin Composition, Protective Film and Process for Forming the Same}

The present invention is particularly preferred as a material for forming a curable resin composition useful as a protective film material, and more particularly as a material for forming a protective film used in an optical device such as a liquid crystal display device (LCD) or a charge coupled device (CCD), and A protective film formed of the composition and a method of forming the protective film.

In the process of manufacturing a square value such as an LCD or a CCD, an immersion treatment with a solvent, an acid, an alkali, or the like is performed on the display element, and when the wiring electrode layer is formed by sputtering, the surface of the element is locally exposed to high temperature. In order to prevent deterioration or damage of a display element by such a process, providing the protective film which is resistant to the said process on the surface of a display element is performed.

Such a protective film is required to have high adhesion to a substrate or a lower layer on which the protective film is to be formed, and further to a layer formed on the protective film. In addition, the protective film itself is smooth and strong, having transparency, having high heat resistance and light resistance, not causing deterioration such as coloring, yellowing or whitening over a long period of time, excellent in water resistance, solvent resistance, acid resistance and alkali resistance, etc. Performance is required. Moreover, the thermosetting composition containing the polymer which has glycidyl group as a material for forming the protective film which has these various performances (refer Unexamined-Japanese-Patent No. 5-78453) is known.

In addition, when such a protective film is used for the color filter of LCD and CCD, it is also required to be able to planarize the level | step difference by the color filter formed on the base substrate.

In a color liquid crystal display device, for example, a color liquid crystal display device such as a super twisted nematic (STN) method or a thin film transistor (TFT) method, after dispersing bead-shaped spacers on the protective film in order to maintain a uniform cell gap of the liquid crystal layer The panel is bonded to each other, and then the liquid crystal cell is sealed by thermocompression bonding the sealing material. It is a problem that the protective film of the part in which a spacer exists exists in the heat and pressure at the time of sealing, and the cell gap is twisted.

In particular, when manufacturing the STN type color liquid crystal display element, high precision is required for the bonding of the color filter and the opposing substrate, and it must be strictly performed. The protection film requires very high level difference planarization performance and heat resistance voltage resistance performance.

Moreover, in recent years, the method of forming a film of wiring electrode (ITO: indium tin oxide) by sputtering on the protective film of a color filter, and patterning ITO by strong acid, strong alkali, etc. is also employ | adopted. Therefore, the protective film is exposed to a high temperature locally at the time of sputtering, or subjected to numerous chemical treatments. Therefore, adhesion to wiring electrodes is also required to withstand these treatments and to prevent ITO from peeling off on the protective film during chemical treatment.                         

In the LCD panel, for the purpose of high brightness, a panel having a transparent structure such as ITO and a TFT element as a laminated structure through a highly transparent interlayer insulating film and having a large opening area has also been developed. In addition, although the color filter and the TFT element are conventionally manufactured using separate substrates, a method of forming the color filter on the TFT element has also been developed when using an interlayer insulating film. Further, under such a technical background, there is a demand for the development of a protective film having high heat resistance and excellent performance (flattening capability) for flattening the step of the color filter formed on the base substrate.

On the other hand, Japanese Unexamined Patent Publication (Kokai) No. 61-197623 combines an epoxy compound and 2-mercaptothiazole to form a curable composition, so that a cured product is accelerated, has excellent adhesion, and has a good gloss. It is disclosed that there is. In addition, Japanese Patent Laid-Open No. 5-230184 combines an epoxy compound and 2-mercaptol thiazole to have low temperature curing properties, excellent storage stability, and improve workability of sealing operations such as electronic and electrical equipment. A one-part thermosetting epoxy resin composition which can be made is disclosed. However, there is no description in these documents suggesting application to a special technical field such as a protective film for color filters.

Although it is preferable to use the curable composition which has the advantage of easily forming the protective film excellent in surface hardness, in forming the protective film for color filters, it not only satisfies the general required performance as a protective film such as transparency, but also meets various requirements as described above. The material which can form the protective film which can respond, and is excellent also in the storage stability as a composition is not known yet.

The present invention has been made on the basis of the above circumstances, and its object is to satisfy the required transparency, heat resistance, surface hardness, and adhesiveness, and to have excellent load resistance even under heating, and to flatten the step of the color filter formed on the base substrate. It is providing the curable resin composition which can form the protective film for optical devices excellent in the performance, the protective film formed from this composition, and the formation method of this protective film.

According to the present invention the above object is

1. A polymer having two or more epoxy groups in the molecule [A], a cationic polymerizable compound [B] (except for the component [A]), [C] thiazoles, thiazolins, sulfenamides, It is achieved by the curable resin composition (henceforth "one-component curable resin composition ((alpha))") containing 1 or more types of compounds chosen from the group which consists of dithiocarbamates and thiurams. .

2. Component [A] is [A1] (a) epoxy group containing polymerizable unsaturated compound, (b1) polymerizable unsaturated carboxylic acid and / or polymerizable unsaturated polyhydric carboxylic anhydride, and (b2) said (a) It is a copolymer of polymerizable unsaturated compounds other than a component and (b1) component, It is achieved by the 1-component curable resin composition ((alpha)).

3. The component [A] is a polymer containing two or more epoxy groups in a molecule of [A2] and at least one structure selected from the group of acetal structures, ketal structures and t-butoxycarbonyl structures. It is achieved by the liquid curable resin composition (α).

4. [A] component is a copolymer of [A3] (a) epoxy group containing polymeric unsaturated compound and (b5) polymeric unsaturated compounds other than said (a) component, In a molecule, a carboxyl group, a carboxylic anhydride group, and acetal It is achieved by the one-component curable resin composition (?), Which is a copolymer having no structure, a ketal structure, and a t-butoxycarbonyl structure.

5. [A3] A copolymer of (a) an epoxy group-containing polymerizable unsaturated compound and (b5) a polymerizable unsaturated compound other than the component (a), wherein the molecule contains a carboxyl group, a carboxylic anhydride group, an acetal structure, a ketal structure, and Curable resin composition containing the copolymer which does not have t-butoxycarbonyl structure, [B] cationically polymerizable compound (except the said [A3] component), the said [C] component, and a [D] hardening | curing agent. (Hereinafter referred to as "one-component curable resin composition (α1)").

6. (1) The 1st component containing the said [A3] component, the [B] cationically polymerizable compound (except the said [A3] component), and the said [C] component, (2) a hardening | curing agent It is achieved by the curable resin composition (henceforth "two-component type curable resin composition ((beta))") containing the combination of the 2nd component to contain.

The term "two-component curable resin composition" used herein refers to a combination of the first component and the second component as a single article unit, but is not mixed with the first component and the second component before being used for the final use. It means the composition which mixes and uses a 1st component and a 2nd component at the time used.                     

7. One or more selected from the group of the above-mentioned [A1] component and the [A2] component, [B] cationically polymerizable compound (except the said [A1] component and [A2] component), and the said [C] It is achieved by the curable resin composition (henceforth "one-component curable resin composition ((alpha) 2)") containing a component and the compound which generate | occur | produces an acid by [E] irradiation and / or heating.

8. It is achieved by the protective film formed from said each 1-component curable resin composition ((alpha)), 1-component curable resin composition ((alpha) 1), 1-component curable resin composition ((alpha) 2), or 2 liquid-type curable resin composition ((beta)).

9. A coating film is formed on a board | substrate using each said 1-component curable resin composition ((alpha)), 1-component curable resin composition ((alpha) 1), or 2-component curable resin composition ((beta)), and is then heat-processed. Is achieved by the method of formation.

10. A film is formed on a board | substrate using 1-component curable resin composition ((alpha) 2), and then it is achieved by the formation method of the protective film characterized by performing a radiation irradiation process and / or heat processing.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Curable Resin Composition

[A] component ([A] polymer)-

The component [A] in the present invention includes a polymer having two or more epoxy groups (hereinafter referred to as "[A] polymer").

The polymer (A) is not particularly limited as long as the above requirements are satisfied, and may be any of an addition polymer, a polyaddition polymer, and a polycondensation polymer.                     

As a preferable [A] polymer of this invention, for example,

[A1] (a) an epoxy group-containing polymerizable unsaturated compound (hereinafter referred to as an "unsaturated compound (a)"), (b1) a polymerizable unsaturated carboxylic acid and / or a polymerizable unsaturated polyhydric carboxylic anhydride (hereinafter, These are collectively referred to as "unsaturated compounds (b1)", and (b2) unsaturated polymers (a) and polymerizable unsaturated compounds other than unsaturated compounds (b1) (hereinafter referred to as "unsaturated compounds (b2)") Copolymers (hereinafter referred to as "copolymer [A1]");

[A2] A polymer containing two or more epoxy groups in a molecule and at least one structure selected from the group consisting of acetal structures, ketal structures and t-butoxycarbonyl structures (hereinafter referred to as "polymer [A2]");

[A3] A copolymer of a polymerizable unsaturated compound (hereinafter referred to as an "unsaturated compound (b5)") other than the unsaturated compound (a) and the (b5) unsaturated compound (a), containing a carboxyl group and a carboxylic anhydride group. And copolymers having no acetal structure, ketal structure and t-butoxycarbonyl structure (hereinafter referred to as "copolymer [A3]").

Moreover, as polymer [A2], polymerizable unsaturated containing one or more structures chosen from the group of a [A2-1] unsaturated compound (a), (b3) acetal structure, ketal structure, and t-butoxycarbonyl structure Air of a polymerizable unsaturated compound (hereinafter referred to as "unsaturated compound (b4)") other than the compound (hereinafter referred to as "unsaturated compound (b3)"), (b4) unsaturated compound (a) and unsaturated compound (b3) More preferred is coalescence (hereinafter referred to as "copolymer [A2-1]").

In addition, the copolymer [A1] may further contain an acetal structure, ketal structure or t-butoxycarbonyl structure, and the polymer [A2] may further contain a carboxyl group or a carboxylic anhydride group.

Examples of the unsaturated compound (a) in the copolymer [A1], the copolymer [A2] and the copolymer [A3] include (meth) acrylic acid glycidyl, α-ethylacrylic acid glycidyl, and α-n-propylacrylic acid. Glycidyl, α-n-butyl acrylate Glycidyl, 3,4-epoxybutyl (meth) acrylate, 3,4-epoxybutyl (alpha) -ethyl acrylate, 6,7-epoxyheptyl (meth) acrylate, α-ethyl Acrylic acid 6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like.

Among these unsaturated compounds (a), (meth) acrylic acid glycidyl, (meth) acrylic acid 6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycid Dyl ether etc. are preferable. These preferable unsaturated compounds (a) have high copolymerization reactivity and are effective for raising the heat resistance and surface hardness of the protective film obtained.

The said unsaturated compound (a) can be used individually or in mixture of 2 or more types.

As an unsaturated compound (b1) in a copolymer [A1], for example

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, α-ethylacrylic acid, α-n-propylacrylic acid, α-n-butylacrylic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

Unsaturated polyhydric carboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, cis-1,2,3,4-tetrahydrophthalic anhydride, and the like.                     

Among these unsaturated compounds (b1), acrylic acid and methacrylic acid are particularly preferable as the unsaturated carboxylic acids, and maleic anhydride is particularly preferable as the unsaturated polyhydric carboxylic acid anhydride. These preferable unsaturated compounds (b1) are high in copolymerization reactivity and are effective in raising the heat resistance and surface hardness of the protective film obtained.

The said unsaturated compound (b1) can be used individually or in mixture of 2 or more types.

Moreover, as an unsaturated compound (b2), for example

(Meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate,

(Meth) acrylic acid alkyl esters such as i-butyl (meth) acrylate, sec-butyl (meth) acrylate and t-butyl (meth) acrylate;

Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo (meth) acrylate (5.2.1.0 2,6 ) decane-8-yl (hereinafter tricyclo [5.2 .1.0 2,6 ] decane-8-yl is referred to as "dicyclopentanyl"),

(Meth) acrylic acid alicyclic esters such as 2-dicyclopentanyloxyethyl (meth) acrylic acid and isoboronyl (meth) acrylate;

(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;

N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl Unsaturated dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridyl) maleimide;

Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide;

Aromatic vinyl compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene;

Indene derivatives such as indene and 1-methylindene;

Vinyl chloride, vinylidene chloride, vinyl acetate, etc. are mentioned besides conjugated diene type compounds, such as 1, 3- butadiene, isoprene, 2, 3- dimethyl- 1, 3- butadiene.

Of these unsaturated compounds (b2), methyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and N-phenylmalee Mid, N-cyclohexyl maleimide, styrene, p-methoxy styrene, 1, 3-butadiene, etc. are preferable. These preferred unsaturated compounds (b2) have high copolymerization reactivity and increase the heat resistance (except for 1,3-butadiene) and surface hardness (except for 1,3-butadiene) of the resulting protective film. Valid for.

The said unsaturated compound (b2) can be used individually or in mixture of 2 or more types.

As a preferable specific example of copolymer [A1],

Glycidyl acrylate / acrylic acid / dicyclopentanyl / styrene copolymers,

Methacrylic acid glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / methacrylic acid / methyl methacrylate / styrene copolymer,

Glycidyl methacrylate / methacrylic acid / cyclohexyl acrylate / p-methoxystyrene copolymer,

Glycidyl acrylate / acrylic acid / N-phenylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / N-phenylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / N-cyclohexylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / 1,3-butadiene copolymer,

Methacrylic acid 6,7-epoxyheptyl / methacrylic acid / methacrylic acid dicyclopentanyl / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / styrene / 1,3-butadiene copolymer,                     

Methacrylic acid 6,7-epoxyheptyl / acrylic acid / maleic anhydride / styrene copolymer,

And methacrylic acid 6,7-epoxyheptyl / acrylic acid / maleic anhydride / methacrylic acid t-butyl copolymer.

More preferably among these copolymers [A1],

Methacrylic acid glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / N-phenylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / N-cyclohexylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / 1,3-butadiene copolymer,

Methacrylic acid glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / styrene / 1,3-butadiene copolymer and the like.

The content of the repeating units derived from the unsaturated compound (a) in the copolymer [A1] is preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight, based on the total repeating units, and a polymerizable unsaturated carboxylic acid. And the total content of repeating units derived from polymerizable unsaturated polyhydric carboxylic anhydride is preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight, based on the total repeating units. The content rate of the repeating unit to be made is preferably 10 to 70% by weight, particularly preferably 20 to 50% by weight based on the total repeating units.

When the content rate of the repeating unit derived from an unsaturated compound (a) is less than 10 weight%, there exists a tendency for the heat resistance and surface hardness of a protective film to fall, and when it exceeds 70 weight%, there exists a tendency for the storage stability of a composition to fall. Moreover, when the total content rate of the repeating unit derived from a polymerizable unsaturated carboxylic acid and a polymerizable unsaturated polyhydric carboxylic anhydride is less than 5 weight%, there exists a tendency for the heat resistance, surface hardness, and chemical-resistance of a protective film to fall, and 40 weight When it exceeds%, there exists a tendency for the storage stability of a composition to fall. Moreover, when the content rate of the repeating unit derived from another polymerizable unsaturated compound is less than 10 weight%, the storage stability of a composition will fall, and when it exceeds 70 weight%, there exists a tendency for the heat resistance and surface hardness of a protective film to fall. .

Subsequently, the polymer [A2] is not particularly limited as long as the above requirements are satisfied, and may be any of an addition polymer, a polyaddition polymer, and a polycondensation polymer.

The acetal structure or the ketal structure in the polymer [A2] can be introduced by bonding the acetal-forming functional group or the ketal-forming functional group as described below to a carbon atom in the polymer [A2] directly or through a bonding water such as a carbonyl group.

As a functional group (henceforth "acetal forming functional group") which can form an acetal structure, it is, for example.

1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i-propoxyethoxy group, 1-n-butoxyethoxy group, 1-i- Butoxyethoxy group, 1-sec-butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyloxyethoxy group, 1-cyclohexyloxyethoxy group, 1-norbornyloxy Ethoxy group, 1-bornyloxyethoxy group, 1-phenoxyethoxy group, 1- (1-naphthyloxy) ethoxy group, 1-benzyloxyethoxy group, 1-phenethyloxyethoxy group,                     

(Cyclohexyl) (methoxy) methoxy group, (cyclohexyl) (ethoxy) methoxy group, (cyclohexyl) (n-propoxy) methoxy group, (cyclohexyl) (i-propoxy) methoxy group, (cyclo Hexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) (benzyloxy) methoxy group, (phenyl) (methoxy) methoxy group, (phenyl) (ethoxy) Methoxy group, (phenyl) (n-propoxy) methoxy group, (phenyl) (i-propoxy) methoxy group, (phenyl) (cyclohexyloxy) methoxy group, (phenyl) (phenoxy) methoxy group, ( Phenyl) (benzyloxy) methoxy group, (benzyl) (methoxy) methoxy group, (benzyl) (ethoxy) methoxy group, (benzyl) (n-propoxy) methoxy group, (benzyl) (i-propoxy) Methoxy group, (benzyl) (cyclohexyloxy) methoxy group, (benzyl) (phenoxy) methoxy group, (benzyl) (benzyloxy) methoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group Etc. can be mentioned.

Among these acetal-forming functional groups, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, etc. desirable.

Moreover, as a functional group (henceforth "a ketal formation functional group") which can form a ketal structure, it is a 1-methyl-1- methoxyethoxy group, 1-methyl-1-ethoxyethoxy group, for example. , 1-methyl

-1-n-propoxyethoxy group, 1-methyl-1-i-propoxyethoxy group, 1-methyl-1-n-butoxyethoxy group, 1-methyl-1-i-butoxy Oxy group, 1-methyl-1-sec-butoxyethoxy group, 1-methyl-1-t-butoxyethoxy group, 1-methyl-1-cyclopentyloxyethoxy group, 1-methyl-1- Cyclohexyloxyethoxy group, 1-methyl-1-norbornyloxyethoxy group, 1-methyl-1-bornyloxyethoxy group, 1-methyl-1-phenoxyethoxy group, 1-methyl- 1- (1-naphthyloxy) ethoxy group, 1-methyl-1-benzyloxyethoxy group, 1-methyl-1-phenethyloxyethoxy group, 1-cyclohexyl-1-methoxyethoxy group, 1-cyclohexyl-1-ethoxyethoxy group, 1-cyclohexyl-1-n-propoxyethoxy group, 1-cyclohexyl-1-i-propoxyethoxy group, 1-cyclohexyl-1- Cyclohexyloxyethoxy group, 1-cyclohexyl-1-phenoxyethoxy group, 1-cyclohexyl-1-benzyloxyethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1 -Ethoxyethoxy group, 1-phenyl-1-n-propoxyethoxy group, 1-phenyl-1-i-prop Foxoxyoxy group, 1-phenyl-1-cyclohexyloxyethoxy group, 1-phenyl-1-phenoxyethoxy group, 1-phenyl-1-benzyloxyethoxy group, 1-benzyl-1-methoxy Ethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-benzyl-1-n-propoxyethoxy group, 1-benzyl-1-i-propoxyethoxy group, 1-benzyl-1- Cyclohexyloxyethoxy group, 1-benzyl-1-phenoxyethoxy group, 1-benzyl-1-benzyloxyethoxy group, 1-methoxycyclopentyloxy group, 1-methoxycyclohexyloxy group, 2 -(2-methyltetrahydrofuranyl) oxy group, 2- (2-methyltetrahydropyranyl) oxy group, etc. are mentioned.

Among these ketal forming functional groups, 1-methyl-1-methoxyethoxy group, 1-methyl-1-cyclohexyloxyethoxy group, etc. are preferable.

Compared with the case where copolymer [A1] is used, polymer [A2] can induce the one-component curable resin composition (?) That has good storage stability and excellent planarization ability of the protective film obtained.

As the unsaturated compound (b3) in the copolymer [A2-1], for example, a norbornene-based compound having one or more structures selected from the group consisting of acetal structures, ketal structures and t-butoxycarbonyl structures (hereinafter, " Specific norbornene-based compounds), (meth) acrylic acid ester compounds having an acetal structure and / or ketal structure (hereinafter referred to as "specific (meth) acrylic acid ester compounds"), (meth) acrylic acid t-butyl, etc. Can be mentioned.

As a specific example of a specific norbornene-type compound,

2,3-di (1-methoxyethoxycarbonyl) -5-norbornene,

2,3-di (1-t-butoxyethoxycarbonyl) -5-norbornene,

2,3-di (1-benzyloxyethoxycarbonyl) -5-norbornene,

2,3-di (1-methyl-1-methoxyethoxycarbonyl) -5-norbornene,

2,3-di (1-methyl-1-i-butoxyethoxycarbonyl) -5-norbornene,

2,3-di [(cyclohexyl) (ethoxy) methoxycarbonyl] -5-norbornene,

2,3-di [(benzyl) (ethoxy) methoxycarbonyl] -5-norbornene,

2,3-di (tetrahydrofuran-2-yloxycarbonyl) -5-norbornene,

2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene,

2,3-di (t-butoxycarbonyl) -5-norbornene etc. are mentioned.

As a specific example of a specific (meth) acrylic acid ester compound, (meth) acrylic acid 1-ethoxyethyl, (meth) acrylic acid 1-n-propoxyethyl, (meth) acrylic acid 1-n-butoxyethyl, (meth) acrylic acid 1- i-butoxyethyl, (meth) acrylic acid 1- (cyclopentyloxy) ethyl, (meth) acrylic acid 1- (cyclohexyloxy) ethyl, (meth) acrylic acid 1- (1,1-dimethylethoxy) ethyl, (Meth) acrylic acid tetrahydro-2H-pyran-2-yl etc. are mentioned.

Among these unsaturated compounds (b3), specific (meth) acrylic acid ester compounds, t-butyl (meth) acrylate are preferable, and (meth) acrylic acid 1-ethoxyethyl, (meth) acrylic acid 1-i-butoxyethyl, ( (Meth) acrylic acid 1- (cyclopentyloxy) ethyl, (meth) acrylic acid 1- (cyclohexyloxy) ethyl, (meth) acrylic acid 1- (1,1-dimethylethoxy) ethyl, (meth) acrylic acid tetrahydro- 2H-pyran-2-yl, t-butyl (meth) acrylate, and the like are preferable. These preferable unsaturated compounds (b3) have high copolymerization reactivity, and exhibit heat resistance and surface hardness of the protective film obtained at the same time as inducing the one-component curable resin composition (α) and the one-component curable resin composition (α2) excellent in storage stability and planarization ability of the protective film. It is effective to increase the.

The said unsaturated compound (b3) can be used individually or in mixture of 2 or more types.

Moreover, as an unsaturated compound (b4), the same thing as the compound illustrated with respect to the said unsaturated compound (b1) and an unsaturated compound (b2) is mentioned, for example.

Of these unsaturated compounds (b4), methyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, N-phenylmaleimide, and N-cyclohexylmaleimide , Styrene, p-methoxystyrene, 1,3-butadiene and the like are preferable. These preferred unsaturated compounds (b4) have high copolymerization reactivity and increase the heat resistance (except for 1,3-butadiene) and surface hardness (except for 1,3-butadiene) of the resulting protective film. Valid for.

The said unsaturated compound (b4) can be used individually or in mixture of 2 or more types.

As a preferable specific example of copolymer [A2-1],

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / methacrylic acid diclofentanil / styrene copolymer,

Methacrylate glycidyl / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / N-phenylmaleimide

/ Styrene copolymer,

Glycidyl methacrylate / methacrylic acid tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / methacrylic acid tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / acrylic acid 1- (cyclohexyloxy) ethyl / methacrylic acid dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylic acid dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / acrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / methacryl dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / 1,3-butadiene copolymer,

Glycidyl methacrylate / methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / 1,3-butadiene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / methyl methacrylate / styrene copolymer,

Glycidyl methacrylate / methacrylate tetrahydro-2H-pyran-2-yl / methyl methacrylate / styrene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / cyclohexyl acrylate / p-methoxystyrene copolymer,

Glycidyl methacrylate / methacrylic acid tetrahydro-2H-pyran-2-yl / cyclohexyl acrylate / p-methoxystyrene copolymer,

Glycidyl acrylate / methacrylic acid t-butyl / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / methacrylic acid t-butyl / N-cyclohexylmaleimide / styrene copolymer,

Methacrylic acid 6,7-epoxyheptyl / acrylic acid tetrahydro-2H-pyran-2-yl / methacrylate t-butyl / maleic anhydride copolymer,                     

Methacrylic acid 6,7-epoxyheptyl / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate t-butyl / maleic anhydride copolymer,

Methacrylic acid 6,7-epoxyheptyl / methacrylic acid t-butyl / methacrylate dicyclopentanyl / styrene copolymer,

Methacrylic acid 6,7-epoxyheptyl / methacrylic acid t-butyl / maleic anhydride / styrene copolymer,

Glycidyl methacrylate / acrylic acid 1- (cyclohexyloxy) ethyl / methacrylate dicyclopentanyl / styrene / 1,3-butadiene copolymer,

And methacrylic acid glycidyl / methacrylic acid 1- (cyclohexyloxy) ethyl / methacrylate dicyclopentanyl / styrene / 1,3-butadiene copolymer.

More preferably among these copolymers [A2-1],

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer,

Methacrylate glycidyl / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / N-phenylmaleimide

/ Styrene copolymer,

Glycidyl methacrylate / methacrylic acid tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / methacrylic acid tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / acrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

Methacrylic acid glycidyl / methacrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer,

Glycidyl methacrylate / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / methacrylic acid dicyclopentanyl / styrene copolymer,

Glycidyl methacrylate / 2,3-di (tetrahydropyran-2-yloxycarbonyl) -5-norbornene / N-cyclohexylmaleimide / styrene copolymer,

And methacrylic acid glycidyl / methacrylic acid t-butyl / N-cyclohexylmaleimide / styrene copolymer.

As for the content rate of the repeating unit derived from an unsaturated compound (a) in copolymer [A2-1], 10-70 weight% is preferable with respect to all the repeating units, and 20-60 weight% is especially preferable. When the content rate of the repeating unit derived from an unsaturated compound (a) is less than 10 weight%, there exists a tendency for the heat resistance and surface hardness of a protective film to fall, and when it exceeds 70 weight%, there exists a tendency for the storage stability of a composition to fall.

Moreover, 5-60 weight% is preferable and, as for the content rate of the repeating unit derived from an unsaturated compound (b3), 10-50 weight% is especially preferable. By carrying out the content rate of the repeating unit derived from an unsaturated compound (b3) in this range, the favorable heat resistance and surface hardness of a protective film can be implement | achieved.

In addition, although the content rate of the repeating unit derived from an unsaturated compound (b4) becomes the quantity which subtracted the total content rate of the repeating unit derived from an unsaturated compound (a) and an unsaturated compound (b3) from 100 weight%, an unsaturated compound (b4) In the case of using unsaturated carboxylic acids or unsaturated polyhydric carboxylic anhydrides as above, if the total content of repeating units derived from these exceeds 40% by weight, the storage stability of the composition may be impaired. It is desirable not to.

Next, as an unsaturated compound (b5) of copolymer [A3], the same thing as the compound illustrated with respect to the said unsaturated compound (b2) is mentioned, for example.

Of these unsaturated compounds (b5), methyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and N-phenylmalee Mid, N-cyclohexyl maleimide, styrene, p-methoxy styrene, 1, 3-butadiene, etc. are preferable. These preferred unsaturated compounds (b5) have high copolymerization reactivity and increase the heat resistance (except for 1,3-butadiene) and surface hardness (except for 1,3-butadiene) of the resulting protective film. Valid for.

The said unsaturated compound (b5) can be used individually or in mixture of 2 or more types.

As a preferable specific example of copolymer [A3],

Acrylic acid glycidyl / styrene copolymer,                     

Methacrylate glycidyl / styrene copolymer,

Glycidyl acrylate / methacrylic acid dicyclopentanyl copolymer,

Methacrylate glycidyl / methacrylate dicyclopentanyl copolymer,

Methacrylic acid 6,7-epoxyheptyl / styrene copolymer,

Methacrylate glycidyl / methacrylate dicyclopentanyl / styrene copolymer,

Methacrylate glycidyl / N-phenylmaleimide / styrene copolymer,

Glycidyl methacrylate / N-cyclohexylmaleimide / styrene copolymer,

Methacrylic acid 6,7-epoxyheptyl / methacrylic acid dicyclopentanyl copolymer,

Methacrylic acid 6,7-epoxyheptyl / N-cyclohexylmaleimide / styrene copolymer and the like.

More preferably among these copolymers [A3] are methacrylic acid glycidyl / styrene copolymers, methacrylic acid glycidyl / methacrylate dicyclopentanyl copolymers and methacrylic acid glycidyl / methacrylate dicyclo Fentanyl / styrene copolymer, methacrylic acid glycidyl / N-cyclohexyl maleimide / styrene copolymer, etc. are mentioned.

As for the content rate of the repeating unit derived from an unsaturated compound (a) in copolymer [A3], 1-90 weight% is preferable with respect to all the repeating units, and 40-90 weight% is especially preferable.

When the content rate of the repeating unit derived from an unsaturated compound (a) is less than 1 weight%, there exists a tendency for the heat resistance and surface hardness of a protective film to fall, and when it exceeds 90 weight%, there exists a tendency for the storage stability of a composition to fall.                     

Copolymer [A1], copolymer [A2-1], and copolymer [A3] can synthesize | combine each unsaturated compound in presence of a suitable solvent and a polymerization initiator, for example by radical polymerization.

As a solvent used for the said superposition | polymerization, for example,

Alcohols such as methanol and ethanol;

Ethers such as tetrahydrofuran and dioxane;

Ethylene glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether and ethylene glycol mono-n-butyl ether;

Ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol-n-propyl ether acetate, and ethylene glycol-n-butyl ether acetate;

Diethylene glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether;

Diethylene glycol alkyl ether acetates such as diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol-n-propyl ether acetate and diethylene glycol-n-butyl ether acetate;

Propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and propylene glycol mono-n-butyl ether:

Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol-n-propyl ether acetate, and propylene glycol-n-butyl ether acetate;

Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol-n-propyl ether propionate and propylene glycol-n-butyl ether propionate;

Aromatic hydrocarbons such as toluene and xylene;

Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and methyl isoamyl ketone;

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate,

Methyl hydroxyacetic acid, ethyl hydroxyacetic acid, hydroxyacetic acid n-propyl, hydroxyacetic acid n-butyl, methoxyacetic acid methyl, methoxyacetic acid ethyl, methoxyacetic acid n-propyl, methoxyacetic acid n-butyl, ethoxy Methyl acetate, ethyl ethoxyacetate, ethoxyacetic acid n-propyl, ethoxyacetic acid n-butyl, n-propoxyacetic acid methyl, n-propoxyacetic acid ethyl, n-propoxyacetic acid n-propyl, n-propoxyacetic acid n-butyl, n-butoxyacetic acid methyl, n-butoxyacetic acid ethyl, n-butoxyacetic acid n-propyl, n-butoxyacetic acid n-butyl, methyl lactate, ethyl lactate, lactic acid n-propyl, lactic acid n- Butyl, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionic acid n-propyl, 3-hydroxypropionic acid n-butyl, 2-methoxypropionic acid methyl, 2-methoxypropionate, 2- Methoxyf N-propyl pyionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate, 2-n Methyl propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-propoxypropionate, n-butyl 2-npropoxypropionate, methyl 2-n-butoxypropionate, 2-n- Ethyl butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate,

3-Methoxypropionate, 3-Methoxypropionate, 3-Methoxypropionate n-propyl, 3-Methoxypropionate n-butyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, 3-ethoxy Propionic acid n-propyl, 3-ethoxypropionic acid n-butyl, 3-n-propoxypropionic acid methyl, 3-n-propoxypropionic acid ethyl, 3-n-propoxypropionic acid n-propyl, 3-n-propoxypropionic acid n-butyl, 3-n-butoxypropionate methyl, 3-n-butoxypropionate, 3-n-butoxypropionic acid n-propyl, 3-n-butoxypropionic acid n-butyl, 2-hydroxy-2 And other esters such as methyl methyl propionate, ethyl 2-hydroxy-2-methyl propionate and methyl 2-hydroxy-3-methylbutanoate.

Among these solvents, diethylene glycol ethers, diethylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates, and the like are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol methyl ether acetate, and propylene Glycol methyl ether acetate, propylene glycol ethyl ether acetate, etc. are preferable.

The said solvent can be used individually or in mixture of 2 or more types.                     

As a polymerization initiator used for the said superposition | polymerization, what is generally known as a radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethyl) Azo compounds such as valeronitrile) and 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; Hydrogen peroxide; And redox initiators containing these peroxides and reducing agents.

These polymerization initiators can be used individually or in mixture of 2 or more types.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography of the polymer [A] is preferably 3,000 to 100,000, more preferably 3,000 to 50,000, and particularly preferably 3,000 to 20,000. By using the polymer [A] having such Mw, a protective film excellent in planarization performance can be obtained.

In the present invention, the polymer [A] may be used alone or in combination of two or more thereof, and in the one-component curable resin composition (α2), one or more kinds of the copolymer [A1] and the polymer [A2] may be used. Can be.

[B] Cationically Polymerizable Compounds-

Component [B] in the present invention includes a cationically polymerizable compound except for the polymer [A].

The cationically polymerizable compound is not particularly limited as long as it can polymerize under acidic conditions. For example, group which can react with addition of the epoxy group in the [A] polymer, such as a compound which has 2 or more in a molecule with 1 or more types chosen from the group of an oxetane ring skeleton, a 3, 4- epoxycyclohexane skeleton, and an epoxy group The compound which has is mentioned.

As a specific example of a cationically polymerizable compound, the following are mentioned.

As a compound which has two or more oxetane ring skeleton in a molecule | numerator, for example

3,7-bis (3-oxetanyl) -5-oxanonane, 3,3 '-[1,3- (2-methylenyl) propanediyl bis (oxymethylene)] bis (3-ethyloxetane) , 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 1,2-bis [(3-ethyl-3-oxetanyl) methoxymethyl] ethane, 1,3 -Bis [(3-ethyl-3-oxetanyl) methoxymethyl] propane,

Ethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, dicyclopentanyl bis [(

3-ethyl-3-oxetanyl) methyl] ether, triethyleneglycol bis [(3-ethyl-3-oxetanyl) methyl] ether, tetraethyleneglycol bis [(3-ethyl-3-oxetanyl) Methyl] ether, tricyclodecanediyldimethylene bis [(3-ethyl-3-oxetanyl) methyl] ether, trimethylolpropane tris [(

3-ethyl-3-oxetanyl) methyl] ether, 1,4-bis [(3-ethyl-3-oxetanyl) methoxy] butane, 1,6-bis [(3-ethyl-3-jade Cetanyl) methoxy] hexane, pentaerythritol tris [(3-ethyl-3-oxetanyl) methyl] ether, pentaerythritol tetrakis [(3-ethyl-3-oxetanyl) methyl] ether, polyethylene Glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol hexakis

[(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol pentakis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol tetrakis [(3-ethyl- 3-oxetanyl) methyl] ether,

Reaction product of dipentaerythritol hexakis [(3-ethyl-3-oxetanyl) methyl] ether with caprolactone, dipentaerythritol pentakis [(3-ethyl-3-oxetanyl) methyl] ether Reaction product of caprolactone, ditrimethylolpropane tetrakis [(3-ethyl-3-oxetanyl) methyl] ether, bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and ethylene jade Reaction product of seed, bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether, reaction product of propylene oxide, hydrogenated bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] Reaction product of ether and ethylene oxide, hydrogenated bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] reaction product of ether and propylene oxide, bisphenol F bis [(3-ethyl-3-oxeta And a reaction product of nil) methyl] ether and ethylene oxide.

As a compound which has 2 or more of 3, 4- epoxycyclohexane frame | skeleton in a molecule | numerator, for example, 3, 4- epoxycyclohexylmethyl-3 ', 4'- epoxycyclohexane carboxylate, 2- (3, 4- Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclo Hexylmethyl) adipate, 3,4

-Epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol bis ( 3,

4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), lactone modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, etc. are mentioned. Can be.

As a compound which has two or more epoxy groups in a molecule | numerator, for example

Bisphenol A diglycidyl ether, Bisphenol F diglycidyl ether, Bisphenol S diglycidyl ether, Hydrogenated bisphenol A diglycidyl ether, Hydrogenated bisphenol F diglycidyl ether, Hydrogenated bisphenol AD diglyl Diglycidyl ethers of bisphenol compounds such as cydyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl ether;

1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triclisidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol digly Polyglycidyl ethers of polyhydric alcohols such as cyl ether;

Polyglycidyl ethers of polyether polyols obtained by reaction of aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin with one or two or more alkylene oxides;

Epoxy resins such as phenol novolac type epoxy resins, cresol novolac type epoxy resins, polyphenol type epoxy resins, and cyclic aliphatic epoxy resins;

Diglycidyl esters of aliphatic long-chain dibasic acids;

Polyglycidyl esters of higher polyvalent fatty acids;

Epoxidized soybean oil, epoxidized linseed oil, etc. are mentioned.

As a commercial item of the compound which has two or more epoxy groups in a molecule | numerator, for example

As polyglycidyl ether of polyhydric alcohol, epolite 100MF (made by Kyoeisha Chemical Co., Ltd.), Epiol TMP (made by Nippon Yushi Corporation);

Epicoat 828, 1001, 1002, 1003, 1004, 1007, 1009, 1010 (above, Japan Epoxy Resin Co., Ltd.) etc. as bisphenol-A epoxy resin;

Epicoat 807 (Japan Epoxy Resin Co., Ltd.) etc. as bisphenol F-type epoxy resin;

Epicoat 152, 154, 157S65 (above, Japan Epoxy Resin Co., Ltd.), DPPN 201, 202 (above, Nippon Kayaku Co., Ltd.) etc. as a phenol novolak-type epoxy resin;

As a cresol novolak type epoxy resin, DOCN 102, 103S, 104S, 1020, 1025, 1027 (above, manufactured by Nippon Kayaku Co., Ltd.), epicoat 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.), and the like;

Epicoat 1032H60, XY-4000 (above, Japan Epoxy Resin Co., Ltd.) etc. as polyphenol-type epoxy resin;

As cyclic aliphatic epoxy resin, CY-175, -177, -179, alaldite CY-182, -192, -184 (above, Ciba Specialty Chemicals make), DRL-4221, -4206,- 4234, -4299 (above, manufactured by UCC Corporation), Shodine 509 (manufactured by Showa Denko Co., Ltd.), Epiclone 200, 400 (above, manufactured by Dainippon Ink, Inc.), Epicoat 871, 872 (more, Japan Epoxy Resin Co., Ltd.), DD-5661, -5662 (above, Celanese Coating Co., Ltd. product), etc. are mentioned.

Among these cationic polymerizable compounds, phenol novolac type epoxy resins, polyphenol type epoxy resins, and the like are preferable.

In this invention, a cationically polymerizable compound can be used individually or in mixture of 2 or more types.

[C] thiazoles, etc.-

[C] component in the present invention is at least one compound selected from the group consisting of thiazoles, thiazolins, sulfenamides, dithiocarbamates and thiurams (hereinafter referred to as "thiazoles"). It includes.                     

Thiazoles etc. are components which act to improve adhesiveness with the board | substrate etc. of the protective film obtained.

Examples of thiazoles include 2-mercaptothiazole, 2-mercaptobenzothiazole, 2-mercapto-6-methylbenzothiazole, 2-mercapto-6-ethylbenzothiazole, and 2-mercapto. -6-n-butylbenzothiazole, 2-methylthiobenzothiazole, 2-methylbenzothiazole, dibenzothiazyl disulfide, 2- (N, N-diethylthiocarbamoylthio) benzothiazole Thiazoles such as 2- (4-morpholinyldithio) benzothiazole, zinc salt of 2-mercaptobenzothiazole and cyclohexylamine salt of 2-mercaptobenzothiazole;

Thiazolins, such as 2-mercaptothiazoline, 2-methylthio-2-thiazoline, and 2-mercaptobenzothiazoline;

N-cyclohexylbenzothiazyl-2-sulfenamide, Nt-butylbenzothiazyl-2-sulfenamide, N-oxydiethylenebenzothiazyl-2-sulfenamide, N, N-di-i-propylbenzothia Sulfenamides such as vagin-2-sulfenamide and N, N-dicyclohexylbenzothiazyl-2-sulfenamide;

Dithiocarbamates such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate and zinc (ethyl) (phenyl) dithiocarbamate;

Thiurams such as tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetra-n-butyl thiuram monosulfide, di (pentamethylene) thiuram tetrasulfide, and the like. Can be.

Among these thiazoles, 2-mercaptothiazole, 2-mercaptobenzothiazole, 2-mercapto-6-methylbenzothiazole, 2- (N, N-diethylthiocarbamoylthio) as thiazoles, etc. Benzothiazole, 2- (4-morpholinyldithio) benzothiazole and the like; N-cyclohexylbenzothiazyl-2- sulfenamide etc. as sulfenamides; As thiurams, tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, etc. are preferable.

Commercially available products such as thiazoles include Sansell M, Sansell MG, Sansell DM, Sansell MZ, Sansell HM, Sansell CM, Sansell NS, Sansell NOB, Sansell DIB, Sansell DZ, Sansell TS, Sanssell TT, Sanssell TET-G, Sanssell TBT-P, Sanssell TRA, Sanssell PZ, Sanssell EZ (above, manufactured by Sanshin Kagaku Kogyo Co., Ltd.); Accelerator M, accelerator MG, accelerator MR, accelerator MS, accelerator DM, accelerator NS, accelerator MZ, accelerator CZ, accelerator TBS-R, accelerator MX-1, accelerator MX-2, accelerator DZ-B, accelerator DS (above, Kawa Gucci Kagaku Kogyo Co., Ltd.) etc. are mentioned.

Thiazoles etc. can be used individually or in mixture of 2 or more types in this invention.

[D] Curing Agent-

The hardening | curing agent in 1-component curable resin composition ((alpha) 1) and 2-component curable resin composition ((beta)) contains the compound which has 1 or more types of functional groups which can react with the epoxy group in copolymer [A3].

As such a hardening | curing agent, a copolymer of polyhydric carboxylic acid, polyhydric carboxylic anhydride, unsaturated polyhydric carboxylic anhydride, and another olefinic unsaturated compound (except the copolymer which has 2 or more epoxy groups) ( Hereinafter, the "carboxylic acid anhydride group containing copolymer") etc. are mentioned.

As said polyhydric carboxylic acid, For example, aliphatic polyhydric carboxylic acids, such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butane tetracarboxylic acid, maleic acid, itaconic acid; Alicyclic polyhydric carboxylic acids such as hexahydrophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid and cyclopentanetetracarboxylic acid; And aromatic polyhydric carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and 1,2,5,8-naphthalenetetracarboxylic acid.

Aromatic polyhydric carboxylic acids are preferable from a viewpoint of the reactivity of curable resin composition among these polyhydric carboxylic acids, the heat resistance of the protective film formed, etc.

As said polyhydric carboxylic anhydride, for example, itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, high Aliphatic dicarboxylic acid anhydrides such as amic acid anhydride; Alicyclic polyhydric carboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride and cyclopentane tetracarboxylic dianhydride; Aromatic polyhydric carboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride and benzophenone tetracarboxylic anhydride; Ester group-containing acid anhydrides such as ethylene glycol bis anhydride trimellitate and glycerin tris anhydrous trimellitate.

Among these polyhydric carboxylic anhydrides, aromatic polyhydric carboxylic anhydrides are preferable, and trimellitic anhydride is particularly preferable in that a protective film having high heat resistance can be obtained.

As unsaturated polyhydric carboxylic anhydride in a carboxylic anhydride group containing copolymer, a maleic anhydride, itaconic anhydride, a citraconic anhydride, a cis-1,2,3,4- tetrahydrophthalic anhydride etc. are mentioned, for example. Can be. These unsaturated polyhydric carboxylic anhydrides can be used individually or in mixture of 2 or more types.

As other olefinically unsaturated compounds, for example, styrene, p-methylstyrene, p-methoxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid i -Propyl, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, etc. Can be mentioned. These other olefinically unsaturated compounds can be used individually or in mixture of 2 or more types.

As a preferable specific example of a carboxylic anhydride group containing copolymer, a maleic anhydride / styrene copolymer, a citraconic anhydride / (meth) acrylic-acid dicyclopentanyl copolymer, etc. are mentioned.

1-80 weight% is preferable and, as for the copolymerization ratio of the unsaturated polyhydric carboxylic anhydride in a carboxylic acid anhydride group containing copolymer, 10-60 weight% is more preferable. By using the copolymer of such a copolymerization ratio, the protective film excellent in the planarization ability can be obtained.

500-50,000 are preferable and, as for Mw of the carboxylic acid anhydride group containing copolymer, 500-10,000 are more preferable. By using the copolymer of such a molecular weight range, the protective film excellent in the planarization ability can be obtained.

The said hardening | curing agent can be used individually or in mixture of 2 or more types.

Moreover, in this invention, a two-component curable resin composition ((beta)) is combined by combining the 1st component containing the 1-component curable resin composition ((alpha)) whose [A] component is a copolymer [A3], and the 2nd component containing a hardening | curing agent. I can do it.

[E] acid generator-

Among the compounds which generate an acid by radiation irradiation and / or heating in a one-component curable resin composition (α2) (hereinafter referred to as an "acid generator"), the generation of acid by radiation irradiation is referred to as "radiation radiation generation." ", And that which generate | occur | produce an acid by heating is called" sensitizing acid generator. "

As a radiation sensitive acid generator, a diaryl iodonium salt, a triaryl sulfonium salt, a diaryl phosphonium salt, etc. are mentioned, for example, Any of these can be used preferably.

As the thermal acid generator, for example, sulfonium salts (excluding the triarylsulfonium salts), benzothiazonium salts, ammonium salts, and phosphonium salts (but the diarylphosphonium salts are excluded). The sulfonium salts and benzothiazonium salts are preferable among these.

As said diaryl iodonium salt in a radiation sensitive acid generator, For example, diphenyl iodonium tetrafluoro borate, diphenyl iodonium hexafluoro phosphonate, diphenyl iodonium hexafluoro arsene Acetate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium p-toluenesulfonate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4 -Methoxyphenylphenyl iodonium hexafluorophosphonate, 4-methoxyphenylphenyl iodonium hexafluoroarsenate, 4-methoxyphenylphenyl iodonium trifluoromethanesulfonate, 4-methoxy Methoxyphenylphenyl iodonium trifluoroacetate, 4-methoxyphenylphenyl iodonium p-toluenesulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butyl Phenyl) iodonium hexafluoroa Cenate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodo And p-toluenesulfonate.

Among these diaryl iodonium salts, diphenyl iodonium hexafluorophosphonate is particularly preferable.

Moreover, as said triarylsulfonium salt, a triphenylsulfonium tetrafluoro borate, a triphenylsulfonium hexafluoro phosphonate, a triphenylsulfonium hexafluoro arsenate, and a triphenylsulfonium trifluoro, for example Methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosph Phonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4 -Methoxyphenyldiphenylsulfonium p-toluenesulfonate, 4-phenylthiophenyldiphenyl tetrafluoroborate, 4-phenylthiophenyldiphenyl hexafluorophosphonate, 4-phenylthiophenyldi Phenyl hexafluoroarsenate, 4-phenylthiophenyldiphenyl trifluoromethanesulfonate, 4-phenylthiophenyldiphenyl trifluoroacetate, 4-phenylthiophenyldiphenyl p-toluenesulfonate, and the like. have.                     

Among these triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate is particularly preferable.

Moreover, as said diaryl phosphonium salt, (1-6- (eta)-cumene) ((eta) -cyclopentadienyl) iron hexafluoro phosphonate, etc. are mentioned, for example.

As diaryl iodonium salt in the commercial item of a radiation sensitive acid generator, For example, UVI-6950, UVI-6970, UVI-6974, UVI-6990 (above, U.C.C company make); MPI-103, BBI-103 (above, Midori Kagaku Co., Ltd.), etc. are mentioned.

As the triarylsulfonium salts, for example, adeka optomer SP-150, adeka optomer SP-151, adeka optomer SP-170, and adeka optomer SP-171 (above, Asahi Denka Kogyo ( Note) manufacture); CI-2481, CI-2624, CI-2639, CI-2064 (above, manufactured by Nippon Sodatsu Co., Ltd.); DTS-102, DTS-103, NAT-103, NDS-103, TPS-103, MDS-103 (above, manufactured by Midori Kagaku Co., Ltd.); CD-1010, CD-1011, CD-1012 (above, Satoma make), etc. are mentioned.

Examples of the diaryl phosphonium salts include Irgacure-261 (manufactured by Ciba Specialty Chemicals Co., Ltd.); PCI-061T, PCI-062T, PCI-020T, PCI-022T (above, Nippon Kayaku Co., Ltd.), etc. are mentioned.

Among these commercially available products, UVI-6970, UVI-6974, UVI-6990, Adekaoptomer SP-170, AdekaOptomer SP-171, CD-1012, MPI-103, etc., have a high surface hardness. Preferred at

Said radiation-sensitive acid generator can be used individually or in mixture of 2 or more types.

Subsequently, as the sulfonium salts in the thermal acid generator, for example,

4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, Dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexa Alkylsulfonium salts such as fluoroantimonate;

Benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl- 4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium Benzylsulfonium salts such as hexafluoroarsenate and 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, dibenzyl-4-acetoxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate Benzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5 dibenzylsulfonium salts such as -t-butylphenylsulfonium hexafluoroantimonate and benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate;

4-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-chlorobenzyl-4-hydroxy Phenylmethylsulfonium hexafluorophosphate, 4-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoro Substituted benzyl sulfonium salts, such as a loantimonate and 2-chlorobenzyl-3- chloro-4- hydroxyphenyl methyl sulfonium hexafluoro antimonate, etc. are mentioned.

Of these sulfonium salts, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroanti Monate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-acetoxyphenylsulfonium hexafluoroantimonate, etc. are preferable.

As the benzothiazonium salts, for example, 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- ( 4-methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate Benzyl benzothiazonium salts, such as these, etc. are mentioned. Among these benzothiazonium salts, 3-benzylbenzothiazonium hexafluoroantimonate is particularly preferable.

As an alkyl sulfonium salt in the commercial item of a thermal acid generator, adeka optomer CP-66, adeka optomer CP-77 (above, Asahi Denka Kogyo Co., Ltd. product) etc. are mentioned, for example.

As the benzylsulfonium salts, for example, SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L (above, Sanshin Kagawa Kogyo Co., Ltd.) etc. are mentioned.

Among these commercial items, the protective film from which SI-80, SI-100, SI-110, etc. are obtained is preferable at the point which has high surface hardness.

The thermal acid generators may be used alone or in combination of two or more thereof.

 Embodiment of Curable Resin Composition

If preferable embodiment of each curable resin composition of this invention is shown more concretely, following (I)-(IV) is mentioned.

(I) [A] polymers (preferably one or more of the group of the copolymer [A1], the polymer [A2] and the copolymer [A3]), the [B] cationic polymerizable compound, the [C] thiazoles, and the like. And optionally further containing the following optional additives, and the amount of the cationically polymerizable compound is preferably 3 to 100 parts by weight, more preferably 5 to 50 parts by weight based on 100 parts by weight of the polymer [A]. Part, and the usage-amount of thiazoles etc. becomes like this. Preferably it is 0.01-20 weight part, More preferably, it is 0.05-10 weight part, The 1-component curable resin composition ((alpha)).

In the one-component curable resin composition (α), a protective film having sufficient surface hardness can be obtained by setting the amount of the cationically polymerizable compound to be in the above range. On the other hand, when the amount of thiazoles or the like used is less than 0.01 part by weight, the effect of improving adhesion is hardly expressed. On the other hand, when the amount of the thiazoles is more than 20 parts by weight, light absorption by thiazoles or the like becomes stronger, and the transparency of the protective film is lowered, or the flattening ability or the coating property is lowered. There is a concern.                     

The one-component curable resin composition (α) is particularly excellent in long-term storage stability.

(II) copolymer [A3], [B] cationically polymerizable compound, [C] thiazole, etc., and [D] hardening | curing agent, and if necessary, further contains the following optional additive component, [A] polymer The amount of the cationically polymerizable compound to 100 parts by weight is preferably 3 to 100 parts by weight, more preferably 5 to 50 parts by weight, and the amount of use of thiazoles is preferably 0.01 to 20 parts by weight, and more. Preferably it is 0.05-10 weight part, the usage-amount of a hardening | curing agent becomes like this. Preferably it is 20-60 weight part, More preferably, it is 20-50 weight part, 1 part type curable resin composition ((alpha) 1).

In the said one-part curable resin composition ((alpha) 1), when the usage-amount of a hardening | curing agent is set to the said range, it shows favorable hardening characteristic and does not impair various characteristics of a protective film.

In addition, it is preferable to use the said one-component curable resin composition ((alpha) 1) within 24 hours after manufacture.

(III) (1) copolymer A combination of the 1st component containing [A3], [B] cationically polymerizable compound, [C] thiazole, etc., and the 2nd component containing (2) hardening | curing agent, The first component and / or the second component optionally further contain the following optional additive components, and the amount of the cationic polymerizable compound is preferably 3 to 100 parts by weight based on 100 parts by weight of the polymer [A], More preferably, it is 5-50 weight part, The usage-amount of thiazoles etc. becomes like this. Preferably it is 0.01-20 weight part, More preferably, it is 0.05-10 weight part, The usage-amount of a hardening | curing agent becomes like this. More preferably 20 to 50 parts by weight of the two-component curable resin composition (β).

In the said two-component curable resin composition ((beta)), when the usage-amount of a hardening | curing agent is set to the said range, it shows favorable hardening characteristic and does not impair various characteristics of a protective film.

Moreover, it is preferable to use the said two-component curable resin composition ((beta)) within 24 hours after mixing of a 1st component and a 2nd component.

When manufacturing the one-component curable resin composition (α1) of (II) and the two-component curable resin composition (β) of (III), the curing agent is preferably used as a solution dissolved in a suitable solvent. 5-50 weight% is preferable and, as for the hardening | curing agent density | concentration in this solution, 10-40 weight% is more preferable. As a solvent used here, the same solvent as what was illustrated as a solvent used for synthesis | combination of a copolymer [A1], a copolymer [A2-1], and a copolymer [A3] can be used.

(IV) one or more of the group of the copolymer [A1] and the polymer [A2] (preferably copolymer [A2-1]), the [B] cationically polymerizable compound, the [C] thiazoles, etc., and [E ] The acid generator is contained, and if necessary, further contains the following optional additional components, and the amount of the cationically polymerizable compound is preferably 3 to 100 parts by weight of the total of the copolymer [A1] and the polymer [A2]. It is 100 weight part, More preferably, it is 5-50 weight part, The usage-amount of thiazoles etc. becomes like this. Preferably it is 0.01-20 weight part, More preferably, it is 0.05-10 weight part, The usage-amount of an acid generator is preferable. Preferably it is 20 weight part or less, More preferably, it is 0.05-20 weight part, Especially preferably, it is 0.1-10 weight part, One-component curable resin composition ((alpha) 2).

In the one-component curable resin composition (α2), by using an acid generator in the above range, good curing characteristics are exhibited and various properties of the protective film are not impaired.

These one-component curable resin compositions (α), one-component curable resin compositions (α1), one-component curable resin compositions (α2), and two-component curable resin compositions (β) have a transparency, heat resistance, and surface for which a protective film formed therefrom is desired. It satisfies the hardness and adhesion, and also has excellent load resistance even under heating, and has excellent performance of flattening the step of the color filter formed on the base substrate.

-Optional Additives-

The curable resin composition of this invention can mix | blend arbitrary additional components other than the above, for example surfactant, an adhesion | attachment adjuvant, etc. as needed in the range which does not impair the effect of this invention.

The surfactant is added to improve the applicability of the composition.

As such surfactant, nonionic surfactant, such as a fluorochemical surfactant, silicone type surfactant, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene dialkyl ester, etc. are mentioned, for example. .

As said polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc. are mentioned, for example, As said polyoxyethylene aryl ether, for example, Polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonylphenyl ether, etc. are mentioned, As said polyoxyethylene dialkyl ester, For example, polyoxyethylene dilaurylate, polyoxyethylene distea The rate etc. are mentioned.

As a fluorine-type surfactant among the commercial items of surfactant, For example, BM-1000 and BM-1100 (above, BEM-imid company make); Megapack F142D, Megapack F172, Megapack F173, Megapack F183 (above, manufactured by Dainippon Ink Chemical Industries, Ltd.); Fluoride FC-135, fluoride FC-170C, fluoride FC-430, fluoride FC-431 (above, Sumitomo 3M Co., Ltd. product); Supron S-112, Supron S-113, Supron S-131, Supron S-141, Supron S-145, Supron S-382, Supron SC-101, Supron SC-102, Supron SC-103, a surflon SC-104, a surflon SC-105, a surflon SC-106 (above, Asahi Glass Co., Ltd. product) etc. are mentioned.

In addition, as a silicone type surfactant, SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, Toray Dow Corning Silicone Co., Ltd. product) is made, for example. ); KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); F-top DF301, f-top DF303, f-top DF352 (above, manufactured by Kasei Co., Ltd.), and the like.

Moreover, as another commercial item of surfactant, polyflow No. 57 which is a (meth) acrylic-acid copolymer, polyflow No. 90 (above, Kyoeisha Chemical Co., Ltd. product), etc. are mentioned.

5 weight part or less is preferable with respect to 100 weight part of [A] polymers, and, as for the compounding quantity of surfactant, 2 weight part or less is more preferable. When the compounding quantity of surfactant exceeds 5 weight part, there exists a tendency for film | membrane roughness of a coating film to occur easily.

In addition, the adhesion assistant is added to improve the adhesion between the protective film and the substrate to be formed.

As such an adhesion | attachment adjuvant, the silane coupling agent which has reactive groups, such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an epoxy group, is preferable, for example.

Specific examples of the adhesion aid include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-glycidoxypropyltri Methoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned.

30 weight part or less is preferable with respect to 100 weight part of [A] polymers, and, as for the compounding quantity of an adhesion | attachment adjuvant, 25 weight part or less is more preferable. When the compounding quantity of an adhesion | attachment adjuvant exceeds 30 weight part, there exists a possibility that the heat resistance of the protective film obtained may become inadequate.

Preparation of Curable Resin Composition

Each curable resin composition of this invention, Preferably, it manufactures as a composition solution which melt | dissolved each component uniformly in the suitable solvent.

As a solvent used for the said composition solution, the thing which melt | dissolves each component which comprises curable resin composition, and does not react with each component is used.

As such a solvent, the same solvent as what was illustrated as a solvent used when synthesize | combining the said copolymer [A1], copolymer [A2], and copolymer [A3] can be used. These solvent can be used individually or in mixture of 2 or more types.                     

The amount of the solvent used is in a range where the total solids in each curable resin composition are preferably 1 to 50% by weight, more preferably 5 to 40% by weight.

Moreover, a high boiling point solvent can be used together with the said solvent.

As the high boiling point solvent, for example, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, Dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid Acid diethyl, gamma -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. These high boiling point solvents can be used individually or in mixture of 2 or more types.

90 weight% or less is preferable with respect to the total amount of solvent, and, as for the usage-amount when using a high boiling point solvent together, 80 weight% or less is more preferable.

In addition, the composition solution prepared in this way may be used after filtration fractionation using a Millipore filter having a pore size of 0.2 to 3.0 μm, preferably about 0.2 to 0.5 μm, and the like.

How to form a protective film

Next, the method of forming the protective film of this invention using each curable resin composition of this invention is demonstrated.

In the case of the one-component curable resin composition (α), the one-component curable resin composition (α1), and the [E] acid generator as the one-component curable resin composition (α2), the composition solution is applied onto a substrate. After forming a film by prebaking and removing a solvent, the target protective film can be formed by heat processing.

In addition, the use of the two-component curable resin composition (β) is mixed with the first component and the second component at the time of use to prepare the composition solution, and preferably, the composition solution is applied onto the substrate within 24 hours after the preparation. After forming a film by prebaking and removing a solvent, the target protective film can be formed by heat processing.

As a board | substrate which forms a protective film, what contains glass, quartz, silicone, a transparent resin, etc. can be used, for example.

As said transparent resin, a polyethylene terephthalate, a polybutylene terephthalate, a polyether sulfone, a polycarbonate, a polyimide, a ring-opening polymer of cyclic olefin, a hydrogenated substance thereof, etc. are mentioned, for example.

As a coating method of a composition solution, the appropriate method, such as the spraying method, the roll coating method, the rotary coating method, the bar coating method, the inkjet method, can be used, for example.

Although the conditions of the said prefiring differ according to the kind, compounding ratio, etc. of each component, Preferably it is about 1 to 15 minutes at 70-90 degreeC.

The heat treatment after film formation can be performed by a suitable heating apparatus, such as a hotplate and oven.

As for the processing temperature at the time of heat processing, about 150-250 degreeC is preferable, About 5 to 30 minutes when using a hotplate as a heating apparatus, about 30 to 90 minutes are preferable when using an oven.                     

In addition, in the case of the one-component curable resin composition (α2) using a radiation-sensitive acid generator as the [E] acid generator, a film is formed by applying a composition solution onto a substrate, prefiring to remove the solvent, and then radiation. The target protective film can be formed by performing an irradiation process (exposure process) and heat-processing after that as needed.

In this case, the same thing as the above can be used as a board | substrate, and the formation method of a coating film can be performed similarly to the above.

As the radiation used for the exposure treatment, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used, but ultraviolet rays containing light having a wavelength of 190 to 450 nm are preferable.

50-20,000 J / m <2> is preferable and 100-10,000 J / m <2> of an exposure amount is more preferable.

As for the processing temperature at the time of heat processing after an exposure process, about 150-250 degreeC is preferable. The treatment time is preferably about 5 to 30 minutes when using a hot plate as a heating device, and about 30 to 90 minutes when using an oven.

The film thickness of the protective film thus formed is, for example, 0.1 to 8 µm, preferably 0.1 to 6 µm, and more preferably 0.1 to 4 µm. However, when a protective film is formed on the board | substrate which has the level | step difference of a color filter, the said film thickness means the thickness from the top of a color filter.

The protective film of the present invention satisfies the desired transparency, heat resistance, surface hardness, adhesion, and the like, and has excellent load resistance even under heating, and has excellent performance of flattening the level difference of the color filter formed on the base substrate, and in particular, a protective film for an optical device. It is preferable as.

<Examples>

Hereinafter, although the synthesis example and the Example are shown and embodiment of this invention is described concretely, this invention is not limited to these Examples.

Here, "part" and "%" which represent concentration are based on weight.

Synthesis of Copolymer [A3]

Synthesis Example 1

6 parts of 2,2'- azobisisobutyronitrile, 6 parts of 2,4-diphenyl-4-methyl-1-pentene, and 200 parts of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 80 parts of glycidyl methacrylate and 20 parts of styrene were added thereto, followed by nitrogen substitution. Then, the mixture was stirred slowly to raise the temperature of the reaction solution to 95 ° C. and maintained at this temperature to polymerize for 4 hours to contain a copolymer [A3]. A polymer solution (solid content concentration = 33%) was obtained. Mw of the obtained copolymer was 8,000. This copolymer is called "copolymer (A-1)".

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 6 parts of 2,2'-azobisisobutyronitrile, 10 parts of 2,4-diphenyl-4-methyl-1-pentene and 200 parts of propylene glycol monoethyl ether acetate were added. Subsequently, 50 parts of glycidyl methacrylate and 50 parts of dicyclopentanyl methacrylate were added thereto, followed by nitrogen substitution. Then, the mixture was stirred slowly to raise the temperature of the reaction solution to 95 ° C. and maintained at this temperature to polymerize for 4 hours. A3] (solid content concentration = 33%) containing A3] was obtained. Mw of the obtained copolymer was 6,000. This copolymer is called "copolymer (A-2)".

&Lt; Synthesis Example 3 &

5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer, followed by 50 parts of styrene and glycidyl methacrylate. 50 parts were added and nitrogen-substituted, and it stirred slowly, raised the temperature of the reaction solution to 70 degreeC, and maintained at this temperature and superposed | polymerized for 5 hours, and obtained the polymer solution (solid content concentration = 33%) containing copolymer [A3]. . Mw of the obtained copolymer was 20,000. This copolymer is called "copolymer (A-3)".

Synthesis of Copolymer [A1]

&Lt; Synthesis Example 4 &

In a flask equipped with a cooling tube and a stirrer, 5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol methylethyl ether were added, followed by 25 parts of styrene, 20 parts of methacrylic acid, 45 parts of glycidyl methacrylate and 10 parts of dicyclopentanyl methacrylate were added thereto, followed by nitrogen substitution. The mixture was stirred slowly to raise the temperature of the reaction solution to 70 ° C. and maintained at this temperature to polymerize for 5 hours. ], A polymer solution (solid content concentration = 33%) was obtained. Mw of the obtained copolymer was 6,000. This copolymer is called "copolymer (A-4)".

&Lt; Synthesis Example 5 &

5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer, followed by 18 parts of styrene and 20 parts of methacrylic acid. , 40 parts of glycidyl methacrylate and 22 parts of cyclohexylmaleimide were added to the mixture, followed by nitrogen stirring. Then, the mixture was stirred slowly to raise the temperature of the reaction solution to 70 ° C. and maintained at this temperature to polymerize for 5 hours. The polymer solution (solid content concentration = 33%) containing this was obtained. Mw of the obtained copolymer was 12,000. This copolymer is called "copolymer (A-5)".

Synthesis of Copolymer [A2-1]

Synthesis Example 6

5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer, followed by 25 parts of styrene and 1- (methacrylic acid). 20 parts of cyclohexyloxy) ethyl, 45 parts of glycidyl methacrylate and 10 parts of dicyclopentanyl methacrylate were added thereto, followed by nitrogen substitution, followed by slow stirring to raise the temperature of the reaction solution to 70 ° C., and maintained at this temperature. And polymerizing for 5 hours to obtain a polymer solution (solid content concentration = 33%) containing a copolymer [A2-1]. Mw of the obtained copolymer was 20,000. This copolymer is called "copolymer (A-6)".

Synthesis Example 7

5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of diethylene glycol methylethyl ether were added to a flask equipped with a cooling tube and a stirrer, followed by 18 parts of styrene and tetrahydro-methacrylate. 20 parts of 2H-pyran-2-yl, 40 parts of glycidyl methacrylate and 22 parts of N-cyclohexylmaleimide were added for nitrogen substitution, and then slowly stirred to raise the temperature of the reaction solution to 70 ° C. The polymer solution (solid content concentration = 33%) containing copolymer [A2-1] was obtained by holding and superposing | polymerizing for 5 hours. Mw of the obtained copolymer was 6,000. This copolymer is called "copolymer (A-7)".

<Example 1 (Evaluation of 2-component curable resin composition (β))>

A solution containing the copolymer (A-1) obtained in Synthesis Example 1 as the component [A] (amount corresponding to 100 parts of the copolymer (A-1)), and a bisphenol A novolac epoxy resin as the component [B]. 10 parts of Epicoat 157S65 "(trade name: manufactured by Japan Epoxy Resin Co., Ltd.), 0.3 part of 2-mercaptobenzothiazole as the [C] component, 15 parts of γ-glycidoxypropyl trimethoxysilane as an adhesion aid, and 0.1 part of SH-28PA (manufactured by Toray Dow Corning Silicon Co., Ltd.) as a surfactant was mixed and propylene glycol monomethyl ether acetate was added so that the solid content concentration was 20%, followed by filtration with a millipore filter having a pore diameter of 0.5 µm. To prepare a solution of the first component.

Subsequently, the composition solution was prepared by adding the 2nd component which melt | dissolved 35 parts of trimellitic anhydrides in 65 parts of diethylene glycol methylethyl ether as [D] component to this 1st component solution.

The obtained composition solution was evaluated by forming a protective film on the substrate as described below. The evaluation results are shown in Table 1 below.

Formation of protective film

The composition solution was applied onto the SiO 2 deep glass substrate using a spinner, then prebaked at 80 ° C. for 5 minutes on a hot plate to form a coating film, and further heated at 230 ° C. for 60 minutes in an oven to form a film thickness on the substrate. A protective film of 2.0 mu m was formed.

-Evaluation of the shield-

Evaluation of Transparency:

About the board | substrate with a protective film, the transmittance | permeability (%) in a wavelength range of 400-800 nm was measured using the spectrophotometer 150-20 type double beam (made by Hitachi Seisakusho Co., Ltd.), and it evaluated by the minimum value It was. When this value is 95% or more, it can be said that transparency of a protective film is favorable.

Evaluation of heat resistant dimensional stability:

The board | substrate with a protective film was heated at 250 degreeC in oven for 1 hour, the film thickness before and behind heating was measured, and it evaluated according to the value computed by the following formula. When this value is 95% or more, it can be said that heat-resistant dimensional stability is favorable.

Heat-resistant dimensional stability (%) = (film thickness after heating) × 100 / (film thickness before heating)

Evaluation of heat discoloration resistance:

The substrate on which the protective film was formed was heated in an oven at 250 ° C. for 1 hour, and the transmittance in the wavelength range of 400 to 800 nm before and after heating was measured, and the minimum was evaluated according to the value calculated by the following equation. . It can be said that heat discoloration resistance is favorable when this value is 5% or less.

Heat discoloration resistance (%) = (minimum value of transmittance before heating)-(minimum value of transmittance after heating)                     

Evaluation of Surface Hardness:

The board | substrate with which the protective film was formed was evaluated by carrying out 8.4.1 pencil scratch test of JISK-5400-1990. When this value is 4H or harder, the surface hardness can be said to be good.

Evaluation of Dynamic Microhardness:

0.1 gf load and 0.0145 gf speed using a Shimadzu Dynamic Microhardness Tester DUH-201 (manufactured by Shimadzu Seisakusho Co., Ltd.) on a substrate on which a protective film was formed, and by a press-fit test of a ridge angle 115 ° triangle indenter (Herkovitch type). It evaluated by making temperature 23 degreeC and 140 degreeC on the conditions of / second and holding time of 5 second.

Evaluation of adhesion:

Pressure test device with respect to a substrate in which a protection film was subjected to (℃ temperature 120, humidity 100%, measured 24 hours), SiO 2 glass substrate by dip 8.5.3 adherent checkerboard grid tape method of JIS K-5400-1990 Adhesion to (labeled as "SiO 2 " in Table 1) was evaluated.

A protective film having a film thickness of 2.0 μm was formed in the same manner as described above except that a Cr substrate was used instead of the SiO 2 deep glass substrate, and the adhesion to the Cr substrate (expressed as “Cr” in Table 1) was evaluated.

The numerical value of Table 1 is the number of remaining checkerboard ticks among 100 checkerboard ticks.

Evaluation of planarization power:                     

A pigment-based color resist (trade name: "JCR RED 689", "JCR GREEN 706", or "CR 8200B"; above, manufactured by JSR Corporation) was coated on a SiO 2 deep glass substrate by a spinner, and then on a hot plate. Pre-baked at 90 degreeC for 150 second, and formed the coating film. Thereafter, g / h / i rays (intensity ratios of wavelengths 436 nm, 405 nm and 365 nm = 2.7: 2.5: 4.8) were obtained through a predetermined pattern mask using an exposure machine Canon PLA50lF (manufactured by Canon Corporation). After exposure to 2,000 J / m2 exposure dose, developed using 0.05% potassium hydroxide aqueous solution, washed with ultrapure water for 60 seconds, heat treated at 230 ° C for 30 minutes in red, green, and blue stripes A color filter (stripe width 100 mu m) was formed.

Subsequently, the surface unevenness | corrugation of the board | substrate which provided the said color filter was made into the measurement length 2,000 micrometers, the measurement range 2,000 micrometers angle, and the measurement score n = 5 using the surface roughness alpha-step (manufactured by Tencol Japan Co., Ltd.), and the measurement direction N is set to two directions in the short axis direction of the stripe line in the red, green, and blue directions, and in the major axis direction of the stripe line of the same color of red, red, green, green, blue, and blue, and n = 5 (total number n = 10 in each direction). It was 1.0 micrometer when measured with).

Further, after applying the composition solution prepared in the same manner to the above using a spinner on the substrate on which the color filter was formed in the same manner as described above, prebaking was carried out at 80 ° C. for 5 minutes on a hot plate to form a coating film. By further heat-processing at 230 degreeC for 60 minute (s) in oven, the protective film whose film thickness from the upper surface of a color filter was 2.0 micrometers was formed on the color filter.

Subsequently, with respect to the substrate which has a protective film on this color filter, the unevenness | corrugation of the protective film surface was made into a measurement length 2,000 micrometers, the measurement range 2,000 micrometers angle | corner using the contact type film thickness measuring apparatus (alpha) -step (manufactured by Tencol Japan). The measurement score is n = 5, and the measurement direction is 2 directions of the stripe line short axis direction of red, green, blue direction and the stripe line major axis direction of the same color of red, red, green, green, blue, and blue, and each direction It measured by n = 5 per sugar (total number n = 10), and measured the height difference (nm) of the highest part and the lowest part at the time of each measurement 10 times, and evaluated by the average value. When this value is 300 nm or less, it can be said that planarization ability is favorable.

<Examples 2 to 4 (Evaluation of Two-Component Curable Resin Composition (β))>

Except having used each component shown in Table 1, it carried out similarly to Example 1, and manufactured the 1st component solution and the 2nd component solution, and prepared the composition solution.

About each obtained composition solution, it carried out similarly to Example 1, and formed and evaluated the protective film on the board | substrate. The evaluation results are shown in Table 1.

<Comparative Examples 1 to 5>

A composition solution was prepared in the same manner as in Example 1 except that each component shown in Table 1 was used.

About each obtained composition solution, it carried out similarly to Example 1, and formed and evaluated the protective film on the board | substrate. The evaluation results are shown in Table 1.

The component [B], the component [C], the component [D] and the solvent in Table 1 are as follows.

B-1: bisphenol A novolak-type epoxy resin (brand name: Epicoat 157S65, Japan epoxy resin Co., Ltd. product)                     

B-2: Bisphenol A type epoxy resin (brand name: Epicoat 828, Japan epoxy resin Co., Ltd. product)

C-1: 2-mercaptobenzothiazole (brand name: Sanseller M, Sanshin Chemical Industries, Ltd. make)

C-2: 2- (4-morpholinyldithio) benzothiazole

C-3: N-cyclohexyl benzothiazyl-2-sulfenamide (brand name: Sanseller CM, Sanshin Chemical Industries, Ltd. make)

C-4: tetramethyl thiuram disulfide (brand name: Sanseller TS, Sanshin Chemical Industries, Ltd. make)

D-1: trimellitic anhydride

S-1: Propylene Glycol Methyl Ether Acetate

S-2: diethylene glycol methyl ether acetate                     

Figure 112004026921716-pat00001

<Example 5 (Evaluation of 1-component curable resin composition (α))>

A solution containing the copolymer (A-4) obtained in Synthesis Example 4 as the component [A] (amount equivalent to 100 parts of the copolymer (A-4)), and a bisphenol A novolac epoxy resin as the component [B]. (Trade name: Epicoat 157S65, manufactured by Japan Epoxy Resin Co., Ltd.) 10 parts, 0.3 part of 2-mercaptobenzothiazole as [C] component, 15 parts of γ-glycidoxypropyl trimethoxysilane as an adhesion aid, and 0.1 part of SH-28PA (manufactured by Toray Dow Corning Silicon Co., Ltd.) as a surfactant was added and propylene glycol monomethyl ether acetate was further added so that the solid content concentration was 20%. The solution of the composition was prepared by filtration. The appearance of this composition solution was colorless and transparent.

The protective film was formed on the board | substrate with the following method about the obtained composition solution, and it carried out similarly to Example 1, and evaluated. The evaluation results are shown in Table 2 below.

-Formation of a protective film-

The composition solution was applied onto a SiO 2 deep glass substrate using a spinner, and then prebaked at 80 ° C. for 5 minutes on a hot plate to form a coating film, and further heated at 230 ° C. for 60 minutes in an oven to form a film on the substrate. A protective film having a thickness of 2.0 mu m was formed.

In addition, a protective film was formed in the same manner as above on the substrate on which the color filter was formed in the same manner as in Example 1.

<Examples 6-7 (evaluation of 1-component curable resin composition ((alpha)))>

A composition solution was prepared in the same manner as in Example 5 except that each component shown in Table 2 was used.

About each obtained solution of composition, it carried out similarly to Example 5, and formed the protective film on the board | substrate, and evaluated similarly to Example 1. The evaluation results are shown in Table 2.

<Example 8 (Evaluation of 1-part curable resin composition ((alpha) 2))>

A solution containing the copolymer (A-5) obtained in Synthesis Example 5 as the component [A] (amount corresponding to 100 parts of the copolymer (A-5)), and trimethylolpropane tris [(3] as the component [B].

15 parts of -ethyl-3-oxetanyl) methyl] ether, 0.3 parts of 2-mercaptobenzothiazole as [C] component, and benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexa as [E] component After adding 2 parts of fluoroantimonate and 0.1 part of SH-28PA (manufactured by Toray Dow Corning Silicon Co., Ltd.) as a surfactant, and further adding diethylene glycol dimethyl ether so that the solid content concentration is 20%, A composition solution was prepared by filtration with a Millipore filter with a pore size of 0.5 μm.

About the obtained composition solution, a protective film was formed on the board | substrate similarly to Example 5, and it carried out similarly to Example 1, and evaluated. The evaluation results are shown in Table 2.

<Example 9 (Evaluation of 1-component curable resin composition (α2))>

A composition solution was prepared in the same manner as in Example 8 except that the components shown in Table 2 were used.

About the obtained each composition solution, the protective film was formed on the board | substrate by the following method, and it carried out similarly to Example 1, and evaluated. The evaluation results are shown in Table 2.

-Formation of a protective film-

The composition solution was applied onto a SiO 2 deep glass substrate using a spinner, and then prebaked at 80 ° C. for 5 minutes on a hot plate to form a coating film.

Subsequently, 2,000 g / h / i rays (intensity ratios of wavelengths 436 nm, 405 nm and 365 nm = 2.7: 2.5: 4.8) were converted to i-rays by using an exposure machine Canon PLA501F (manufactured by Canon Corporation) in the formed coating film. After exposing at an exposure amount of J / m 2, a heat treatment was performed at 230 ° C. for 60 minutes in an oven to form a protective film having a thickness of 2.0 μm on the substrate.

In addition, a protective film was formed in the same manner as above on the substrate on which the color filter was formed in the same manner as in Example 1.

The component [B], the component [C], the component [E] and the solvent in Table 2 are as follows.

B-1: bisphenol A novolak-type epoxy resin (brand name: Epicoat 157S65, Japan epoxy resin Co., Ltd. product)

B-3: trimethylolpropane tris [(3-ethyl-3-oxetanyl) methyl] ether

C-1: 2-mercaptobenzothiazole (brand name: Sanseller M, Sanshin Chemical Industries, Ltd. make)

C-2: 2- (4-morpholinyldithio) benzothiazole

C-3: N-cyclohexyl benzothiazyl-2-sulfenamide (brand name: Sanseller CM, Sanshin Chemical Industries, Ltd. make)

C-4: tetramethyl thiuram disulfide (brand name: Sanseller TS, Sanshin Chemical Industries, Ltd. make)

E-1: Benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate

E-2: triphenylsulfonium trifluoromethanesulfonate

S-1: Propylene Glycol Methyl Ether Acetate

S-3: diethylene glycol dimethyl ether                     

Figure 112004026921716-pat00002

<Examples 10-12 (Evaluation of 1-component curable resin composition ((alpha)))>

A composition solution was prepared in the same manner as in Example 5 except for using the components shown in Table 3 below.

About each obtained solution of composition, it carried out similarly to Example 5, and formed the protective film on the board | substrate, and evaluated similarly to Example 1. The evaluation results are shown in Table 3.

<Example 13 (Evaluation of 1-part curable resin composition ((alpha) 2))>

A composition solution was prepared in the same manner as in Example 8 except that the components shown in Table 3 were used.

About each obtained solution of composition, it carried out similarly to Example 5, and formed the protective film on the board | substrate, and evaluated similarly to Example 1. The evaluation results are shown in Table 3.

<Example 14 (Evaluation of 1-component curable resin composition (α2))>

A composition solution was prepared in the same manner as in Example 9 except that the components shown in Table 3 were used.

About the obtained composition solution, it carried out similarly to Example 9, formed the protective film on the board | substrate, and evaluated similarly to Example 1. The evaluation results are shown in Table 3.

<Comparative Examples 6 to 7>

A composition was prepared in the same manner as in Example 5 except that the components shown in Table 3 were used.

About each obtained solution of composition, it carried out similarly to Example 5, and formed the protective film on the board | substrate, and evaluated similarly to Example 1. The evaluation results are shown in Table 3.

The component [B], the component [E] and the solvent in Table 3 are as follows.

B-1: bisphenol A novolak-type epoxy resin (brand name: Epicoat 157S65, Japan epoxy resin Co., Ltd. product)

B-3: trimethylolpropane tris [(3-ethyl-3-oxetanyl) methyl] ether                     

C-1: 2-mercaptobenzothiazole (brand name: Sanseller M, Sanshin Chemical Industries, Ltd. make)

C-2: 2- (4-morpholinyldithio) benzothiazole

C-3: N-cyclohexyl benzothiazyl-2-sulfenamide (brand name: Sanseller CM, Sanshin Chemical Industries, Ltd. make)

C-4: tetramethyl thiuram disulfide (brand name: Sanseller TS, Sanshin Chemical Industries, Ltd. make)

E-1: Benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate

E-2: triphenylsulfonium trifluoromethanesulfonate

S-1: Propylene Glycol Methyl Ether Acetate

S-3: diethylene glycol dimethyl ether                     

Figure 112004026921716-pat00003

As described above, the present invention satisfies various characteristics conventionally required as the protective film, specifically transparency, heat resistance, surface hardness, and adhesion, and is excellent in load resistance even under heating, and the step of the color filter formed on the base substrate. The curable resin composition which can form the protective film for optical devices which is excellent in the performance which planarizes can be obtained.

Claims (11)

  1. [A] A polymer containing two or more epoxy groups in a molecule, [B] a cationically polymerizable compound (except for the component [A] above), and [C] thiazoles, thiazolins, sulfenamides, and Diti Curable resin composition containing 1 or more types of compounds chosen from the group which consists of orcarbamates and thiurams.
  2. The component (A) according to claim 1, wherein the component (A) is a polymerizable unsaturated compound containing (a) an epoxy group, (b1) a polymerizable unsaturated carboxylic acid and / or a polymerizable unsaturated polyhydric carboxylic anhydride, and (b2) Curable resin composition which is a copolymer of polymerizable unsaturated compounds other than the said (a) component and (b1) component.
  3. The curable composition according to claim 1, wherein the component [A] is a polymer containing two or more epoxy groups in the [A2] molecule and at least one structure selected from the group consisting of acetal structures, ketal structures and t-butoxycarbonyl structures. Resin composition.
  4. The at least one component according to claim 3, wherein the component [A2] is selected from the group consisting of [A2-1] (a) an epoxy group-containing polymerizable unsaturated compound, (b3) an acetal structure, a ketal structure and a t-butoxycarbonyl structure Curable resin composition which is a copolymer of the polymerizable unsaturated compound containing a structure, and (b4) components other than the said (a) component and (b3) component.
  5. A component according to claim 1, wherein component [A] is a copolymer of [A3] (a) an epoxy group-containing polymerizable unsaturated compound and (b5) a polymerizable unsaturated compound other than the component (a), wherein a carboxyl group and a carboxylic acid are present in the molecule. Curable resin composition which is a copolymer which does not have an anhydride group, an acetal structure, a ketal structure, and t-butoxycarbonyl structure.
  6. Curable resin composition of Claim 5 which further contains a [D] hardening | curing agent.
  7. (1) Two-component curable resin composition containing the combination of the 1st component containing curable resin composition of Claim 5, and the 2nd component containing (2) hardening | curing agent.
  8. [A1] (a) an epoxy group-containing polymerizable unsaturated compound, (b1) a polymerizable unsaturated carboxylic acid and / or a polymerizable unsaturated polyhydric carboxylic anhydride, and (b2) other than the components (a) and (b1) Of a polymer component containing a copolymer component of a polymerizable unsaturated compound of 1 and at least two epoxy groups in the molecule [A2] and at least one structure selected from the group consisting of acetal structures, ketal structures and t-butoxycarbonyl structures. 1 or more types selected from the group, [B] cationically polymerizable compound (except the said [A1] component and [A2] component), the [C] component of Claim 1, and [E] irradiation, and (Or) Curable resin composition containing the compound which generate | occur | produces an acid by heating.
  9. The protective film formed from the curable resin composition of any one of Claims 1-6, or the two-component curable resin composition of Claim 7.
  10. The film is formed on the board | substrate using the curable resin composition of any one of Claims 1-6, or the two-component curable resin composition of Claim 7, and then heat-processed, The formation of the protective film characterized by the above-mentioned Way.
  11. A film is formed on the board | substrate using the curable resin composition of Claim 8, and then a irradiation process and / or heat processing are performed, The formation method of the protective film characterized by the above-mentioned.
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JP2005338831A (en) * 2004-05-25 2005-12-08 Samsung Electronics Co Ltd Photoresist composition for organic film of liquid crystal display, spinless coating method thereof, fabrication method of organic film pattern using the same, and liquid crystal display fabricated by the same
JP2006228578A (en) * 2005-02-17 2006-08-31 Dainippon Printing Co Ltd Color filter base plate for organic electroluminescent element
JP2006257257A (en) * 2005-03-17 2006-09-28 Sumitomo Chemical Co Ltd Curable resin composition and protective film formed by the same
JP4735818B2 (en) * 2005-08-12 2011-07-27 Jsr株式会社 Resin composition, method for forming color filter protective film, and color filter protective film
JP2007119720A (en) * 2005-09-29 2007-05-17 Dainippon Printing Co Ltd Curable resin composition
JP2007100020A (en) * 2005-10-07 2007-04-19 Jsr Corp Curable resin composition, over coat, and method for producing the same
JP4851359B2 (en) * 2006-02-16 2012-01-11 東京応化工業株式会社 Photosensitive resin composition and pattern forming method using the same
US8617795B2 (en) 2006-02-16 2013-12-31 Tokyo Ohka Kogyo Co., Ltd. Photosensitive resin composition and pattern forming method using the same
JP4635935B2 (en) * 2006-03-29 2011-02-23 Jsr株式会社 Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element
JP5524480B2 (en) * 2006-05-18 2014-06-18 日本化薬株式会社 Thermosetting resin composition and cured product thereof
JP2008144124A (en) * 2006-11-14 2008-06-26 Jsr Corp Thermosetting resin composition, method for forming color filter protective film and color filter protective film
JP4637221B2 (en) * 2007-09-28 2011-02-23 富士フイルム株式会社 Positive photosensitive resin composition and cured film forming method using the same
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