KR20100029034A - Curable resin composition, set for forming resin cured film, protective film and process for forming protective film - Google Patents

Abstract

PURPOSE: A curable resin composition is provided to form a curable film with excellent flatness, to ensure high transparency and surface hardness, heat resistance and pressure resistance, and excellent alkali resistance and anti-sputtering property. CONSTITUTION: A curable resin composition comprises (A) a polymer having a repeating unit derived from a polymerizable unsaturated compound with an oxyranyl group or oxetanyl group, and (B) polyorganosiloxane represented by chemical formula 1. In chemical formula 1, R^1~R^6 are independently a group represented by chemical formula 2, hydrogen atom, C1~4 alkoxy group, C3~8 cycloalkyloxy group or phenoxy group; and n is an integer of 2~30.

Description

CURABLE RESIN COMPOSITION, SET FOR FORMING RESIN CURED FILM, PROTECTIVE FILM AND PROCESS FOR FORMING PROTECTIVE FILM}

The present invention relates to a curable resin composition, a method for forming a protective film from the curable resin composition, and a protective film. More specifically, curable resin composition which is very suitable as a material for forming the protective film used for the color filter for liquid crystal display elements (LCD), and the color filter for charge coupling elements (CCD), and the formation of the protective film using this curable resin composition. A protective film formed from a method and its composition.

Optical devices such as LCDs and CCDs are immersed in a display element by a solvent, an acid or an alkaline solution during the manufacturing process thereof, and when the wiring electrode layer is formed by sputtering, the surface of the element is locally exposed to high temperatures. do. Therefore, in order to prevent deterioration or damage of an element by such a process, forming the protective film which consists of a thin film which is resistant to these processes is performed on the surface of an element.

Such a protective film should have high adhesion to the substrate or base layer on which the protective film should be formed, or a layer formed on the protective film, the film itself should be smooth and strong, have transparency, heat resistance and light resistance It is required to have high performance, such as not causing deterioration such as coloring, yellowing, and whitening over a long period of time, and having excellent water resistance, solvent resistance, acid resistance, and alkali resistance. As a material for forming the protective film which satisfy | fills these various characteristics, the thermosetting resin composition containing the polymer which has glycidyl group, for example is known (patent document 1 and 2).

In addition, in a color liquid crystal display device, for example, a color liquid crystal display device of a super twisted nematic (STN) method or a thin film transistor (TFT) method, beads are used to uniformly maintain a cell gap that defines the thickness of the liquid crystal layer. The panel is bonded after spreading a spacer having a shape of) onto a protective film. Thereafter, the liquid crystal cell is sealed by thermocompression bonding the sealing material. However, a phenomenon in which the protective film in the portion where the beads are present is dent due to the heat and pressure applied at that time is a problem that the cell gap is misaligned. In particular, when manufacturing an STN type color liquid crystal display element, bonding of a color filter and an opposing board | substrate must be performed with extremely precise precision, and extremely high leveling performance of a level difference and heat-resistant withstand voltage are calculated | required by a protective film.

In recent years, a wiring electrode made of, for example, indium tin oxide (ITO), indium zinc oxide (IZO), or the like is formed on the protective film of the color filter by sputtering, and ITO or IZO is patterned with strong acid, strong alkali, or the like. The method is also being adopted. For this reason, the surface of a color filter protective film is exposed to high temperature locally at the time of sputtering, or to various chemicals. Therefore, the adhesiveness with the wiring electrode is also required to withstand these treatments and to prevent the ITO or IZO from peeling off from the protective film during chemical treatment.

In order to provide adhesiveness as mentioned above to cured resin, the method of adding an adhesion | attachment adjuvant to curable resin composition for forming this, for example is proposed (patent document 3). However, there exists a problem that the adhesion | attachment adjuvant which provides the said adhesive contaminates the inside of a coating machine as a sublimation at the time of protective film formation, and requires maintenance, washing | cleaning, etc. In recent years, not only an adhesion | attachment adjuvant from this viewpoint, but the trend of low-out gasification of a material is also seen. Moreover, the curable resin composition which added the conventionally known adhesion | attachment adjuvant is inadequate in the "patterning characteristic" of the wiring electrode calculated | required from a panel maker by the refinement | miniaturization of the wiring electrode accompanying high resolution and enlargement of a panel. There may be a case. That is, in a panel maker, in order to eliminate the etching nonuniformity between board | substrates, there exists a tendency to lengthen an etching time. If the margin for this etching is insufficient, tapering or undercut occurs as the end of the wiring electrode becomes impossible to obtain a desired pattern, which may cause disconnection, leading to deterioration in yield. Moreover, the composition containing the adhesion | attachment adjuvant not only has the problem that the shelf life of the composition itself is very short, but also requires frequent maintenance of the coating machine for apply | coating this, and it became more complicated in operation.

After satisfying the general required performance as the protective film, a protective film which satisfies the above-mentioned production performance can be formed simply and easily, and a material excellent in storage stability as a composition is not yet known.

In addition, although Patent Document 4 discloses a thermosetting composition containing a latent carboxyl compound used in paints, inks, adhesives, and molded articles, nothing is considered about the application of the color filter to the protective film, which requires such performance. Not.

[Patent Document 1] Japanese Patent Application Laid-Open No. 5-78453

[Patent Document 2] Japanese Patent Application Laid-Open No. 2001-91732

[Patent Document 3] Japanese Patent Application Laid-Open No. 5-171099

[Patent Document 4] Japanese Patent Application Laid-Open No. 4-218561

The present invention has been made on the basis of the above circumstances, and an object thereof is to form a cured film having high flatness even on a gas having low surface flatness, and also to have high transparency and surface hardness, and to provide heat resistance, acid resistance and alkali resistance. A composition which is excellent in various resistances such as sputtering resistance and excellent in patterning characteristics of wiring electrodes, can be suitably used, and has excellent storage stability, a method of forming a protective film using the composition, and It is to provide a protective film formed from the composition.

Still other objects and advantages of the present invention will become apparent from the following description.

According to this invention, the said objective and advantage of this invention are 1st,

[A] A polymer having a repeating unit derived from a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group, and

[B] A curable resin composition containing a polyorganosiloxane (hereinafter referred to as "[B] polyorganosiloxane") represented by the following formula (1) is achieved.

In Formula 1, R ¹ to R ⁶ are each independently represented by the following Formula (2):

(In formula (2), R <^7> -R <^11> is mutually independently a hydrogen atom, a fluorine atom, a C1-C4 alkyl group, a phenyl group, or a C1-C4 perfluoroalkyl group, and a is an integer of 1-6.) Is a group, a hydrogen atom, an alkoxyl group having 1 to 4 carbon atoms, a cycloalkyloxyl group having 3 to 8 carbon atoms or a phenoxy group, n is an integer of 2 to 30, provided that at least one of R ¹ to R ⁶ A group represented by the formula (2).)

[A] polymer contained in the curable resin composition is preferably a polymerizable unsaturated compound having [A1] (a) an oxiranyl group or an oxetanyl group, and (b1) a polymerizable unsaturated carboxylic acid and a polymerizable unsaturated polyvalent. (多 價) at least one selected from the group consisting of carboxylic anhydrides, (b3) oxiranyl groups, oxetanyl groups, carboxyl groups, acid anhydride groups, acetal ester structures of carboxylic acids, ketal ester structures of carboxylic acids, Copolymer with a polymerizable unsaturated compound having neither a 1-alkylcycloalkyl ester structure of carboxylic acids nor a t-butyl ester structure of carboxylic acids (hereinafter referred to as "copolymer [A1]"), [A2] molecule In the above, two or more oxiranyl groups or oxetanyl groups, acetal ester structure of carbonic acid, ketal ester structure of carbonic acid, 1-alkylcycloalkylester structure of carbonic acid, and t-butylester sphere of carbonic acid At least a polymer having the structure of one selected from the group consisting of (referred to as "polymer [A2]" hereinafter), or

[A3] (a) A polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group, (b3) An oxiranyl group, an oxetanyl group, a carboxyl group, an acid anhydride group, an acetal ester structure of a carboxylic acid, a ketal of a carboxylic acid It is a copolymer (henceforth "copolymer [A3]") with the polymerizable unsaturated compound which has neither an ester structure, the 1-alkyl cycloalkyl ester structure of carboxylic acid, and the t-butyl ester structure of carboxylic acid.

According to this invention, the said objective and advantage of this invention are 2nd,

[A] A first liquid comprising a curable resin composition wherein the polymer is the copolymer [A3],

(C) It is achieved by the set for forming the resin cured film which consists of a 2nd liquid containing a hardening | curing agent.

According to this invention, the said objective and advantage of this invention are 3rd,

It is achieved by the protective film formed from the said curable resin composition or set.

According to this invention, the said objective and advantage of this invention are 4th,

The film is formed on a board | substrate using the said curable resin composition, and then heat-processing is achieved by the formation method of the protective film characterized by the above-mentioned.

According to this invention, the said objective and advantage of this invention are 5th,

It is achieved by the formation method of the protective film which mixes the 1st liquid and 2nd liquid of the set for forming the said resin cured film, forms a film on a board | substrate using this mixture, and then heat-processes.

According to the present invention, even in a gas having a low surface flatness, a cured film having high flatness can be formed thereon, having high transparency and surface hardness, and excellent in various resistances such as heat resistance, acid resistance, alkali resistance, sputtering resistance, and the like. Can be suitably used in order to form a protective film for an optical device requiring particularly good patterning characteristics of the wiring electrode, and furthermore, a curable resin composition excellent in storage stability, a method of forming a protective film using the curable resin composition, and the curable resin composition A protective film formed from is provided.

(The best form to carry out invention)

Hereinafter, each component of the resin composition of this invention is demonstrated.

[A] Polymer

[A] polymer used for this invention is a polymer which has a repeating unit derived from the polymerizable unsaturated compound which has an oxiranyl group or an oxetanyl group.

[A] The polymer is not limited as long as the above conditions are satisfied, and may be any of an addition polymer, a heavy addition polymer, and a polycondensation polymer.

As such [A] polymer, it is, for example

[A1] (a) A polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group (hereinafter referred to as an "unsaturated compound (a)"), and (b1) a polymerizable unsaturated carbonic acid and a polymerizable unsaturated polycarboxylic anhydride At least one member selected from the group consisting of hereinafter (unsaturated compound (b1)), (b3) an oxiranyl group, an oxetanyl group, a carboxyl group, an acid anhydride group, an acetal ester structure of a carboxylic acid, carbon Air with a polymerizable unsaturated compound (hereinafter referred to as an "unsaturated compound (b3)") having neither a ketal ester structure of an acid, a 1-alkylcycloalkyl ester structure of a carboxylic acid, or a t-butyl ester structure of a carboxylic acid. In the copolymer (copolymer [A1]) and [A2] molecule, two or more oxiranyl groups or oxetanyl groups, acetal ester structures of carboxylic acids, ketal ester structures of carboxylic acids, and 1-alkylcycloalkyl esters of carboxylic acids Structure and carbonic acid Copolymer of a polymer (polymer [A2]), an [A3] unsaturated compound (a), and an unsaturated compound (b3) having at least one structure selected from the group consisting of a t-butyl ester structure (copolymer [A3 ) And the like.

As a group which forms the acetal ester structure of the carbonic acid in the said polymer [A2], it is a 1-methoxyethoxy group, 1-ethoxyethoxyl group, 1-n-propoxyoxyxyl group, 1, for example. -i-propoxyoxyl group, 1-n-butoxyethoxyl group, 1-i-butoxyethoxyl group, 1-sec-butoxyethoxyl group, 1-t-butoxyethoxyl group, 1 -Cyclopentyloxyethoxyl group, 1-cyclohexyloxyethoxyl group, 2-tetrahydrofuranyloxyl group, 2-tetrahydropyranyloxyl group, etc. are mentioned.

Among these, 1-ethoxyethoxyl group, 1-n-propoxy ethoxyl group, 1-cyclohexyloxyethoxyl group, 2-tetrahydrofuranyloxyl group, 2-tetrahydropyranyloxyl group, etc. are preferable.

As a group which forms the ketal ester structure of a carboxylic acid, it is a 1-methyl-1- methoxyethoxy group, 1-methyl-1- ethoxy ethoxyl group, 1-methyl-1-n-propoxy, for example. Toxyl group, 1-methyl-1-i-propoxyethoxy group, 1-methyl-1-n-butoxyethoxyl group, 1-methyl-1-i-butoxyethoxyl group, 1-methyl-1 -sec-butoxyethoxyl group, 1-methyl-1-t-butoxyethoxyl group, 1-methyl-1-cyclohexyloxyethoxyl group, etc. are mentioned.

Among these, 1-methyl-1-methoxyethoxyl group, 1-methyl-1-cyclohexyloxyethoxyl group, etc. are preferable.

Examples of the group forming the 1-alkylcycloalkyl ester structure of the carboxylic acid include 1-methylcyclopropyl group, 1-methylcyclobutyl group, 1-methylcyclopentyl group, 1-methylcyclohexyl group, and 1-methyl. Cycloheptyl group, 1-methylcyclooctyl group, 1-methylcyclononyl group, 1-methylcyclodecyl group, 1-ethylcyclopropyl group, 1-ethylcyclobutyl group, 1-ethylcyclopentyl group, 1-ethylcyclo Hexyl group, 1-ethylcycloheptyl group, 1-ethylcyclo octyl group, 1-ethylcyclononyl group, 1-ethylcyclodecyl group, etc. are mentioned.

Curable resin composition containing a polymer [A2] can provide curable resin composition excellent in storage stability compared with the case of using copolymer [A1], and also excellent in the planarization performance of the protective film formed.

As such a polymer [A2], for example,

[A2-1] Group of unsaturated compounds (a) and (b2) acetal ester structure of carbonic acid, ketal ester structure of carbonic acid, 1-alkylcycloalkylester structure of carbonic acid and t-butylester structure of carbonic acid A copolymer of a polymerizable unsaturated compound (hereinafter referred to as "unsaturated compound (b2)") and an unsaturated compound (b3) having at least one structure selected from (hereinafter, "copolymer [A2-1]) ), [A2-2] copolymer of an unsaturated compound (a), an unsaturated compound (b1), an unsaturated compound (b2) and an unsaturated compound (b3) (hereinafter referred to as "copolymer [A2-2 )) ") And the like.

Such [A] polymer is, in copolymer [A1], the unsaturated compound (a), unsaturated compound (b1) and unsaturated compound (b3); In the copolymer [A2-1], an unsaturated compound (a), an unsaturated compound (b2), and an unsaturated compound (b3); In the copolymer [A2-2], an unsaturated compound (a), an unsaturated compound (b1), an unsaturated compound (b2), and an unsaturated compound (b3); In the copolymer [A3], the unsaturated compound (a) and the unsaturated compound (b3) are each preferably reacted in the presence of a suitable polymerization initiator in the presence of a suitable polymerization initiator, for example, by radical polymerization. It can manufacture.

As an unsaturated compound (a) used in order to manufacture copolymer [A1], copolymer [A2-1], copolymer [A2-2], or copolymer [A3], it is (meth) acrylic-acid glycidyl, for example. , α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, (meth) acrylate 3,4-epoxybutyl, α-ethyl acrylate 3,4-epoxybutyl (Meth) acrylic acid 6,7-epoxyheptyl, α-ethylacrylic acid 6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, etc. are mentioned.

Among these unsaturated compounds (a), (meth) acrylic acid glycidyl, (meth) acrylic acid 6,7-epoxyheptyl, p-vinylbenzyl glycidyl ether, 3-methyl-3- (meth) acryloyloxymethyl Oxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 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.

Examples of the unsaturated compound (b1) used for producing the copolymer [A1] or the copolymer [A2-2] include unsaturated carbon acids such as (meth) acrylic acid and crotonic acid; And unsaturated polyhydric carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride.

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

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

As an unsaturated compound (b2) used in order to manufacture copolymer [A2-1] or copolymer [A2-2], it is selected from the group which consists of acetal ester structure of carboxylic acid and a ketal ester structure of carboxylic acid, for example. Norbornene compounds having at least one structure; (Meth) acrylic acid having at least one structure selected from the group consisting of acetal ester structures of carboxylic acids, ketal ester structures of carboxylic acids, 1-alkylcycloalkyl ester structures of carboxylic acids, and t-butyl ester structures of carboxylic acids Ester compounds; and the like.

As a norbornene compound which has at least 1 sort (s) of structure chosen from the group which consists of the acetal ester structure of the said carboxylic acid and the ketal ester structure of a carboxylic acid, for example

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

2,3-di-trimethylsilanyloxycarbonyl-5-norbornene,

2,3-di-triethylsilanyloxycarbonyl-5-norbornene,

2,3-di-t-butyldimethylsilanyloxycarbonyl-5-norbornene,

2,3-di-t-butyloxycarbonyl-5-norbornene,

2,3-di-benzyloxycarbonyl-5-norbornene and the like;

As a specific example of the (meth) acrylic acid ester compound which has the acetal ester structure of the said carboxylic acid or the ketal ester structure of a carboxylic acid, for example, 1-ethoxyethyl (meth) acrylate and tetrahydro-2H-pyran-2- Mono (meth) acrylate, 1- (cyclohexyloxy) ethyl (meth) acrylate, 1- (2-methylpropoxy) ethyl (meth) acrylate, 1- (1,1-dimethyl-ethoxy) Ethyl (meth) acrylate, 1- (cyclohexyloxy) ethyl (meth) acrylate, and the like;

As a specific example of the (meth) acrylic acid ester compound which has the 1-alkyl cycloalkyl ester structure of the said carboxylic acid, it is, for example

1-methylcyclopropyl (meth) acrylate, 1-methylcyclobutyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 1-ethylcyclopropyl ( Meth) acrylate, 1-ethylcyclobutyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate, 1-ethylcycloheptyl (meth) acrylate, 1 -Ethylcyclooctyl (meth) acrylate, 1-ethylcyclononyl (meth) acrylate, 1-ethylcyclodecyl (meth) acrylate, and the like;

As a specific example of the (meth) acrylic acid ester compound which has the t-butyl ester structure of the said carboxylic acid, t-butyl (meth) acrylate etc. are mentioned, respectively.

Among these, a (meth) acrylic acid ester compound having an acetal ester structure of carbonic acid, a ketal ester structure of carbonic acid, a 1-alkylcycloalkyl ester structure of carbonic acid or a t-butylester structure of carbonic acid is preferable, and 1- Ethoxyethyl methacrylate, tetrahydro-2H-pyran-2-yl (meth) acrylate, 1- (2-methylpropoxy) ethyl methacrylate, 1- (1,1-dimethyl-ethoxy) Ethyl methacrylate, 1- (cyclohexyloxy) ethyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-ethylcyclohexyl (meth) acrylate or t-butyl methacrylate is used It is particularly preferable to. These preferable unsaturated compounds (b2) are effective in increasing the heat resistance and surface hardness of the protective film obtained while providing a one-component curable resin composition having high copolymerization reactivity and excellent storage stability and planarization performance of the protective film.

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

As an unsaturated compound (b3) used in order to manufacture copolymer [A1], copolymer [A2-1], copolymer [A2-2], or copolymer [A3], it is (meth) acrylic acid 2-hydride, for example. (Meth) acrylic acid hydroxyalkyl esters such as hydroxyethyl and (meth) acrylic acid 2-hydroxypropyl;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-methacrylate (meth) acrylate (Meth) acrylic acid alkyl esters such as butyl and t-butyl (meth) acrylate; (Meth) acrylic acid cyclopentyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (hereinafter referred to as "tricyclo [ 5.2.1.0 ^2,6 ] decan-8-yl "is called" dicyclopentanyl ") (meth) acrylic acid alicyclic type, such as (meth) acrylic acid 2-dicyclopentanyloxyethyl and (meth) acrylic acid isoboroyl ester; (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 itaconate;

Unsaturated dicarbonyls such as N-phenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate Mid derivatives;

Aromatic vinyl compounds such as styrene, α-methylstyrene and p-methoxystyrene; Indene derivatives such as indene and 1-methylindene; And conjugated dienes such as 1,3-butadiene.

Among these unsaturated compounds (b3), methyl methacrylate, t-butyl methacrylate, cyclohexyl acrylate, dicyclopentanyl methacrylate, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexyl maleimide, Styrene, p-methoxystyrene, 1,3-butadiene and the like are preferred. These preferred unsaturated compounds (b3) have high copolymerization reactivity, and also have heat resistance (except 1,3-butadiene) or surface hardness (except 1,3-butadiene) of the protective film formed. Effective for raising

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

As a preferable specific example of copolymer [A1], for example, methacrylic acid glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / styrene copolymer, methacrylic acid glycidyl / methacrylic acid / N-phenylmaleimide / Styrene copolymer, glycidyl methacrylate / methacrylic acid / N-cyclohexyl maleimide / styrene copolymer, methacrylate glycidyl / methacrylic acid / methacrylic acid dicyclopentanyl / 1,3-butadiene air Copolymer, glycidyl methacrylate / methacrylic acid / methacrylic acid dicyclopentanyl / styrene / 1,3-butadiene copolymer, 3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / Dicyclopentanyl / styrene copolymer, 3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / N-phenylmaleimide / styrene copolymer, 3-ethyl-3- (meth) Acryloyloxymethyloxetane / methacrylic acid / N-cyclohexylmaleimide / styrene copolymerization Sieve, 3-ethyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / methacrylic dicyclopentanyl / styrene / 1,3-butadiene copolymer, 3-methyl-3- (meth) acrylo Iloxymethyloxetane / methacrylic acid / methacrylic acid dicyclopentanyl / styrene copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / N-phenylmaleimide / styrene copolymer , 3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylic acid / N-cyclohexylmaleimide / styrene copolymer.

In the copolymer [A1], the content rate of the repeating unit derived from an unsaturated compound (a) is preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight relative to all the repeating units. The content rate of the repeating unit derived from an unsaturated compound (b1) becomes like this. Preferably it is 5-40 weight% with respect to all the repeating units, Especially preferably, it is 10-30 weight%. The content rate of the repeating unit derived from an unsaturated compound (b3) becomes like this. Preferably it is 10-70 weight% with respect to all the repeating units, Especially preferably, it is 20-50 weight%. In the copolymer [A1], the repeating unit derived from the repeating unit + unsaturated compound (b3) derived from the unsaturated compound (a) is 100% by weight. 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%, when the storage stability of the curable resin composition obtained is insufficient. There is. Moreover, when the content rate of the repeating unit derived from an unsaturated compound (b1) is less than 5 weight%, the heat resistance, surface hardness, and chemical resistance of the protective film formed may be insufficient, and when it exceeds 40 weight%, storage stability of a composition There is a lack of this. Moreover, when the content rate of the repeating unit derived from an unsaturated compound (b3) is less than 10 weight%, the storage stability of a composition may be inadequate, and when it exceeds 70 weight%, the heat resistance and surface hardness of a protective film may be insufficient. .

As a preferable specific example of copolymer [A2-1], for example, glycidyl methacrylate / tetrahydro-2H-pyran-2yl methacrylate / dicyclopentanyl / styrene methacrylate, glycidyl methacrylate / Methacrylic acid tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer, methacrylic acid glycidyl / acrylic acid tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene Copolymer, glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer, glycidyl methacrylate / 1- (cyclohexyloxy) Ethyl / N-cyclohexylmaleimide / styrene copolymer, glycidyl methacrylate / methacrylic acid 1- (cyclohexyloxy) ethyl / N-cyclohexylmaleimide / styrene copolymer, glycidyl methacrylate T-butyl methacrylate / N-cyclohexylmaleimide / styrene copolymer, Glycidyl methacrylate / tetrahydro-2H-pyran-2-yl / methyl methacrylate / styrene copolymer,

3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylate tetrahydro-2H-pyran-2-yl / methacrylate dicyclopentanyl / styrene copolymer, 3-methyl-3- (meth ) Acryloyloxymethyloxetane / methacrylic acid tetrahydro-2H-pyran-2-yl / N-phenylmaleimide / styrene copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / Methacrylic acid tetrahydro-2H-pyran-2-yl / N-cyclohexylmaleimide / styrene copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / t-butyl methacrylate / N -Cyclohexylmaleimide / styrene copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / 1-ethylcyclopentyl methacrylate / N-phenylmaleimide / styrene copolymer.

In the copolymer [A2-1], the content rate of the repeating unit derived from the unsaturated compound (a) is preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight relative to all the repeating units. When the content rate of the repeating unit derived from an unsaturated compound (a) is less than 10 weight%, the heat resistance and surface hardness of the protective film formed may be insufficient, and when it exceeds 70 weight%, when the storage stability of the curable resin composition obtained is insufficient. There is.

Moreover, the content rate of the repeating unit derived from an unsaturated compound (b2) becomes like this. Preferably it is 5 to 60 weight%, Especially preferably, it is 10 to 50 weight%. By making the content rate of the repeating unit derived from an unsaturated compound (b2) into this range, the more favorable heat resistance and higher surface hardness of the protective film formed can be implement | achieved.

Moreover, the content rate of the repeating unit derived from an unsaturated compound (b3) becomes like this. Preferably it is 10-60 weight% with respect to all the repeating units, Especially preferably, it is 20-50 weight%.

In copolymer [A2-1], it is a repeating unit derived from the repeating unit + unsaturated compound (b3) derived from a repeating unit + unsaturated compound (b2) derived from an unsaturated compound (a) = 100 weight%.

As a preferable specific example of copolymer [A2-2], for example, glycidyl methacrylate / 1-ethylcyclopentyl acrylate / N-phenylmaleimide / styrene / methacrylic acid copolymer or glycidyl methacrylate / 1-ethylcyclopentyl methacrylate / N-phenylmaleimide / styrene / methacrylic acid copolymer.

In the copolymer [A2-2], the content rate of the repeating unit derived from the unsaturated compound (a) is preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight relative to all the repeating units.

The content rate of the repeating unit derived from an unsaturated compound (b1) becomes like this. Preferably it is 10-40 weight%, Especially preferably, it is 15-30 weight%. In the copolymer [A2-2], when the content rate of the repeating unit derived from an unsaturated compound (b1) exceeds 40 weight%, the storage stability of the obtained curable resin composition may be lost, and it is unpreferable.

The content rate of the repeating unit derived from an unsaturated compound (b2) becomes like this. Preferably it is 5-60 weight%, Especially preferably, it is 10-50 weight%.

Moreover, the content rate of the repeating unit derived from an unsaturated compound (b3) becomes like this. Preferably it is 10-60 weight% with respect to all the repeating units, Especially preferably, it is 20-50 weight%.

It originates in the repeating unit + unsaturated compound (b3) derived from repeating unit + unsaturated compound (b2) derived from a repeating unit + unsaturated compound (b1) derived from a copolymer (A2-2) in copolymer [A2-2]. Repeating unit to be 100% by weight.

As a preferable specific example of copolymer [A3], for example, methacrylate glycidyl / styrene copolymer, methacrylate glycidyl / methacrylate dicyclopentanyl copolymer, methacrylate glycidyl / methacrylate dicyclo Fentanyl / styrene copolymer, glycidyl methacrylate / N-cyclohexylmaleimide / styrene copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / styrene copolymer, 3-methyl-3 -(Meth) acryloyloxymethyloxetane / methacrylic acid dicyclopentanyl copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / methacrylate dicyclopentanyl / styrene copolymer, 3-methyl 3- (meth) acryloyloxymethyloxetane / N-cyclohexylmaleimide / styrene copolymer.

In copolymer [A3], the content rate of the repeating unit derived from an unsaturated compound (a) is 1-90 weight% with respect to all the repeating units, Especially preferably, it is 40-90 weight%. 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 the protective film formed to fall, and when it exceeds 90 weight%, the heat resistance of a protective film and the curable resin composition obtained There exists a tendency for the storage stability of to fall.

In addition, in copolymer [A3], the content rate of the repeating unit derived from an unsaturated compound (b3) becomes the quantity which subtracted the content rate of the repeating unit derived from an unsaturated compound (a) from 100 weight%.

[A] The polymer preferably has a polystyrene reduced weight average molecular weight (hereinafter sometimes referred to as "Mw") measured by gel permeation chromatography (elution solvent: tetrahydrofuran), and more preferably 1,000 to 100,000. Is 2,000 to 50,000, particularly preferably 3,000 to 40,000. In this case, when Mw is less than 1,000, the applicability | paintability of the curable resin composition obtained may become inadequate, or the heat resistance of the protective film formed may be inadequate, and when Mw exceeds 100,000, planarization performance may become inadequate.

Moreover, molecular weight distribution (Mw / Mn) of [A] polymer becomes like this. Preferably it is 5.0 or less, More preferably, it is 3.0 or less. However, said "Mn" is polystyrene conversion number average molecular weight measured by the gel permeation chromatography (elution solvent: tetrahydrofuran).

As a solvent used for manufacture of [A] polymer, diethylene glycol methyl ethyl ether, a propylene glycol monomethyl ether acetate, etc. are mentioned, for example. The use ratio of a solvent becomes like this. Preferably it is 150-300 weight part with respect to a total of 100 weight part of the unsaturated compound to be used.

As a polymerization initiator used for manufacture of [A] polymer, For example, 2,2'- azobisisobutyronitrile (AIBN), 2,2'- azobis (2, 4- dimethylvaleronitrile), etc. A radical polymerization initiator can be mentioned. The use ratio of the polymerization initiator is preferably 0.5 to 10 parts by weight based on 100 parts by weight in total of the unsaturated compound to be used.

The polymerization temperature is preferably 70 to 100 ° C, and the polymerization time is preferably 3 to 10 hours.

(B) Polyorganosiloxane

[B] polyorganosiloxane used in the present invention is a polyorganosiloxane represented by the formula (1).

As the alkoxyl group having 1 to 4 carbon atoms of R ¹ ~R ⁶ in the above formula, for example, such as a methoxy group, an ethoxy group, n- propoxy group, isopropoxy group, n- butoxy group;

As a C3-C8 cycloalkyloxyl group, a cyclohexyloxyl group, a cycloheptyloxyl group, etc. are mentioned, for example.

As a C1-C4 alkyl group in the said General formula (2), For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group etc .;

As a C1-C4 perfluoroalkyl group, a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluoro butyl group, etc. are mentioned, for example. In said Formula (2), it is preferable that R <^7> is a hydrogen atom, a fluorine atom, a C1-C4 alkyl group, a phenyl group, or a C1-C4 perfluoroalkyl group, and all of R <^8> -R <^11> is a hydrogen atom. . As a in the said General formula (2), 1 is preferable. As R <^7> , a hydrogen atom or a C1-C4 alkyl group is preferable, and a hydrogen atom, a methyl group, or an ethyl group is especially preferable.

[B] As the polyorganosiloxane, all of R ¹ to R ⁶ in the formula (1) are preferably a group represented by the formula (2), and a polyorganosiloxane represented by the following formula (3) is particularly preferable.

(In Formula 3, n is as defined in the formula (1).)

As n in the said General formula (1), it is preferable that it is an integer of 5-20. In addition, this n value should be understood as the average value calculated | required by calculation from the value and structure of the weight average molecular weight (Mw) of [B] polyorganosiloxane demonstrated next.

[B] The polyorganosiloxane has a polystyrene reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC), preferably 500 to 10,000, more preferably 1,000 to 5,000, still more preferably 1,000 It is preferable that it is -3,000. If Mw is less than 500, the protective film obtained may not have sufficient adhesiveness, and sufficient sputtering resistance may not be obtained. On the other hand, if Mw exceeds 10,000, the coating property of the composition is inferior and uniform. The coating film may not be obtained.

The polyorganosiloxane [B] may be synthesized by any method as long as it has the above structure, but can be synthesized by any of the following methods, for example.

As a first method, a compound represented by the following formula (4) is hydrolyzed and condensed to obtain a polyorganosiloxane represented by the following formula (5), and then reacted with this compound represented by the following formula (6), or represented by the following formula (7) The compound to be hydrolyzed and condensed to obtain a polyorganosiloxane represented by the following formula (8), and then synthesized by a method of reacting this and the compound represented by the formula (6).

Si (R ¹² ) ₂ (R ¹³ ) ₂

In Formula 4, R ¹² And R ¹³ are each an alkoxyl group having 1 to 4 carbon atoms, a cycloalkyloxyl group having 3 to 8 carbon atoms, or a phenoxyl group, except that Si-R ¹² The hydrolyzability of the bond is Si-R ¹³ Greater than the hydrolysis of the bond.)

In Formula 5, R ¹² And R ¹³ are each as defined in Chemical Formula 4, and n is as defined in Chemical Formula 1.

In Formula 6, R ⁷ to R ¹¹ And a are as defined in Formula 2, respectively.)

SiH ₂ (R ¹⁴ ) ₂

In Formula 7, R ¹⁴ Is an alkoxyl group having 1 to 4 carbon atoms, a cycloalkyloxyl group having 3 to 8 carbon atoms, or a phenoxyl group.)

In Formula 8, R ¹⁴ Are as defined in the formula (7), n is as defined in the formula (1).)

As the compound represented by the formula (4), for example, dimethoxy diethoxy silane, dimethoxy dipropoxy silane, dimethoxy diphenoxy silane, dimethoxy dicyclohexyloxy silane, diethoxy dicyclohexyloxy silane and the like ;

As a compound represented by the said General formula (7), dimethoxysilane, diethoxysilane, etc. are mentioned, for example.

The hydrolysis / condensation reaction of the compound represented by the above formula (4) or (7) is preferably carried out by reacting these compounds with water in accordance with the hydrolysis / condensation reaction of a known silane compound in the presence of a suitable organic solvent and catalyst. Can be.

As an organic solvent used for this hydrolysis-condensation reaction, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, t-butyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl A water-soluble solvent, such as a ketone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, tetrahydrofuran, dioxane, acetonitrile, is mentioned. Since these water-soluble solvents are preferably removed in a subsequent step, those having a low boiling point are suitable, and in particular, methanol, ethanol, n-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, propylene glycol monomethyl ether, methyl isobutyl Ketone or tetrahydrofuran is preferable, Among these, ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, are more preferable from a viewpoint of the solubility of a raw material compound, Most preferable is methyl isobutyl ketone. As a usage ratio of a solvent, it is preferable to set it as the ratio which is 50-300 weight part with respect to 100 weight part of said compounds in the said Formula (4) or (7) in a solution, and it is more preferable to set it as the ratio which becomes 100-200 weight part. Do.

As a catalyst used for the said hydrolysis / condensation reaction, an acid catalyst, a base catalyst, etc. are mentioned, for example, As these acid catalysts, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, phosphoric acid, acetic acid are mentioned as an acid catalyst, for example. Trifluoroacetic acid, trifluoromethanesulfonic acid, acidic ion exchange resins, various Lewis acids and the like;

As the base catalyst, for example, ammonia, primary amine, secondary amine, tertiary amine, nitrogen-containing aromatic compound (e.g. pyridine), basic ion exchange resin, hydroxide (e.g. sodium hydroxide), carbonate ( For example, potassium carbonate), a carbonate (for example, sodium acetate), various Lewis bases, etc. are mentioned, respectively. It is preferable to use an acid catalyst among these, and it is preferable to use oxalic acid or phosphoric acid especially from a molecular weight control viewpoint. As a usage ratio of a catalyst, it is preferable to set it as 0.1-20 weight part with respect to 100 weight part of compounds represented by the said Formula (4) or (7), and it is more preferable to set it as 0.5-10 weight part.

As a ratio of the water used for the said hydrolysis / condensation reaction, it is preferable to set it as 0.5-5 mol with respect to 1 mol of silicon atoms in the compound represented by the said General formula (4) or (7), and it is more preferable to set it as 1-3 mol.

The reaction temperature of the hydrolysis and condensation reaction is preferably 40 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours.

Thus, the solution containing the polyorganosiloxane represented by the said Formula (5) or (8) can be obtained. Hereinafter, the reaction of the polyorganosiloxane obtained above with the compound represented by the formula (6) is divided into the case of the polyorganosiloxane represented by the formula (5) and the case of the polyorganosiloxane represented by the formula (8) in order. Explain.

The polyorganosiloxane represented by the formula (5) may be provided to the reaction with the compound represented by the formula (6) in the following step after isolating and purifying from the solution, but the solution is intact in view of the simplicity of the process. It is preferable to provide to the next process. The reaction of the polyorganosiloxane represented by the formula (5) with the compound represented by the formula (6) is therefore preferably performed in the presence of the same organic solvent and catalyst as in the hydrolysis / condensation reaction. As a ratio of the compound represented by the said General formula (6) used here, Preferably it is 0.1-1.0 mol with respect to 1 mol of the silicon atoms in the polyorganosiloxane represented by the said Formula (5), More preferably, it is 0.3-1.0 mol. The reaction temperature of this reaction becomes like this. Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC. The reaction time is preferably 2 to 36 hours, more preferably 3 to 24 hours.

On the other hand, it is preferable that the polyorganosiloxane represented by the formula (8) is isolated and purified from a solution and then used for the reaction with the compound represented by the formula (6) in the next step. This reaction can be carried out in the presence of water and preferably a suitable organic solvent and catalyst.

As a ratio of the compound represented by the said Formula (6) used in reaction of the polyorganosiloxane represented by the said Formula (8) and the compound represented by the said Formula (6), 1 mol of silicon atoms in the polyorganosiloxane represented by the said Formula (8) With respect to, Preferably it is 0.1-1.0 mol, More preferably, it is 0.3-1.0 mol.

As a ratio of the water used at the time of the hydrolysis-condensation reaction of the polyorganosiloxane represented by the said Formula (8) and the compound represented by the said Formula (6), it is 0.5 with respect to 1 mol of silicon atoms of the polyorganosiloxane represented by the said Formula (8). It is preferable to set it as -5 mol, and it is more preferable to set it as 1-3 mol.

Organic solvents and catalysts used in the reaction of the polyorganosiloxane represented by the formula (8) with the compound represented by the formula (6) are preferably used for the hydrolysis / condensation reaction of the compounds represented by the formula (4) or (7), respectively. As the thing, the same thing as the organic solvent and catalyst which were illustrated above can be mentioned. As a usage ratio of a solvent, it is preferable to make into the ratio which the concentration of the polyorganosiloxane represented by the said Formula (8) in a solution become 30 to 90 weight%, and it is more preferable to set it as the ratio which becomes 50 to 80 weight%. Do. Especially as a catalyst, it is preferable to use oxalic acid, phosphoric acid, sodium hydroxide, potassium carbonate, etc. As a usage ratio of a catalyst, it is preferable to set it as 0.1-20 weight part with respect to 100 weight part of polyorganosiloxane represented by the said Formula (8), and it is more preferable to set it as 0.5-10 weight part.

The reaction temperature in the reaction of the polyorganosiloxane represented by the formula (8) with the compound represented by the formula (6) is preferably 40 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours.

It is preferable to provide the [B] polyorganosiloxane synthesize | combined in this way to prepare the curable resin composition of this invention after removing the solvent and catalyst which were used for the synthesis reaction.

[B] As a polyorganosiloxane, as long as it has the above structure, a commercial item can also be used. As such a commercial item, Aaron oxetane OXT-191 (made by TOAGOSEI CO., LTD.) Etc. is mentioned, for example.

[C] hardener

In the present invention, the [C] curing agent is added to the curable resin composition of the present invention in order to further improve the heat resistance and hardness of the protective film formed when the [A] polymer is a copolymer [A1] or a polymer [A2]. In addition to being able to use it arbitrarily, when [A] polymer is the said copolymer [A3], it can be used as follows. That is, by using [C] hardener together with copolymer [A3] and [B] polyorganosiloxane, it can be set as 1-component curable resin composition, or curable containing copolymer [A3] and [B] polyorganosiloxane. The set which consists of the 1st liquid which consists of a resin composition, and the 2nd liquid containing [C] hardening | curing agent can be used suitably as a set for forming a resin cured film.

Such a [C] hardener includes a polymer containing a repeating unit derived from a polymerizable unsaturated compound having a (C-1) carboxylic acid anhydride group (except those corresponding to the [A] polymer. 1) a polymer having a carboxylic acid anhydride group] and (C-2) polyvalent carboxylic acid anhydride.

The polymer which has the said (C-1) carbonic anhydride group can mention the polymer of unsaturated polyhydric carboxylic acid anhydride, or the copolymer of unsaturated polyhydric carboxylic acid anhydride and another olefinic unsaturated compound.

As unsaturated polyhydric carboxylic anhydride, itaconic anhydride, citraconic anhydride, maleic anhydride, and cis 1,2,3,4-tetrahydrophthalic anhydride etc. are mentioned, for example.

As said other olefinically unsaturated compound, For example, styrene, p-methylstyrene, p-methoxy styrene, methyl methacrylate, t-butyl methacrylate, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] Decan-8-yl, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexyl maleimide, etc. are mentioned.

Preferred examples of the polymer having a (C-1) carbonic anhydride group include, for example, maleic anhydride copolymer / styrene and citric anhydride / methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl air Coalescence, etc. are mentioned.

The copolymerization ratio of the unsaturated polyvalent carbonic anhydride in the polymer having a (C-1) carbonic anhydride group is preferably 1% by weight or more, more preferably 1 to 80% by weight, still more preferably 10 to 60% by weight. By setting it as such a copolymerization ratio, the protective film excellent in planarization performance can be formed.

About the polymer which has a (C-1) carbonic anhydride group, polystyrene conversion weight average molecular weight (Mw) measured by GPC becomes like this. Preferably it is 500-50,000, More preferably, it is 500-10,000. By using the copolymer of such a molecular weight range, the protective film excellent in the planarization performance can be formed.

Synthesis | combination of the polymer which has a (C-1) carbonic anhydride group can be performed according to the synthesis method of [A] polymer except using what was described above as a monomer.

As said (C-2) polyhydric carboxylic anhydride, aromatic polyhydric carboxylic anhydrides, such as itaconic anhydride, succinic anhydride, citraconic anhydride, trimellitic anhydride, maleic anhydride, hexahydrophthalic anhydride, are mentioned, for example. have. Among these, aromatic polyhydric carboxylic acid anhydride, particularly trimellitic anhydride, is preferable in that a cured film having high heat resistance can be obtained.

[C] When the ratio of the curing agent is used in combination with the copolymer [A1] or the polymer [A2], it is preferably 50 parts by weight or less based on 100 parts by weight of the copolymer [A1] or the polymer [A2]. More preferably, it is 20 weight part or less.

[C] When the curing agent is used in the one-component curable resin composition containing the copolymer [A3], it is preferably 20 to 80 parts by weight, more preferably 30 to 30 parts by weight of the copolymer [A3]. It is 70 weight part, More preferably, it is 35-60 weight part. If this value is less than 20 weight part, sufficient crosslinking density may not be obtained for the protective film formed, and the various resistances of a protective film may be insufficient. On the other hand, when it exceeds 80 weight part, unreacted [C] hardening agent remains in the protective film formed, As a result, the property of a protective film may become unstable, or the adhesiveness of a board | substrate and a protective film may be insufficient.

When the [C] hardener is used in the second liquid set for forming a resin cured film, the [C] hardener is prepared as a solution state dissolved in a solvent. As a solvent, the same thing as what is mentioned later can be used as a solvent which can be used as a solvent of curable resin composition of this invention. The concentration of the [C] curing agent in the second liquid of the set for forming the resin cured film is preferably 20 to 80% by weight, more preferably 30 to 70% by weight.

Other additives

The curable resin composition (including the case where it is used as a 1st liquid of a set for forming a resin cured film) of this invention contains the [A] polymer and [B] polyorganosiloxane as an essential component as mentioned above. In addition, although it contains a [C] hardening agent as needed, you may contain other additives in the range which does not impair the effect of this invention as needed. In addition, although the 2nd liquid of the set for forming a resin cured film contains [C] hardening | curing agent as mentioned above, you may contain other additives in the range which does not impair the effect of this invention as needed.

Examples of such other additives include [D] adhesive aids, [E] polyfunctional compounds, [F] curing accelerators, [G] surfactants, [H] thermosensitive acid generators, and the like.

[D] adhesion aid

Said [D] adhesion | attachment adjuvant can be added in order to improve the adhesiveness of the protective film formed and a board | substrate further.

As such [D] adhesion | attachment adjuvant, the functional silane coupling agent which has a reactive substituent can be used, for example. As said reactive substituent, a carboxyl group, methacryloyl group, an isocyanate group, an oxiranyl group, etc. are mentioned, for example. As a specific example of [D] adhesion | attachment adjuvant, for example, trimethoxy silyl benzoic acid, (gamma)-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, (gamma)-isocyanatopropyl trie Oxysilane, (gamma)-glycidoxy propyl trimethoxysilane, (gamma)-glycidoxy propyl triethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyl trimethoxysilane, etc. are mentioned.

The use ratio of the [D] adhesion | attachment adjuvant in curable resin composition of this invention is 30 weight part or less with respect to 100 weight part of [A] polymers, More preferably, it is 30-25 weight part. When the use ratio of the adhesive assistant (D) exceeds 30 parts by weight, the heat resistance of the resulting protective film may be insufficient.

On the other hand, the use ratio of the [D] adhesion | attachment adjuvant in the 2nd liquid of a set for forming a resin cured film is per 100 weight part of [C] hardening | curing agents, Preferably it is 40 weight part or less, More preferably, 30 weight Or less.

(E) Multifunctional  compound

[E] The polyfunctional compound can be used in the present invention in order to further improve the hardness of the protective film formed.

As [E] polyfunctional compound arbitrarily used for this invention, a cationically polymerizable compound, a polyfunctional (meth) acryl compound, etc. are mentioned, for example.

A cationically polymerizable compound is a compound which has 2 or more oxiranyl group or oxetanyl group in a molecule | numerator except a thing corresponding to [A] polymer. As a compound which has two or more oxiranyl groups or an oxetanyl group in the said molecule, the compound which has two or more oxiranyl groups in a molecule | numerator, the compound which has a 3, 4- epoxycyclohexyl group, etc. are mentioned, for example.

Examples of the compound having two or more oxiranyl groups in the molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and the like. Diglycidyl ether of a bisphenol compound;

Polyglycidyl ethers of polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, and trimethylolpropane triglycidyl ether; Polyethers obtained by adding one or two or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;

Polyglycidyl ethers of polyols; Phenol novolac type epoxy resins;

Cresol novolac type epoxy resins; Polyphenol type epoxy resin etc. are mentioned.

As a commercial item of the compound which has two or more oxiranyl groups in the said molecule | numerator, it is a bisphenol-A epoxy resin, for example, Epicoat 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010, copper 828 ( Japan Epoxy Resins Co., Ltd.), etc .; As bisphenol F-type epoxy resin, Epicoat 807 (made by Japan Fan Epoxy Resin Co., Ltd.) etc .;

As a phenol novolak-type epoxy resin, Epicoat 152, Copper 154, Bisphenol A novolak-type epoxy resin, Epicoat 157S65 (above, Japan Epoxy Resin Co., Ltd.), EPPN 201, Copper 202 (above, Nippon Kayaku (Manufactured by NIPPON KAYAKU CO., LTD.);

As a cresol novolak-type epoxy resin, EOCN 102, copper 103S, copper 104S, copper 1020, copper 1025, copper 1027 (above, Nippon KAYAKU CO., LTD. Product), epicoat 180S75 ( Japan Epoxy Resin Co., Ltd.);

As a polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, Japan Epoxy Resin Co., Ltd. product) etc. are mentioned; As cyclic aliphatic epoxy resin, Araldite CY-175, copper 177, copper 179, copper 182, copper 192, copper 184 (above, Chiba Specialty Chemicals Co., Ltd. make) (CIBA JAPAN KK) , ERL-4234, 4299, 4221, 4206 (above, manufactured by UCC Corporation), Epicoat 871, 872 (above, manufactured by Japan Epoxy Resin Co., Ltd.), and the like.

Examples of the compound having two or more 3,4-epoxycyclohexyl groups in the molecule include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 2- (3,4- Epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclo Hexyl methyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopenta Diene epoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4-epoxycyclohexanecarboxylate) and the like.

Among these cationic polymerizable compounds, a phenol novolak type epoxy resin or a polyphenol type epoxy resin is preferable.

On the other hand, as a polyfunctional (meth) acrylate compound, for example, 1,9-nonanediol (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxy Siethanolfluorene diacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, triacryloyloxypentaerythritol succinic acid {alias: succinic acid (3-acryloyloxy-2,2-bisacryloyloxymethyl- Propyl) ester}, diacryloyloxy pentaerythritol succinic acid {alias: succinic acid (3-acryloyloxy-2-acryloyloxymethyl-propyl) ester}, pentaacryloyloxypenta Thritol succinic acid {alias: succinic acid [3- (3-acryloyloxy-2,2-bis-acryloyloxymethyl-propyl) -2,2-bis-acryloyloxymethyl-propyl] ester}, Tetraacryloyloxy dipentaerythritol succinic acid {alias: succinic acid [3- (3-acryloyloxy-2,2-bis-acryloyloxymethyl-propyl) -2-acryloyloxymethyl-propyl] ester} Etc. can be mentioned.

As these commercial items, for example, Aronix M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M -7100, East M-8030, East M-8060 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, East HX-220, East R-604, East TMPTA, East DPHA, East DPCA-20, East DPCA-30, East DPCA-60, East DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Biscot 260, East 312, East 335HP, East 295, East 300, East 360, East GPT, East 3PA, East 400 (Osaka Yukika) Gakuko Bridge Co., Ltd. (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.).

These can be used individually or in combination.

The use ratio of the [E] polyfunctional compound in curable resin composition of this invention is per 100 weight part of [A] polymers, Preferably it is 100 weight part or less, More preferably, it is 20-80 weight part.

On the other hand, the use ratio of the [E] polyfunctional compound in the set 2nd liquid for forming a resin cured film is per 100 weight part of [C] hardening | curing agents, Preferably it is 50 weight part or less, More preferably, 20 weight Or less.

[F] hardening accelerator

[F] The curing accelerator can be used for the purpose of further improving the heat resistance and hardness of the protective film formed when the curable resin composition of the present invention contains the [C] curing agent or in the set for forming the resin cured film of the present invention. Can be.

As a specific example of such [F] hardening accelerator, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methyl, Midazole, 2-phenyl-4-methylimidazole-5-hydroxymethylimidazole, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-S -Triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ')]-ethyl-S-triazine, etc. are mentioned.

The use ratio of the [F] hardening accelerator in curable resin composition of this invention is per 100 weight part of [A] polymers, Preferably it is 10 weight part or less, More preferably, it is 0.0001-10 weight part, More preferably Preferably it is 0.001-1 weight part.

On the other hand, the use ratio of the [F] hardening accelerator in the 2nd liquid of a set for forming a resin cured film is per 100 weight part of [C] hardening | curing agents, Preferably it is 10 weight part or less, More preferably, 1 weight Or less.

[G] surfactant

A surfactant can be used to further improve the coating performance of the curable resin composition of the present invention.

As such surfactant, a fluorochemical surfactant and silicone type surfactant are mentioned, for example.

As said fluorine-type surfactant, it is a commercial item, For example, DIC Co., Ltd. brand name: Megapack F142D, copper F172, copper F173, copper F183, Neos Co., Ltd. (NEOS COMPANY LIMITED) brand names: Pentgent 250, copper 251, 222F, FTX-218, etc. are mentioned.

As said silicone type surfactant, it is a commercial item manufactured, for example, from Dow Corning Silicon Co., Ltd. (trade name: SH-28PA, SH-190, SH-193, SZ-6032, SF) -8428, DC-57, DC-190, 8019ADDITIVE, FZ-2101, east 77, east 2118, L-7001, L-7002, Toray Dow Corning Silicone Co., Ltd. product brand name: PAINTAD19, BIC Chemie Japan ( Note) The manufacture, brand name: Byk-344, etc. are mentioned.

The use ratio of the [G] surfactant in the curable resin composition of the present invention is preferably 5 parts by weight or less, more preferably 2 parts by weight or less per 100 parts by weight of the polymer (A).

On the other hand, the use ratio of the [G] surfactant in the second solution of the set for forming the resin cured film is preferably 5 parts by weight or less, more preferably 2 parts by weight per 100 parts by weight of the [C] curing agent. Or less. When the use ratio of the [G] surfactant exceeds the above range, roughness of the coating film may easily occur.

(H) thermosensitive Acid generator

As said [H] thermosensitive acid generator, a sulfonium salt, a benzothiazonium salt, an ammonium salt, a phosphonium salt, etc. are mentioned, for example, A sulfonium salt or a benzothiazonium salt can be used preferably among these.

menstruum

The second liquid of the set for forming the curable resin composition and the resin cured film of the present invention is preferably prepared as a solution in which each of the above components is dissolved in a suitable solvent. As a solvent which can be used here, it is preferable to melt | dissolve each component and to not react with each component.

Examples of such a solvent include ether, glycol ether, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol alkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, ketone, ester and the like. These solvents can also be used together with a high boiling point solvent.

As these specific examples, For example, as ether, Tetrahydrofuran etc .;

Examples of the glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;

As diethylene glycol monoalkyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc .;

As diethylene glycol dialkyl ether, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As propylene glycol alkyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol methyl pentyl ether, etc .;

As propylene glycol alkyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, etc .;

As propylene glycol alkyl ether propionate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, etc .;

Examples of the ketone include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, and the like;

As the ester, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl lactate, methyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionate, 3-methoxy Butyl propionate, methyl 3-ethoxy propionate, and the like.

Among these, propylene glycol alkyl ether acetates and diethylene glycol dialkyl ethers are preferable.

Embodiment of curable resin composition

If the preferable embodiment of this invention is shown more concretely, the following (I)-(III) is mentioned, for example.

(I) A one-component curable containing [A] polymer (preferably at least one member selected from the group consisting of copolymer [A1], polymer [A2] and copolymer [A3]) and [B] polyorganosiloxane Resin composition ((alpha) 1). This 1 part type curable resin composition ((alpha) 1) is especially excellent in long-term storage stability.

(II) 1-component curable resin composition ((alpha) 2) containing copolymer [A3], [B] polyorganosiloxane, and [C] hardening | curing agent. This one-component curable resin composition (α2) exhibits good curing characteristics and does not deteriorate the characteristics of the protective film. This one-component curable resin composition (? 2) is preferably provided to be used within 24 hours after preparation.

(III) Copolymer [A3] and [B] A set (β) for forming a resin cured film, comprising a combination of a first liquid containing a polyorganosiloxane and a second liquid containing a [C] hardener.

How to form a protective film

Next, the method of forming a protective film (preferably the protective film for optical devices, more preferably the protective film of a color filter) using each curable resin composition of this invention is demonstrated.

The protective film of this invention can be formed by forming a film on a board | substrate using the set for forming curable resin composition or resin cured film of this invention, and then heat-processing.

In the case of the one-component curable resin composition (α1) or the one-component curable resin composition (α2), this is coated on a substrate, prebaked to form a film by removing the solvent, and then subjected to heat treatment to form a target protective film. Can be formed.

On the other hand, in the case of the set ((beta)) for forming a resin cured film, when using, the 1st liquid and the 2nd liquid are mixed, and the coating composition is prepared and used. The target protective film can be formed by apply | coating the said coating composition on a board | substrate, prebaking, removing a solvent, and forming a film, and heat-processing. In this case, the mixing ratio of the first liquid and the second liquid is preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight based on 100 parts by weight of the copolymer [A3]. And more preferably 30 to 50 parts by weight. The mixture is preferably provided for use within 24 hours after mixing the first liquid and the second liquid.

As a board | substrate which forms a protective film, what consists of glass, quartz, silicone, a transparent resin, etc. can be used, for example. Examples of the transparent resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, ring-opening polymers of cyclic olefins, hydrogenated substances thereof and the like. The set for forming curable resin composition and resin cured film of this invention may be a board | substrate which has a level | step difference in the surface, for example, a color filter etc. are formed on a board | substrate.

As the coating method, for example, a spraying method, a roll coating method, a rotary coating method, a bar coating method, an inkjet method, or the like can be adopted. Particularly, a spin coater, a slit and spin coater, and a spinless (registration) can be adopted. The coating can be performed using a coater or a slit die coater. Although the conditions of the said prebaking differ also according to the kind, compounding ratio, etc. of each component, Preferably it is about 1 to 15 minutes at 70-140 degreeC. As the film thickness of the coating film after prebaking, Preferably it is 0.15-8.5 micrometers, More preferably, it is 0.15-6.5 micrometers, More preferably, it is 0.15-4.5 micrometers.

The heat treatment after coating film formation can be performed with appropriate heating apparatuses, such as a hotplate and oven. As for the process temperature at the time of heat processing, about 150-250 degreeC is preferable, and also as for processing time, when using a hotplate as a heating apparatus, about 5 to 30 minutes is preferable, and when using an oven, about 30 to 90 minutes are preferable.

Shield

The film thickness of the thus formed protective film is preferably 0.1 to 8 µm, more preferably 0.1 to 6 µm, still more preferably 0.1 to 4 µm. In addition, when the protective film of the present invention is formed on a substrate having a step of the color filter, the film thickness should be understood as the thickness from the top of the color filter.

As is apparent from the examples described below, the protective film of the present invention satisfies adhesion, surface hardness, transparency, heat resistance, light resistance, solvent resistance, and the like, and does not dent under load applied with heat. Moreover, since it is excellent in the performance which planarizes the level | step difference formed on the base substrate, it is suitable as a protective film for optical devices, especially a protective film for color filters.

It has been proved that the protective film of the present invention has sufficient heat resistance even when exposed to high temperatures in the panel manufacturing process by having sufficient dimensional stability even by additional heating at 250 ° C in the following examples.

EXAMPLE

Although an Example is shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

[A] Synthesis of Polymer

<Synthesis of Copolymer [A1]>

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added. Subsequently, 20 parts by weight of styrene, 20 parts by weight of N-cyclohexylmaleimide, 20 parts by weight of methacrylic acid, and 40 parts by weight of glycidyl methacrylate were added, and after nitrogen replacement, the stirring was started gently. The solution temperature was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A1-1). Solid content concentration (The ratio which the polymer weight in a polymer solution occupies for the whole quantity of a polymer solution. The same applies below) of the obtained polymer solution was 32.6 weight%.

Mw (polystyrene reduced weight average molecular weight measured by gel permeation chromatography.) Of this copolymer (A1-1) was 12,000.

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added. Subsequently, 40 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane, 15 parts by weight of methacrylic acid, 30 parts by weight of dicyclopentanyl methacrylate and 15 parts by weight of 1,3-butadiene were added, followed by nitrogen substitution. Stirring was started. The solution temperature was raised to 70 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A1-2). Solid content concentration of the obtained polymer solution was 32.0 weight%.

Mw of this copolymer (A1-2) was 11,000.

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added. Subsequently, 15 parts by weight of styrene, 20 parts by weight of N-phenylmaleimide, 25 parts by weight of methacrylic acid, and 40 parts by weight of glycidyl methacrylate were added, followed by nitrogen substitution, and gently stirring was started. The solution temperature was raised to 70 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A1-3). Solid content concentration of the obtained polymer solution was 33.0 weight%.

Mw of this copolymer (A1-3) was 12,500.

<Synthesis of Copolymer [A2-1]>

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were charged. Subsequently, 35 parts by weight of glycidyl methacrylate, 15 parts by weight of styrene, 20 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate and 30 parts by weight of dicyclopentanyl methacrylate were added, followed by nitrogen substitution and gentle stirring. Started. The solution temperature was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing a copolymer (A2-1-1). Solid content concentration of the obtained polymer solution was 33.1 weight%.

Mw of this copolymer (A2-1-1) was 12,000.

Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were charged. Then, 40 parts by weight of glycidyl methacrylate, 20 parts by weight of styrene, 20 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate and 20 parts by weight of methyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. it started. The solution temperature was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A2-1-2). Solid content concentration of the obtained polymer solution was 32.9 weight%.

Mw of this copolymer (A2-1-2) was 11,000.

Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of propylene glycol monomethyl ether acetate were charged. Then, 40 parts by weight of glycidyl methacrylate, 15 parts by weight of styrene, 15 parts by weight of N-cyclohexylmaleimide, and 30 parts by weight of methacrylic acid 1- (cyclohexyloxy) ethyl were added, followed by nitrogen substitution and gentle stirring. Started. The solution temperature was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A2-1-3). Solid content concentration of the obtained polymer solution was 33.0 weight%.

Mw of this copolymer (A2-1-3) was 11,500.

<Synthesis of Copolymer [A3]>

Synthesis Example 7

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 80 parts by weight of glycidyl methacrylate and 20 parts by weight of styrene were added, and after nitrogen replacement, the stirring was started gently. The solution temperature was raised to 95 ° C, and this temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A3-1). Solid content concentration of the obtained polymer solution was 33.3 weight%.

Mw of this copolymer (A3-1) was 13,000.

Synthesis Example 8

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of diethylene glycol ethylmethyl ether were placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 20 parts by weight of N-cyclohexylmaleimide and 60 parts by weight of glycidyl methacrylate were added, and after nitrogen replacement, the stirring was started gently. The solution temperature was raised to 95 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A3-2). Solid content concentration of the obtained polymer solution was 32.7 weight%.

Mw of this copolymer (A3-2) was 12,000.

Synthesis Example 9

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of diethylene glycol ethylmethyl ether were placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 25 parts by weight of styrene and 75 parts by weight of 3-methyl-3-methacryloyloxymethyloxetane were added thereto, and after nitrogen substitution, gentle stirring was started. The solution temperature was raised to 95 ° C., and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer (A3-3). Solid content concentration of the obtained polymer solution was 32.4 weight%.

Mw of this copolymer (A3-3) was 12,500.

Synthesis Example 10

5 parts by weight of 2,2'-azobis-isobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer. Subsequently, 25 parts by weight of styrene, 15 parts by weight of dicyclopentanyl methacrylate and 60 parts by weight of 3-methyl-3-methacryloyloxymethyloxetane were added thereto, and after stirring with nitrogen, gentle stirring was started. The solution temperature was raised to 95 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing a copolymer (A3-4). Solid content concentration of the obtained polymer solution was 33.0 weight%.

Mw of this copolymer (A3-4) was 11,500.

Preparation and Evaluation of Curable Resin Compositions

Example 1

<Preparation of curable resin composition>

[A] A solution containing the copolymer (A1-1) obtained in Synthesis Example 1 as the polymer (amount equivalent to 100 parts by weight (solid content) in terms of copolymer (A1-1)), [B] 5 parts by weight of polyorganosiloxane represented by the above formula (3) as an organosiloxane (where n has an average value of 10), [D] 10 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adjuvant, and [E] pipe 20 parts by weight of Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd.) as the functional compound and 0.1 part by weight of SH-28PA (manufactured by Dow Dow Corning Silicon Co., Ltd.) as the [G] surfactant were further added. After adding propylene glycol monomethyl ether acetate and diethylene glycol ethyl methyl ether in the ratio of 8 to 2 (weight ratio) so that it might become 20 weight%, curable resin composition was prepared by filtering by the Millipore filter of 0.5 micrometer of pore diameters.

<Formation of protective film>

In the curable resin composition, using a spinner SiO ₂ After apply | coating on a dip glass board | substrate, the coating film was formed by prebaking at 80 degreeC and 5 minutes on a hotplate, and further, heat-processing at 230 degreeC for 60 minutes in oven, The protective film of the film thickness of 2.0 micrometers was formed on the board | substrate. .

<Evaluation of the protective film>

(1) evaluation of transparency

For the substrate having the protective film formed as described above, a glass substrate having no protective film formed on the object side by using a spectrophotometer (150-20 type double beam (manufactured by Hitachi Seisakusho Co., Ltd.)). The transmittance | permeability of 400-800 nm was measured. The minimum value of the transmittance | permeability of 400-800 nm is shown in Table 2. When this value is 95% or more, it can be said that transparency of a protective film is favorable.

(2) Evaluation of heat resistance dimensional stability

About the board | substrate which has a protective film formed as mentioned above, it heated further on the conditions of 1 hour at 250 degreeC in oven, and measured the film thickness before and behind heating. Table 2 shows the heat-resistant dimensional stability calculated according to 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) / (film thickness before heating) x 100

(3) Evaluation of heat discoloration resistance

About the board | substrate with a protective film formed as mentioned above, it heated further at 250 degreeC in oven for 1 hour, and the transparency before and behind heating was measured similarly to said (1). Table 2 shows the heat discoloration resistance calculated according to the following formula. When this value is 5% or less, it can be said that heat discoloration resistance is favorable.

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

(4) measurement of pencil hardness

About the board | substrate which has a protective film formed as mentioned above, the surface hardness of the protective film was measured by the 8.4.1 pencil drawing test of JISK-5400-1990. This value is shown in Table 2. When this value is 4H or harder, the surface hardness can be said to be good.

(5) Evaluation of adhesiveness

After the pressure cooker test (120 degreeC, 100% of humidity, 4 hours) was performed with respect to the board | substrate which has the protective film formed as mentioned above, it is a protective film by 8.5.3 adhesive checkerboard graduation tape method of JISK-5400-1990. the evaluated adhesion (adhesion to SiO _2). Table 2 shows the number of remaining checkerboard ticks among the checkerboard ticklists.

In addition, as an evaluation of the adhesion to Cr, SiO ₂ A protective film having a film thickness of 2.0 µm was formed in the same manner as above except that a Cr substrate was used instead of the dip glass substrate, and the evaluation was performed in the same manner by the checkerboard graduation tape method. The results are shown in Table 2.

(6) Evaluation of ITO Patterning Characteristics

With respect to the substrate having the protective film formed as described above, (the main) ULVAC manufacture, High rate Sputtering equipment (by type "SH-550-C12", ITO target (ITO filling rate above _{95%, In 2 O 3 /} SnO ₂ = 90/10 weight ratio), and ITO sputtering was performed at 60 ° C. The atmosphere at this time was 1.0 × 10 ⁻⁵ Pa at a reduced pressure, 3.12 × 10 ⁻³ m ³ / h, and an O ₂ gas flow rate. It was 1.2x10 <^-5> m <3> / h About the board | substrate after sputtering, it heated at 240 degreeC for 60 minutes in the clean oven, and performed annealing.

Next, the said board | substrate was set to the spinner, JSR Co., Ltd. product, g line | wire positive resist (article name "PER 3650-21cp") was dripped on the board | substrate, and 30 seconds of coating was performed at the rotation speed of 3,500 rpm. Subsequently, this board | substrate was heated at 90 degreeC on the hotplate for 2 minutes, the solvent was removed, and the coating film of the positive resist was formed.

About the coating film of the forge resist formed above, the intensity | strength of ghi line | wire (wavelength 436nm, 405nm, 365nm) using the exposure machine Canon PLA501F (Canon Corporation make) through the pattern mask of 10 micrometers / 10 micrometers Ratio = 2.7: 2.5: 4.8) was irradiated at an exposure dose of roughness 40 W / m 2 and 250 J / m 2 in terms of i-line, and then developed by immersion for 3 minutes at room temperature with a 2.4% by weight aqueous tetramethylammonium hydroxide solution. After rinsing with ultrapure water for 60 seconds, the resultant was air dried and further post-baked at 150 ° C. for 60 minutes in a clean oven to form a resist pattern on the ITO film of the substrate.

The substrate was immersed in an etchant formed by mixing nitric acid / hydrochloric acid in a weight ratio of 1/3, and the substrate was taken out and observed every 10 seconds to determine the just etching time for forming an ITO line of 10 mu m. And the ITO line width of 1.2 time of just etching time was measured with the optical microscope. This result is shown in Table 2. In this case, the higher the retention rate of the ITO line width of 10 μm, the better the ITO patterning characteristics.

(7) Evaluation of alkali resistance

About the board | substrate with a protective film formed as mentioned above, after immersion for 30 minutes in 30 degreeC 5weight% NaOH aqueous solution, the film thickness after heating for 10 minutes at 120 degreeC with the hotplate and removing water was measured. The value computed according to the following formula was shown in Table 2 as alkali resistance value. When this value is 95% or more, it can be said that alkali resistance is favorable.

Alkali resistance (%) = (film thickness after water removal) / (film thickness before immersion) x 100

(8) Evaluation of Storage Stability of Curable Resin Composition

The viscosity at 25 degrees C of the curable resin composition prepared above was measured using Tokyo Keiki Inc. make and an ELD type viscometer. Then, the solution viscosity in 25 degreeC was measured every day, leaving this composition at 25 degreeC. The number of days required for 5% viscosity increase was calculated | required based on the viscosity immediately after preparation, and this day is shown in Table 2. When this number of days is 15 days or more, it can be said that storage stability is favorable.

(9) Evaluation of Flattening Performance (Flatness) of Protective Film

On the SiO ₂ dip glass substrate, using a pigment-based color resist ("JCR RED 689", "JCR GREEN 706" and "CR 8200B" manufactured by JSR Corporation), red, green and blue 3 A color stripe-like color filter was formed. That is, using a spinner, one color of the color resist was applied to a SiO ₂ dip glass substrate, and prebaked at 90 ° C. for 150 seconds on a hot plate to form a coating film. Subsequently, using an exposure machine Canon PLA501F (manufactured by Canon Corporation), a ghi line (intensity ratio of wavelength 436 nm, 405 nm, 365 nm = 2.7: 2.5: 4.8) was 2,000J in i-line conversion through a predetermined pattern mask. It was irradiated with an exposure amount of / m &lt; 2 &gt;, and then developed using a 0.05 mass% potassium hydroxide aqueous solution, followed by rinsing with ultrapure water for 60 seconds. Subsequently, further heat treatment at 230 ° C. for 30 minutes in an oven, thereby forming a monochromatic stripe color filter. By repeating this operation for every three colors, the stripe color filter (stripe width 200 micrometers) of three colors of red, green, and blue was formed.

Measuring length 2,000 μm, measuring range 2,000 μm Angle, measuring direction of red, green, blue stripe direction of short axis and red, red, green, green, blue, blue In the direction, the unevenness of the surface of the color filter substrate is measured by the measurement score n = 5 (n number of total is 10) in each direction, and a contact film thickness measuring apparatus (KLA Tencor Corporation) It was 1.0 micrometer as a result of measuring by the "(alpha) -step" of manufacture. After apply | coating each thermosetting resin composition to the board | substrate with this color filter with a spinner, it pre-baked at 90 degreeC on a hotplate for 5 minutes. After forming a coating film, it post-baked further at 230 degreeC for 60 minutes in a clean oven, and formed the protective film whose film thickness from the upper surface of a color filter is about 2.0 micrometers.

About the board | substrate which has a protective film on the color filter formed in this way, the unevenness | corrugation of the protective film surface was measured with the contact-type film thickness measuring apparatus ("alpha-step" by KLA Tencor Corporation). The measurement is performed by measuring the measurement length 2,000 m, the measurement range 2,000 m each, and measuring the direction of the stripe line short axis in the red, green, and blue directions, and the stripe line major axis directions of the same color of red, red, green, green, blue, and blue. Direction, the measurement score n = 5 (n number of totals is 10) for each direction, and the ten times average value of the height difference (nm) of the highest part and the lowest part for each measurement is obtained, and the flattening performance (flatness) of the protective film is obtained. It showed in Table 2 as evaluation of. When this value is 200 nm or less, it can be said that the planarization performance of a protective film is favorable.

Examples 2-15 and Comparative Examples 1-5

Curable resin compositions were prepared and evaluated in the same manner as in Example 1, except that the type and amount of each component of the curable resin composition was as shown in Table 1.

In Examples 2, 3, 6 to 9 and 15 and Comparative Examples 1 and 2, two kinds of [E] polyfunctional compounds were used, respectively. In addition, "-" of the kind column of each component shows that the component corresponding to the said column was not used.

The evaluation results are shown in Table 2.

In addition, in Table 1, abbreviated-name of each component has the following meanings, respectively.

[B] polyorganosiloxane

B-1: polyorganosiloxane represented by the formula (3), wherein n has an average value of 10

[C] hardener

C-1: hexahydro phthalic anhydride

C-2: trimellitic anhydride

[D] adhesion aid

D-1: γ-methacryloxypropyltrimethoxysilane

D-2: γ-glycidoxypropyltrimethoxysilane

[E] Polyfunctional Compound

E-1: Bisphenol-A epoxy resin (Japan Epoxy Resin Co., Ltd. make, brand name: Epicoat 828)

E-2: Phenol novolak-type epoxy resin (Japan Epoxy Resin Co., Ltd. make, brand name: Epicoat 154)

E-3: dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. make, brand name KAYARAD DPHA)

E-4: pentaacryloyloxydipentaerythritol succinic acid {alias: succinic acid [3- (3-acryloyloxy-2,2-bis-acryloyloxymethyl-propyl) -2,2-bis-acrylo Iloxymethyl-propyl] ester, abbreviated: PADPS}

[F] hardening accelerator

F-1: 2-phenyl-4-methylimidazole

F-2: 2-phenyl-4-methylimidazole-5-hydroxymethylimidazole

F-3: 2-phenyl-1-benzylimidazole

[G] surfactant

G-1: Silicone type surfactant (Toray Dow Corning Silicone Co., Ltd. brand name: SH-28PA)

G-2: Silicone type surfactant (BIC Chemi Japan Co., Ltd. make, brand name: Byk-344)

G-3: Fluorine-type surfactant (Neo Co., Ltd. make, brand name: Pgentant FTX-218)

G-4: Silicone type surfactant (Toray Dow Corning Silicone Co., Ltd. product name: PAINTAD19)

Claims (13)

[A] A polymer having a repeating unit derived from a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group, and [B] A curable resin composition comprising a polyorganosiloxane represented by the following formula (1). Formula 1

In Formula 1, R ¹ to R ⁶ are each independently represented by the following Formula (2): (Formula 2)

(In formula (2), R <^7> -R <^11> is mutually independently a hydrogen atom, a fluorine atom, a C1-C4 alkyl group, a phenyl group, or a C1-C4 perfluoroalkyl group, and a is an integer of 1-6.) Is a group, a hydrogen atom, an alkoxyl group having 1 to 4 carbon atoms, a cycloalkyloxyl group having 3 to 8 carbon atoms or a phenoxy group, n is an integer of 2 to 30, provided that at least one of R ¹ to R ⁶ is A group represented by the formula (2).) The method of claim 1, [A] The polymer is at least one selected from the group consisting of a polymerizable unsaturated compound having [A1] (a) an oxiranyl group or an oxetanyl group, and (b1) a polymerizable unsaturated carbonic acid and a polymerizable unsaturated polyhydric carbonic anhydride. Species, (b3) Oxyranyl group, oxetanyl group, carboxyl group, acid anhydride group, acetal ester structure of carbonic acid, ketal ester structure of carbonic acid, 1-alkylcycloalkylester structure of carbonic acid and t of carbonic acid Curable resin composition which is a copolymer with the polymerizable unsaturated compound which does not have any of a butyl ester structure. The method of claim 1, [A] The polymer contains two or more oxiranyl groups or oxetanyl groups in the [A2] molecule, an acetal ester structure of carbonic acid, a ketal ester structure of carbonic acid, a 1-alkylcycloalkylester structure of carbonic acid and a carbonic acid Curable resin composition which is a polymer which has at least 1 sort (s) of structure chosen from the group which consists of t-butyl ester structures of the above. The method of claim 3, [A2] The polymer has a polymerizable unsaturated compound having [A2-1] (a) an oxiranyl group or an oxetanyl group, and (b2) an acetal ester structure of carbonic acid, a ketal ester structure of carbonic acid and 1- of carbonic acid. A polymerizable unsaturated compound having at least one structure selected from the group consisting of an alkylcycloalkyl ester structure and a t-butyl ester structure of carboxylic acid, and (b3) an oxiranyl group, an oxetanyl group, a carboxyl group, an acid anhydride group Curable resin composition which is a copolymer with a polymerizable unsaturated compound which has none of the acetal ester structure of carboxylic acid, the ketal ester structure of carboxylic acid, the 1-alkyl cycloalkyl ester structure of carboxylic acid, and the t-butyl ester structure of carboxylic acid . The method of claim 3, [A2] The polymer is selected from the group consisting of [A2-2] (a) a polymerizable unsaturated compound having an oxiranyl group or an oxetanyl group, and (b1) a polymerizable unsaturated carbonic acid and a polymerizable unsaturated polycarboxylic anhydride At least one kind and at least one kind selected from the group of (b2) acetal ester structures of carboxylic acids, ketal ester structures of carboxylic acids, 1-alkylcycloalkyl ester structures of carboxylic acids, and t-butyl ester structures of carboxylic acids (B3) Oxyranyl group, oxetanyl group, carboxyl group, acid anhydride group, acetal ester structure of carbonic acid, ketal ester structure of carbonic acid, 1-alkylcycloalkyl ester of carbonic acid Curable resin composition which is a copolymer with the synthetic unsaturated compound which has neither a structure and t-butylester structure of a carboxylic acid. The method of claim 1, [A] Polymer has acetal ester structure of (A3) (a) polymerizable unsaturated compound which has oxiranyl group or oxetanyl group, and (b3) oxiranyl group, oxetanyl group, carboxyl group, acid anhydride group, and carboxylic acid The curable resin composition which is a copolymer with the polymerizable unsaturated compound which does not have any of the ketal ester structure of carboxylic acid, the 1-alkyl cycloalkyl ester structure of carboxylic acid, and the t-butyl ester structure of carboxylic acid. The method of claim 6, Moreover, curable resin composition containing a [C] hardening | curing agent. The method according to any one of claims 1 to 7, Moreover, [D] curable resin composition containing a polyfunctional compound. It consists of the 1st liquid which consists of curable resin composition of Claim 6, and the 2nd liquid containing [C] hardening | curing agent, The set for forming the resin cured film characterized by the above-mentioned. The method of claim 9, The first liquid further contains the [D] polyfunctional compound. The protective film formed from the curable resin composition of any one of Claims 1-7, or the set of Claim 9 or 10. The film is formed on a board | substrate using the curable resin composition in any one of Claims 1-7, and then heat-processed, The formation method of the protective film characterized by the above-mentioned. The method of forming a protective film, which comprises mixing the first liquid and the second liquid of the set according to claim 9 or 10, using the mixture to form a film on the substrate, and then performing a heat treatment.