KR20110046331A - Radiation-sensitive composition, protective film, interlayer insulating film and method of forming them - Google Patents

Abstract

PURPOSE: A radiation-sensitive composition, a passivation film, an interlayer insulation film, and a method for forming the same are provided to increase the crack resistance property of passivation film and the interlayer insulation film with respect to metal wiring. CONSTITUTION: A radiation-sensitive composition includes siloxane polymer, a polymer with a repeating unit, a radiation-sensitive acid generator, or a radiation-sensitive base generator. The repeating unit is represented by chemical formula 1. In the chemical formula 1, R1 is hydrogen or C1 to C4 alkyl group. R2 to R6 is respectively hydrogen, hydroxyl group, or C1 to C4 alkyl group. B represents a single bond, -COO-*, or -CONH-*. m is the integer of 0 to 3. At least one of R2 to R6 is hydroxyl group. The * is combined with the carbon of (CH_2)m.

Description

Radiation-sensitive composition, protective film, interlayer insulating film and formation method thereof {RADIATION-SENSITIVE COMPOSITION, PASSIVATION FILM, INTERLAYER INSULATION FILM AND METHOD FOR FORMING THE SAME}

The present invention provides a radiation-sensitive composition which is very suitable as a material for forming a protective film and an interlayer insulating film of a display device such as a liquid crystal display device (LCD), an organic EL display device (OLED), a protective film and an interlayer insulating film formed from the composition, and And a method for forming the protective film and the interlayer insulating film.

The display element is immersed by a solvent, an acid or an alkaline solution, etc. during the manufacturing process. In addition, in such a display element, when forming a wiring electrode layer by sputtering, the element surface is locally exposed to high temperature. Therefore, in order to prevent deterioration or damage of a display element by the immersion process by such a solvent, or high temperature process, forming the protective film which is resistant to these processes on the surface of an element is performed.

Such a protective film has adhesiveness to a substrate or a lower layer on which the protective film should be formed, or a layer formed on the protective film, has transparency, and can preserve transparency without being discolored even under high temperature conditions. Performance, such as a thing having sufficient surface hardness, being excellent in scratch resistance, and the like. As a material for forming the protective film which satisfy | fills these manufacturing performances, the negative radiation sensitive composition containing the polymer which has glycidyl group, for example is known (refer Unexamined-Japanese-Patent No. 5-78453). Generally, as a radiation sensitive composition for protective film formation, since it is advantageous in terms of cost rather than positive type, what has negative radiation sensitivity is widely used.

Moreover, acrylic resin is mainly used as a component of the radiation sensitive composition for protective film formation. In contrast, attempts have been made to use polysiloxane materials having better heat resistance and transparency than acrylic resins as components of radiation-sensitive compositions (see Japanese Patent Laid-Open No. 2004-001648 and Japanese Patent Laid-Open No. 2006-178436). However, a polysiloxane material has a problem that it is not suitable as a protective film because adhesion with an ITO (indium tin oxide) transparent conductive film is not sufficient and cracks are easily generated in the cured film. In addition, the adhesion of the protective film to metal wirings such as molybdenum (Mo), tungsten (W), titanium (Ti), tantalum (Ta), niobium (Nb), copper (Cu), and aluminum (Al) in the display element is insufficient. In this case, the protective film may be cracked or peeled off from this wiring. Accordingly, there is a strong demand for the development of a polysiloxane radiation sensitive composition having excellent heat resistance and transparency and sufficiently high adhesion to metal wiring such as an ITO transparent conductive film or molybdenum even under strict conditions of high temperature and high humidity.

On the other hand, an interlayer insulation film is formed in order to insulate between the wiring arrange | positioned generally in layer shape in a display element. The interlayer insulating film of this display element requires pattern formation of a contact hole for wiring. As a material for forming an interlayer insulating film of a display element, development of a cost-effective negative radiation-sensitive composition has been carried out (see Japanese Laid-Open Patent Publication No. 2000-162769), but as such a negative composition, a level that can be practically used. It is difficult to form a contact hole having a hole diameter of. Therefore, in view of the superiority of contact hole formation at present, a positive radiation-sensitive curable composition is widely used to form an interlayer insulating film of a display element (see Japanese Patent Laid-Open No. 2001-354822).

As described above, various kinds of radiation-sensitive compositions are used for the manufacture of display elements depending on the purpose and the process thereof. Recently, in view of cost reduction, unification of a kind of radiation-sensitive composition has been attempted, and one type of radiation-sensitive composition is a protective film and an interlayer insulating film which overlap the required characteristics such as transparency, heat resistance (heat transparency) and surface hardness. It is desired to be able to form. Therefore, development of a radiation sensitive composition having negative radiation radiation characteristics generally used as a material for forming a protective film, satisfying all of the above required characteristics, and having the contact hole forming ability required as a material for forming an interlayer insulating film, has been developed. It is required.

Specifically, a protective film and an interlayer insulating film excellent in transparency, heat resistance (heat resistance and transparency), adhesion to a metal wiring such as a substrate with ITO or molybdenum, crack resistance, surface hardness and scratch resistance can be formed easily, and are practical. The development of the polysiloxane negative radiation sensitive composition which expresses the resolution which can form the usable contact hole is strongly desired.

Japanese Patent Application Laid-open No. Hei 5-78453 Japanese Laid-Open Patent Publication No. 2000-001648 Japanese Patent Laid-Open No. 2006-178436 Japanese Laid-Open Patent Publication No. 2000-162769 Japanese Laid-Open Patent Publication No. 2001-354822

This invention is made | formed based on the above circumstances, The objective is an ITO transparent conductive film and molybdenum under the high temperature, high humidity, and strict conditions, while being excellent in transparency, heat resistance (heat resistance transparency), surface hardness, and scratch resistance. Polysiloxane-based negative radiation-sensitive composition, which is very suitably used to form a protective film and an interlayer insulating film having high adhesion to metal wiring and crack resistance, and having sufficient resolution, and a protective film and an interlayer formed from the composition It is to provide an insulating film, and a method of forming the protective film and the interlayer insulating film.

The invention made to solve the above problems,

[A] siloxane polymer,

[B] a polymer having a repeating unit represented by the following Formula (1), and

[C] radiation-sensitive acid generators or radiation-sensitive base generators

It is a radiation sensitive composition containing a.

[In formula (1), R <^1> is a hydrogen atom or a C1-C4 alkyl group, R <^2> -R <^6> is a hydrogen atom, a hydroxyl group, or a C1-C4 alkyl group each independently, B is a single bond, -COO- ^* or -CONH- ^* , m is an integer of 0 to 3; Provided that at least one of R ² to R ⁶ is a hydroxy group, and the bond of each ^* in -COO- ^* or -CONH- ^* is bonded to carbon of (CH ₂ ) _m ].

The radiation sensitive composition has negative radiation sensitivity and, in addition to the components [A] and [C], contains a component [B] of a polymer having a repeating unit having a specific structure, thereby providing transparency and heat resistance ( It satisfies the general required characteristics such as heat resistance transparency, surface hardness and scratch resistance in a balanced manner, and also has excellent adhesion and crack resistance to metal wiring such as ITO transparent conductive film and molybdenum under strict conditions of high temperature and high humidity. A protective film and an interlayer insulating film for display elements can be formed. Moreover, the said radiation sensitive composition expresses the high resolution which can form a contact hole. Since the protective film or interlayer insulation film obtained from the said radiation sensitive composition is excellent in the above-mentioned characteristics, it can be used especially suitably for a display element.

It is preferable that the [A] siloxane polymer of the said radiation sensitive composition is a hydrolysis-condensation product of the hydrolyzable silane compound represented by following formula (2).

[In formula (2), R <^7> is a C1-C20 non-hydrolyzable organic group, R <^8> is a C1-C4 alkyl group and q is an integer of 0-3.].

ITO of the protective film and interlayer insulation film which are formed by using the hydrolysis-condensation product of the hydrolyzable silane compound represented by said Formula (2) as said [A] siloxane polymer in the said radiation sensitive composition. The adhesion and crack resistance to metal wirings such as a transparent conductive film and molybdenum are further improved, and higher resolution can be obtained.

It is preferable that the said radiation sensitive composition further contains the [D] dehydrating agent. Thus, by containing a dehydrating agent further, it becomes possible to raise the storage stability of the said radiation sensitive composition.

It is preferable that the said radiation sensitive composition further contains [E] ethylenically unsaturated compound. Thus, by containing an ethylenically unsaturated compound further, it becomes possible to improve the crack resistance of the said radiation sensitive composition.

It is preferable that the [C] radiation sensitive acid generator of the said radiation sensitive composition is at least 1 sort (s) chosen from the group which consists of a triphenylsulfonate salt and tetrahydrothiophenium salt. Moreover, it is preferable that the [C] radiation sensitive base generator of the said radiation sensitive composition is at least 1 sort (s) chosen from the group which consists of 2-nitrobenzyl cyclohexyl carbamate and O-carbamoyl hydroxyamide. By using these compounds as a radiation sensitive acid generator or a radiation sensitive base generator, the resolution of a radiation sensitive composition can be improved further.

Moreover, the formation method of the protective film or interlayer insulation film for display elements of this invention,

(1) forming a coating film of the radiation sensitive composition on a substrate;

(2) irradiating at least a part of the coating film formed in step (1) with radiation;

(3) developing the coating film irradiated with radiation in step (2), and

(4) Step of heating the coating film developed in Step (3)

It includes.

In this method, a protective film or interlayer for a display element having a fine and elaborate pattern is easily formed by forming a pattern by exposure and development using radiation sensitivity using the radiation sensitive composition expressing excellent resolution. An insulating film can be formed. In addition, the protective film and the interlayer insulating film thus formed have general characteristics required for these films, that is, transparency, heat resistance (heat transparency), surface hardness and scratch resistance, and adhesion to metal wiring such as an ITO transparent conductive film or molybdenum, and All crack resistances are well balanced.

As described above, the radiation-sensitive composition of the present invention includes the components [A], [B], and [C], so that the general required properties of transparency, heat transparency, surface hardness, and scratch resistance are balanced. It is possible to form a protective film and an interlayer insulating film which satisfies and exhibit excellent adhesion and crack resistance to metal wiring such as an ITO transparent conductive film and molybdenum even under severe conditions of high temperature and high humidity. The protective film or interlayer insulating film thus formed can be particularly suitably used for a display element. Moreover, the said radiation sensitive composition expresses sufficient resolution of the grade which can form a contact hole. Moreover, the said radiation sensitive composition has a negative radiation sensitive characteristic and is advantageous in cost compared with the composition which has a conventional positive radiation sensitive characteristic.

(Form to carry out invention)

 The radiation sensitive composition of this invention is a [A] siloxane polymer, a polymer which has a repeating unit represented by [B] said Formula (1), a [C] radiation sensitive acid generator, or a radiation sensitive base generator, and a necessity. And other optional components ([D] dehydrating agent, [E] ethylenically unsaturated compound, etc.).

[A] Component: siloxane polymer

The siloxane polymer of the component [A] is not particularly limited as long as it is a polymer of a compound having a siloxane bond. This [A] component is an acid (acidic active species) or base which generate | occur | produced from the [C] radiation sensitive acid generator or radiation sensitive base generator mentioned later by irradiating the radiation sensitive composition containing this component with radiation. (Base active species) is used as a catalyst for condensation (in some cases, condensation with a silane compound having a specific structure of the component [E] of any component) to form a cured product.

As the siloxane polymer of component [A], it is preferable that it is a hydrolysis-condensation product of the hydrolyzable silane compound represented by said Formula (2). The term “hydrolyzable group” of the hydrolyzable silane compound in the present application is usually hydrolyzed by heating within a temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the absence of a catalyst and excess water. It refers to a group capable of producing a play or a group capable of forming a siloxane condensate. On the other hand, a "non-hydrolyzable group" refers to the group which exists stably, without generating hydrolysis or condensation under such hydrolysis conditions. In the hydrolysis reaction of the hydrolyzable silane compound represented by the formula (2), some hydrolyzable groups may remain in the state of unhydrolysis. In addition, the "hydrolysis-condensation product of a hydrolyzable silane compound" here means the hydrolysis-condensation product which some silanol groups of the hydrolyzed silane compound reacted and condensed.

As a C1-C20 non-hydrolyzable organic group represented by said R <^7> , the C1-C12 unsubstituted, the alkyl group substituted by 1 or more of C1-C12, a (meth) acryloyl group, or an epoxy group, C6-C20 12 aryl group, a C7-12 aralkyl group, etc. are mentioned. These may be linear, branched, or cyclic, or a combination thereof when a plurality of R ^{7 's} are present in the same molecule. In addition, R ⁷ may contain the structural unit which has a hetero atom. As such a structural unit, ether, ester, sulfide, etc. are mentioned, for example.

As an example of the C1-C4 alkyl group represented by said R <^8> , a methyl group, an ethyl group, n-propyl group, i-propyl group, a butyl group, etc. are mentioned. Among these R ⁸ , a methyl group and an ethyl group are preferable from the viewpoint of ease of hydrolysis. The subscript q is an integer of 0 to 3, more preferably an integer of 0 to 2, particularly preferably 0 or 1, and most preferably 1. When q is an integer of 0-2, advancing of a hydrolysis-condensation reaction becomes easier, As a result, the speed | rate of the condensation reaction of [A] component (and [F] component) becomes larger, and also of the said composition Resolution and the adhesiveness with respect to the board | substrate of the protective film formed can be improved.

The hydrolyzable silane compound represented by Formula (2) is a silane compound substituted with four hydrolyzable groups, a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, two non-hydrolyzable groups and two hydrolyzable groups. Substituted silane compounds, silane compounds substituted with three non-hydrolyzable groups and one hydrolyzable group, or mixtures thereof.

As a specific example of the hydrolyzable silane compound represented by the said Formula (2),

As a silane compound substituted with four hydrolyzable groups, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, tetra-i-propoxy Silanes and the like;

As the silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , Vinyltri-n-propoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like;

As the silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane and the like;

Examples of the silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group include tributylmethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tributylethoxysilane, and the like.

Of the hydrolyzable silane compounds represented by these formulas (2), silane compounds substituted with four hydrolyzable groups and silane compounds substituted with one non-hydrolyzable group and three hydrolyzable groups are preferable, and one non-hydrolyzable compound is preferable. Particular preference is given to silane compounds substituted with groups and three hydrolyzable groups. Specific examples of preferred hydrolyzable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane and ethyltrimeth Methoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl triethoxysilane is mentioned. These hydrolyzable silane compounds may be used individually by 1 type, or may be used in combination of 2 or more type.

The conditions which hydrolyze and condense the hydrolyzable silane compound represented by said Formula (2) hydrolyze at least one part of the hydrolyzable silane compound represented by said Formula (2), convert a hydrolysable group into a silanol group, and condensation reaction. Although it does not specifically limit as long as it raise | generates, As an example, it can carry out as follows.

As water used for hydrolysis and condensation of the hydrolyzable silane compound represented by the formula (2), it is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, distillation or the like. By using such purified water, side reaction can be suppressed and the reactivity of hydrolysis can be improved. The amount of water to be used is preferably 0.1 to 3 moles, more preferably 0.3 to 2 moles, and even more preferably 1 mole of the total amount of the hydrolyzable group (-OR ⁸ ) of the hydrolyzable silane compound represented by Formula (2). Preferably in an amount of 0.5 to 1.5 moles. By using such an amount of water, the reaction rate of hydrolysis and condensation can be optimized.

Although it does not specifically limit as a solvent which can be used for hydrolysis and condensation of the hydrolyzable silane compound represented by said Formula (2), Usually, the same thing as the solvent used for preparation of the radiation sensitive composition mentioned later can be used. Preferable examples of such a solvent include ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid esters. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate or methyl 3-methoxypropionate are particularly preferable.

The hydrolysis-condensation reaction of the hydrolyzable silane compound represented by the formula (2) is preferably an acid catalyst (eg hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethane). Nitrogen-containing compounds such as sulfonic acid, phosphoric acid, acidic ion exchange resins, various Lewis acids, base catalysts (e.g., ammonia, primary amines, secondary amines, tertiary amines, pyridine), basic ion exchange resins, sodium hydroxide, and the like. Hydroxides, carbonates such as potassium carbonate, carbonates such as sodium acetate, various Lewis bases, or alkoxides (e.g., zirconium alkoxides, titanium alkoxides, aluminum alkoxides). For example, triethylamine can be used as the tertiary amine and tetra-i-propoxy aluminum can be used as the aluminum alkoxide. As the usage-amount of a catalyst, it is 0.2 mol or less with respect to 1 mol of monomers of a hydrolyzable silane compound from a viewpoint of the acceleration of a hydrolysis-condensation reaction, More preferably, it is 0.00001-0. 1 mole.

The reaction temperature and reaction time in hydrolysis and condensation of the hydrolyzable silane compound represented by said formula (2) are set suitably. For example, the following conditions can be adopted. Reaction temperature becomes like this. Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. By setting it as such reaction temperature and reaction time, a hydrolysis and condensation reaction can be performed most efficiently. In this hydrolysis / condensation, the hydrolyzable silane compound, water, and catalyst may be added to the reaction system at once, and the reaction may be performed in one step, or the hydrolyzable silane compound, water, and catalyst may be added several times in the reaction system. , Hydrolysis and condensation reaction may be carried out in multiple stages. After the hydrolysis and condensation reaction, water and the resulting alcohol can be removed from the reaction system by adding a dehydrating agent followed by evaporation. Since the dehydrating agent used in this step is generally absorbed or entrapped with excess water, and the dehydration ability is completely lost or removed by evaporation, the dehydrating agent of the component [D] described later added to the radiation-sensitive composition It does not belong to category of dehydrating agent.

The molecular weight of the hydrolyzed condensate of the hydrolyzable silane compound represented by the formula (2) can be measured as the number average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as the mobile phase. . And it is preferable to set it as the value within the range of 500-10000 normally, and, as for the number average molecular weight of a hydrolysis-condensation product, it is more preferable to set it as the value within the range of 1000-5000. The film-forming property of the coating film of a radiation sensitive composition can be improved by making the value of the number average molecular weight of a hydrolysis-condensation product into 500 or more. On the other hand, when the value of the number average molecular weight of a hydrolysis-condensation product is 10000 or less, the radiation-sensitive fall of a radiation sensitive composition can be prevented.

[B] component: having a repeating unit of a specific structure Polymer

Component [B] is a polymer having a repeating unit represented by Formula (1). By using a polymer having a repeating unit having such a specific structure, the radiation-sensitive composition satisfactorily satisfies the general required properties of transparency, heat resistance (heat transparency), surface hardness and scratch resistance, and under the strict conditions of high temperature and high humidity. Even under the present invention, it is possible to form a protective film for a display element and an interlayer insulating film which exhibit very high adhesion and crack resistance with respect to metal wiring such as an ITO transparent conductive film or molybdenum.

As a polymer which has a repeating unit represented by said Formula (1), the copolymer of the phenolic hydroxyl group containing unsaturated compound represented by following formula (3) and another unsaturated compound copolymerizable with this is used preferably. As another unsaturated compound copolymerizable with the phenolic hydroxyl group containing unsaturated compound represented by Formula (3), Preferably, an epoxy group containing unsaturated compound (containing an oxetanyl group containing unsaturated compound) can be used.

[In Formula (3), R <^1> is a hydrogen atom or a C1-C4 alkyl group, R <^2> -R <^6> is a hydrogen atom, a hydroxyl group, or a C1-C4 alkyl group each independently, B is a single bond -COO- ^* or -CONH- ^* , m is an integer of 0 to 3; Provided that at least one of R ² to R ⁶ is a hydroxy group, and the bond of each ^* in -COO- ^* or -CONH- ^* is bonded to carbon of (CH ₂ ) _m ].

The polymer which has a repeating unit represented by said Formula (1) is a polymerization initiator (for example, 2,2'- azobis (2, 4- dimethylvaleronitrile)) and a chain transfer agent (for example, in a solvent). 2,4-diphenyl-4-methyl-1-pentene), a phenolic hydroxyl group-containing unsaturated compound represented by the formula (3) and other unsaturated compounds copolymerizable therewith, and other monomers, if necessary, radicals. It can manufacture by superposing | polymerizing. Although the solvent used for this synthesis reaction is not specifically limited, For example, diethylene glycol methyl ethyl ether can be used. The ratio of the phenolic hydroxyl group-containing unsaturated compound of formula (3) to the total mass of the monomer mixture for forming this polymer is preferably 5 to 60% by mass, particularly preferably 5 to 50% by mass. . By using the phenolic hydroxyl group-containing unsaturated compound in such a ratio, even under strict conditions of high temperature and high humidity, it has very high adhesion and crack resistance to metal wiring such as an ITO transparent conductive film or molybdenum, and also has transparency and heat resistance. A protective film and an interlayer insulating film excellent in balance with various properties such as (heat resistance and transparency) can be formed.

As a phenolic hydroxyl group containing unsaturated compound represented by said formula (3), the compound etc. which are represented by following formula (4)-(8) are mentioned according to the definition of B and m in the said formula. The phenolic hydroxyl group containing unsaturated compound represented by these formula (3) can be used individually or in combination of 2 or more types.

[In formula (4), p is an integer of 1-3, and the definition of R <^1> , R <^2> , R <^3> , R <^4> , R <^5> and R <^6> is the same as the definition in said Formula (3) .;

[In formula (5), the definition of R <^1> , R <^2> , R <^3> , R <^4> , R <^5> and R <^6> is the same as the definition in said Formula (3) .;

[In formula (6), r is an integer of 1-3, and the definition of R <^1> , R <^2> , R <^3> , R <^4> , R <^5> and R <^6> is the same as the definition in said Formula (3) .;

[In formula (7), the definition of R <^1> , R <^2> , R <^3> , R <^4> , R <^5> and R <^6> is the same as the definition in said Formula (3) .;

[In formula (8), the definition of R <^1> , R <^2> , R <^3> , R <^4> , R <^5> and R <^6> is the same as the definition in said Formula (3).

When forming the polymer which has a repeating unit represented by said Formula (1), the epoxy group containing unsaturated compound (oxetanyl group containing unsaturated compound used for copolymerizing with the phenolic hydroxyl group containing unsaturated compound represented by Formula (3) is included. ), Glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-propyl acrylate, glycidyl α-butyl acrylate, glycidyl acrylate-3,4- Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl Glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, and the like.

Among these epoxy group-containing unsaturated compounds, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl Ether, 3, 4- epoxy cyclohexyl methacrylate, etc. are used preferably from the point of improving copolymerization reactivity and the heat resistance (heat transparency) and surface hardness of the protective film and interlayer insulation film obtained.

Specific examples of the oxetanyl group-containing unsaturated compound include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, and 3- (acryloyloxymethyl) -3- Ethyl oxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyl oxetane, 3- (acryloyloxymethyl ) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (acryloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2- Ethyl oxetane, 3- (2-acryloyloxyethyl) -3-ethyl oxetane, 3- (2-acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-acrylo Yloxyethyl) -2-pentafluoroethyloxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) -2,2-difluoro Looxe , 3- (2-acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane Acrylic acid esters;

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- ( Methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2- Phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (Methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) 2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-Methacryloyloxyethyl) -2-pentafluoroethyl oxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl ) -2,2-difluorooxetane, 3- (2-meth Methacrylic acid, such as kryloyloxyethyl) -2,2,4-trifluorooxetane and 3- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane Ester etc. are mentioned. These epoxy group containing unsaturated compounds can be used individually or in combination of 2 or more types.

When forming the polymer which has a repeating unit represented by said Formula (1), as an example of the other monomer used in order to copolymerize with the phenolic hydroxyl group containing unsaturated compound represented by Formula (3), unsaturated carboxylic acid, unsaturated carboxylic anhydride, meta Methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid ester having a hydroxyl group, acrylic cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, bicyclo unsaturated compound, maleimide Compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, unsaturated compounds having a furan skeleton, unsaturated compounds having a tetrahydropyran skeleton, unsaturated compounds having a pyran skeleton, a skeleton represented by the following formula (9) Unsaturated compounds having, and other unsaturated The compound can be mentioned.

[In formula (9), R <^15> is a hydrogen atom or a methyl group, n is an integer of 1 or more.

As a specific example of such other monomers,

As unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, monocarboxylic acid, such as acrylic acid, methacrylic acid, and crotonic acid, dicarboxylic acid, such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, is illustrated as a dicarboxylic acid here. Anhydrides of dicarboxylic acids such as anhydrides of one compound, mono [(meth) of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] Mono (meth) acrylate, 5-carboxybicyclo [2.2.1] hepto of a polymer having a carboxyl group and a hydroxyl group at the sock end, such as) acryloyloxyalkyl] ester and ω-carboxypolycaprolactone mono (meth) acrylate -2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5- Ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-ethylbar [2.2.1] hept-2-ene, 5,6-dicarboxy-bicyclo [2.2.1] hept-2-ene polycyclic compounds and anhydrides thereof having a carboxyl group such as anhydride, and the like;

As methacrylic acid chain alkyl ester, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl Methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate and the like; As methacrylic acid cyclic alkylesters, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, tricyclo [5.2.1.0 ^{2, 6} ] decane-8-yloxyethyl methacrylate, isobornyl methacrylate and the like; As methacrylic acid ester which has a hydroxyl group, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethyl glycoside, 4-hydroxyphenyl methacrylate, and the like; As acrylic acid cyclic alkylester, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8 -Yloxyethyl acrylate, isobornyl acrylate and the like; As methacrylic acid aryl ester, Phenyl methacrylate, benzyl methacrylate, etc .;

As acrylic acid aryl ester, Phenyl acrylate, Benzyl acrylate, etc .; As unsaturated dicarboxylic acid diester, Diethyl maleate, diethyl fumarate, diethyl itaconic acid etc .; As bicyclo unsaturated compounds, bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene , 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto- 2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxycarbo Nylbicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2.2 .1] hepto-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1 ] Hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1] hepto-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5- Methylbicyclo [2.2.1] hepto-2-ene and the like;

As the maleimide compound, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzyl maleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N- Succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate , N- (9-acridinyl) maleimide and the like; As an unsaturated aromatic compound, Styrene, (alpha) -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxy styrene etc .; Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like; As an unsaturated compound containing a tetrahydrofuran skeleton, tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxy tetrahydrofuran-2 -On and the like; As an unsaturated compound containing a furan skeleton, 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-ene-2 -One, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2- Mono-hex-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethylester, 6- (2-furyl) -6-methyl-1-hepten-3-one, and the like;

As an unsaturated compound containing tetrahydropyran skeleton, (tetrahydropyran-2-yl) methylmethacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -octo-1-ene- 3-one, 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, and the like; As an unsaturated compound containing a pyran skeleton, 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran, 4- (1,5-dioxa-6-oxo -7-octenyl) -6-methyl-2-pyran and the like; As an unsaturated compound containing the skeleton represented by said formula (9), polyethyleneglycol (n = 2-10) mono (meth) acrylate, polypropylene glycol (n = 2-10) mono (meth) acrylate, etc .; As other unsaturated compound, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, etc. are mentioned, respectively.

The usage-amount of [B] component in the said radiation sensitive composition becomes like this. Preferably it is 0.1 mass part-30 mass parts, More preferably, it is 0.5 mass part-20 mass parts with respect to 100 mass parts of [A] component. By using the amount of component (B) in an amount of 0.1 parts by mass to 30 parts by mass, it is possible to provide a high level of metal wiring such as an ITO transparent conductive film or molybdenum without causing a decrease in characteristics generally required such as transparency and heat resistance (heat resistance and transparency). A protective film and an interlayer insulating film having adhesion and crack resistance of can be formed.

[C] Ingredients: Radiation  Acid generator, Radiation  base Generator

The radiation sensitive acid generator or the radiation sensitive base generator of the component [C] is irradiated with radiation to thereby hydrolyze the siloxane polymer of the component [A] (preferably the hydrolyzable silane compound represented by the formula (2)). An acidic active substance or a basic active substance which acts as a catalyst for promoting condensation and curing reaction of a condensate) or a silane compound having a specific structure of component [A] and the component [F] described later. It is defined as a compound that can be released. In addition, as radiation to decompose component [C] to generate cations of acidic active substances or anions of basic active substances, visible rays, ultraviolet rays, infrared rays, X rays, α rays, β rays, γ rays and the like are used. Can be mentioned. Among these radiations, it is preferable to use ultraviolet rays because they have a constant energy level and can achieve a large curing rate, and the irradiation apparatus is relatively inexpensive and compact.

Moreover, it is also preferable to use together the radical polymerization initiator mentioned later with the radiation sensitive acid generator or radiation sensitive base generator of component [C]. The radical, which is a neutral active substance generated from the radical polymerization initiator, does not promote the condensation reaction of the hydrolyzable silane compound, but when the component [A] has a radical polymerizable functional group, it can promote polymerization of such functional group. have.

As the radiation sensitive acid generator of component [C], diphenyl iodonium salt, triphenylsulfonium, and tetrahydrothiophenium salt are preferable, and triphenylsulfonium salt and tetrahydrothiophenium salt are especially preferable. As a specific example of diphenyl iodonium salt, diphenyl iodonium tetrafluoro borate, diphenyl iodonium hexafluoro phosphonate, diphenyl iodonium hexafluoro arsenate, diphenyl iodonium trifluoro Romethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium butyltris (2,6-difluorophenyl) borate, 4-methoxy Phenylphenyl iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate, bis (4- t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate And bis (4-t-butylphenyl) iodonium camphor sulfonic acid.

Specific examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, and triphenylsulfonium-p. -Toluene sulfonate, triphenyl sulfonium butyl tris (2, 6- difluorophenyl) borate, etc. are mentioned.

Specific examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiopheniumtrifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl ) Tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro-2 -(Norbornane-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo [ 2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- ( 6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4,7-dibutoxy-1- Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, etc. are mentioned.

Among these radiation-sensitive acid generators, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, 1- (4,7-dibutoxy-1) from the viewpoint of improving radiation sensitivity of the radiation-sensitive composition Naphthalenyl) tetrahydrothiopheniumtrifluoromethanesulfonate is particularly preferred.

Examples of the radiation sensitive base generator of component [C] include 2-nitrobenzylcyclohexylcarbamate, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, N- (2-nitrobenzyl Oxycarbonyl) pyrrolidine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyl oxime, 4- (Methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone, hexaamine cobalt (III) tris (triphenylmethylborate), and the like. Among the radiation-sensitive base generators of the component [C], 2-nitrobenzylcyclohexyl carbamate and O-carbamoylhydroxyamide are particularly preferable from the viewpoint of improving radiation sensitivity of the radiation-sensitive composition.

A radiation sensitive acid generator or a radiation sensitive base generator of component [C] may be used individually by 1 type, and may mix and use 2 or more types. The amount of the component (C) used is preferably 0.1 parts by mass to 20 parts by mass, and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the component [A]. By setting the amount of the component [C] to 0.1 part by mass to 20 parts by mass, the radiation sensitivity, the surface hardness of the protective film and the interlayer insulating film to be formed, the heat resistance (heat transparency), and the adhesion to metal wiring such as an ITO transparent conductive film or molybdenum And a radiation sensitive composition excellent in the balance of crack resistance can be obtained.

Other optional ingredients

In addition to the above-mentioned [A]-[C] components, the radiation sensitive composition of this invention is a [D] dehydrating agent, a [E] ethylenically unsaturated compound, [ F] Other optional components, such as a silane compound which has a specific structure, [G] acid diffusion control agent, [H] radical polymerization initiator, and [I] surfactant, can be contained.

The dehydrating agent of the component [D] is defined as a substance capable of converting water into a substance other than water by chemical reaction, or trapping water by physical adsorption or inclusion. By optionally containing [D] dehydrating agent in the radiation-sensitive composition, water invading from the environment can be reduced. Therefore, by using the [D] dehydrating agent, it is possible to reduce the moisture in the composition, and as a result, the storage stability of the composition can be improved. As such a [D] dehydrating agent, at least one compound selected from the group consisting of carboxylic acid esters, acetals (including ketals), and carboxylic acid anhydrides can be preferably used.

Preferable examples of the carboxylic acid esters include orthocarboxylic acid esters and carboxylic acid silyl esters. Specific examples of orthocarboxylic acid esters include methyl ortho formate, ethyl ortho formate, propyl ortho formate, butyl ortho formate, methyl ortho acetate, ortho acetate, ortho acetate, butyl ortho acetate, methyl orthopropionate, ethyl orthopropionate, and the like. Can be. Moreover, ortho formic acid ester, such as methyl ortho formate, is especially preferable among these orthocarboxylic acid esters. Specific examples of the carboxylic acid silyl esters include trimethylsilyl acetate, tributylsilyl acetate, trimethylsilyl formate, trimethylsilyl oxalate, and the like.

Preferred examples of acetals include aldehydes or ketones with alcohols, aldehydes or ketones with dialcohols, and kethenyl acetals. Specific examples of the reactants of aldehydes or ketones with alcohols include dimethyl acetal, diethyl acetal, dipropyl acetal, and the like.

Preferable examples of the carboxylic acid anhydride include formic acid anhydride, acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and benzoic anhydride acetate. Among these carbonic anhydrides, acetic anhydride and succinic anhydride are preferred in view of dehydration effect.

The quantity in the case of using the [D] dehydrating agent becomes like this. Preferably it is 0.1-50 mass parts with respect to 100 mass parts of [A] components, More preferably, it is 0.5-30 mass parts, Especially preferably, it is 1-10 mass It is wealth. By setting the amount of the dehydrating agent to 0.1 to 50 parts by mass, the storage stability of the radiation-sensitive composition can be optimized.

Monomer, bifunctional, or trifunctional or more (meth) acrylic acid ester is preferable from a viewpoint that the component (E) has good polymerizability and the intensity | strength of the cured film obtained improves.

As monofunctional (meth) acrylic acid ester, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2 -Acryloyloxyethyl) (2-hydroxypropyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, (omega)-carboxy polycaprolactone monoacrylate, etc. are mentioned. As a commercial item, Aronix M-101, M-111, M-114, M-5300 (above, Toagosei Co., Ltd.); KAYARADTC-110S, TC-120S (above, Nippon Kayaku Co., Ltd.); Biscot 158, 2323 (above, Osaka Yukikagaku Kogyo Co., Ltd.), etc. are mentioned.

As a bifunctional (meth) acrylic acid ester, for example, ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimetha, Acrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanedioldiacrylate, 1,6-hexanedioldimethacrylate, 1,9-nonanedioldiacrylate, 1 And 9-nonanediol dimethacrylate. As a commercial item, For example, Aronix M-210, M-240, M-6200 (above, Toagosei Co., Ltd.); KAYARADHDDA, HX-220, R-604 (above, Nippon Kayaku Co., Ltd.); Biscot 260, 312, 335HP (above, Osaka Yuki Kagaku Kogyo Co., Ltd.); Light acrylate 1, 9-NDA (Kyoeisha Chemical Co., Ltd.) etc. are mentioned.

As (meth) acrylic acid ester more than trifunctional, for example, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate Mixture, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, succinic acid modified penta Erythritol triacrylate, succinic acid modified dipentaerythritol In addition to the acrylate and the tris (acryloxyethyl) isocyanurate, a compound having a linear alkylene group and an alicyclic structure and having at least two isocyanate groups, at least one hydroxyl group in the molecule, and 3, 4 The polyfunctional urethane acrylate type compound etc. which are obtained by making it react with the compound which has a dog or five (meth) acryloyloxy group are mentioned. As a commercial item, for example, Aronix M-309, East M-315, East M-400, East M-405, East M-450, East M-7100, East M-8030, East M-8060, East TO- 1450 (above, Toagosei Co., Ltd.); KAYARADTMPTA, copper DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120, copper DPEA-12 (above, Nippon Kayaku Co., Ltd.); Biscot 295, East 300, East 360, East GPT, East 3PA, East 400 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.); As a commercial item containing a polyfunctional urethane acrylate type compound, New Frontier R-1150 (Daiichi Kogyo Seyaku Co., Ltd.), KAYARAD DPHA-40H (above, Nippon Kayaku Co., Ltd.), etc. are mentioned.

Ω-carboxypolycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and di of these [E] components Pentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate mixture, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaeryte Commercially available products containing litolitriacrylate, succinic acid modified dipentaerythritol pentaacrylate, and polyfunctional urethane acrylate compounds are preferable. Especially, trifunctional or more than (meth) acrylic acid ester is preferable and the mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate is especially preferable.

The component [E] may be used alone or in combination of two or more thereof. As for the usage-amount of [E] component, 5-300 mass parts is preferable with respect to a total of 100 mass parts of [A] component and [B] component, 10-200 mass parts is more preferable, 20-100 mass parts is especially preferable. . By using the usage-amount of the component (E) in the said range, the sensitivity of the said composition, the surface hardness of the cured film obtained, and a crack resistance will become more favorable.

[F] component is a silane compound represented by following formula (10) or (12). This [F] component irradiates the radiation sensitive composition containing the said component, and the acid (acidic active species) or base (base activity) which generate | occur | produced from the said [C] radiation sensitive acid generator or a radiation sensitive base. Species) as a catalyst, and condensed together with the siloxane polymer of component [A] (preferably a hydrolysis condensation product of the hydrolyzable silane compound represented by the formula (2)) to form a cured product. In the radiation-sensitive composition, in addition to the component [B], by containing a silane compound having such a specific structure as the component [F], a metal film such as an ITO transparent conductive film, molybdenum, or the like of the protective film and the interlayer insulating film formed. Adhesion and crack resistance can be further improved.

[In formula (10), R <^9> and R <^11> is respectively independently a C1-C4 alkyl group, R <^10> is a C1-C6 alkylene group, a phenylene group, or group represented by Formula (11); In formula (11), a is an integer of 1-4; In formula (12), R <^12> , R <^13> and R <^14> is a C1-C4 alkyl group each independently, and b is an integer of 1-6.].

As a preferable specific example of R <^9> and R <^11> of Formula (10), a methyl group, an ethyl group, a propyl group, and a butyl group are mentioned. Among these alkyl groups, methyl group and ethyl group are more preferable. As a preferable specific example of R <^10> of Formula (10), a methylene group, an ethylene group, a propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, and phenylene group are mentioned. Among these groups, a methylene group, an ethylene group, and a phenylene group are more preferable. In addition, when R <^10> is group represented by Formula (11), 1 or 2 is preferable as a in Formula (11). Reactivity with [A] component improves by using the silane compound of Formula (10) of such a preferable structure as a [F] component.

As a preferable specific example of R <^12> , R <^13> and R <^14> of Formula (12), a methyl group, an ethyl group, a propyl group, and a butyl group are mentioned from a reactive viewpoint with [A] component. Among these alkyl groups, methyl groups are more preferable. In addition, it is preferable that b in Formula (12) is an integer of 1-3 from a viewpoint of reactivity and compatibility with [A] component.

In the said radiation sensitive composition, [F] component may be used individually by 1 type, or may be used in combination of 2 or more type. The silane compound which has the isocyanur ring represented by Formula (12) among the silane compounds of Formula (10) and (12) is more preferable. Thus, by using the silane compound which has the isocyanur ring which three trialkoxy silyl group couple | bonded in one molecule, the radiation sensitive composition which shows high radiation sensitivity is obtained, and the crosslinking degree of the protective film and interlayer insulation film formed from this composition are obtained. Can improve. Moreover, from the radiation sensitive composition containing such an isocyanur ring containing silane compound, it is a protective film which was remarkably excellent in adhesiveness and crack resistance with respect to metal wiring, such as an ITO transparent conductive film, molybdenum, even under strict conditions of high temperature and high humidity, and It is possible to form an interlayer insulating film.

Specific examples of the silane compound represented by formulas (10) and (12) include bis (triethoxysilyl) ethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, bis-1,2- ( Trimethoxysilyl) ethane, bis-1,2- (triethoxysilyl) ethane, bis-1,6- (trimethoxysilyl) hexane, bis-1,6- (triethoxysilyl) hexane, bis -1,4- (trimethoxysilyl) benzene, bis-1,4- (triethoxysilyl) benzene, 1,4-bis (trimethoxysilylmethyl) benzene, 1,4-bis (trimethoxy Silylethyl) benzene, 1,4-bis (triethoxysilylmethyl) benzene, 1,4-bis (triethoxysilylethyl) benzene, tris- (3-trimethoxysilylmethyl) isocyanurate, tris -(3-triethoxysilylmethyl) isocyanurate, tris- (3-trimethoxysilylethyl) isocyanurate, tris- (3-triethoxysilylethyl) isocyanurate, tris- ( 3-trimethoxysilylpropyl) isocyanurate, tris- (3-triethoxysilyl Lofil) isocyanurate, etc. are mentioned. Among them, 1,4-bis (trimethoxysilylmethyl) benzene, bis () from the viewpoint of improving the adhesion and crack resistance to metal wiring such as ITO transparent conductive film and molybdenum of the radiation sensitivity, the protective film and the interlayer insulating film obtained. Triethoxysilyl) ethane, tris- (3-trimethoxysilylethyl) isocyanurate, tris- (3-trimethoxysilylpropyl) isocyanurate, tris- (3-triethoxysilylpropyl) Isocyanurate is particularly preferred.

The quantity in the case of using the silane compound which has a specific structure of [F] component becomes like this. Preferably it is 5 mass parts-70 mass parts, More preferably, 10 mass parts-50 mass parts with respect to 100 mass parts of [A] component. to be. By using the amount of the component [F] in an amount of 5 parts by mass to 70 parts by mass, the radiation sensitivity and the radiation resistance excellent in a good balance of adhesion and crack resistance to metal wiring such as an ITO transparent conductive film or molybdenum of the protective film and interlayer insulating film obtained are well balanced. A composition can be obtained.

When the acid diffusion control agent of the [G] component uses a radiation sensitive acid generator as [C] component of a radiation sensitive composition, it controls the diffusion in the composition coating film of the acidic active substance which generate | occur | produced by irradiating radiation, , It has an effect of suppressing the curing reaction in the non-exposed areas. By using such an acid diffusion control agent together with the radiation sensitive acid generator of component [C], resolution of the radiation sensitive composition (radiation characteristics capable of accurately forming a desired pattern including a contact hole of an interlayer insulating film) Can be further improved.

Examples of the acid diffusion control agent include monoalkylamines, dialkylamines, trialkylamines, aromatic amines, alkanolamines, aliphatic amines, amide group-containing compounds, urea compounds, imidazoles, pyridines, and other nitrogen-containing heterocyclic compounds. Nitrogen containing compounds, such as these, are mentioned.

As a specific example of these acid diffusion control agents, for example

As monoalkylamines, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, etc .;

As dialkylamines, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n -Decylamine etc .;

As trialkylamines, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine , Tri-n-nonylamine, tri-n-decylamine and the like;

As aromatic amines, aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, 1-naphthyl Amine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2'- Bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4 -Aminophenyl) -1-methylethyl] benzene and the like;

Examples of alkanolamines include ethanolamine, diethanolamine, triethanolamine, and the like;

As aliphatic amines, ethylenediamine, N, N, N ', N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, N, N, N', N'-tetrakis (2-hydroxyethyl) ethylene Diamine, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, polyethyleneimine, polyallylamine, dimethylaminoethylacrylamide and the like;

As the amide group-containing compound, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, 2-pyrroli Don, N-methylpyrrolidone, etc .;

As the urea compound, urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea and the like;

As imidazole, imidazole, benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 4-methyl-2-phenylimidazole Etc;

As pyridines, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid Amides, quinoline, 8-oxyquinoline, acridine and the like;

Other nitrogen-containing heterocyclic compounds include pyrazine, pyrazole, pyridazine, quinoxaline, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2 ] Octane, 2,4 6-tri (2-pyridyl) -1,3,5-triazine, etc. are mentioned, respectively.

Among these nitrogen-containing compounds, trialkylamines and pyridines are preferable. Particularly preferred trialkylamines include triethylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine and tri-n-octylamine. Moreover, especially preferable pyridines are 2,4,6-tri (2-pyridyl) -1,3,5-triazine, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4- Ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxyquinoline, and acridine. These acid diffusion control agents may be used individually by 1 type, or may mix and use 2 or more types.

The quantity in the case of using the acid diffusion control agent [G] is 15 mass parts or less with respect to 100 mass parts of [A] components normally, Preferably it is 0.001-15 mass parts, More preferably, it is 0.005-5 mass parts. to be. By setting the amount of the acid diffusion control agent to 0.001 to 15 parts by mass, it is possible to form a protective film or an interlayer insulating film having a pattern with good accuracy while suppressing a decrease in the radiation sensitivity of the radiation-sensitive composition.

In the said radiation sensitive composition, you may mix | blend a [H] radical polymerization initiator (radical generator) in combination with the radiation sensitive acid generator or radiation sensitive base generator of [C] component. A radical polymerization initiator is a compound which has a function which decompose | disassembles by receiving a radiation, generate | occur | produces a radical, and starts the polymerization reaction of a radically polymerizable functional group by this radical. For example, when component [A] is a compound containing a (meth) acryloyl group in Formula (2), the polymerization reaction of [A] components is accelerated | stimulated by using [H] radical polymerization initiator, The degree of crosslinking as a whole cured film can be improved.

As such a radical polymerization initiator, for example, acetophenone, acetophenonebenzyl ketal, anthraquinone, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone , 4-chlorobenzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone type compound, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholino-propan-2-one, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl)- Butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, Bis (2,6-dimethoxybenzoyl) -2,4,4-tri-methylpentylphosphineoxide, benzyldimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenyl Propane-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone , Benzophenone derivative, Michler's ketone, 3-methylacetophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl oxime) etc. are mentioned. These radical generators may be used alone, or may be used in combination of two or more thereof.

The quantity in the case of using [H] radical polymerization initiator becomes like this. Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts with respect to 100 mass parts of [A] component. By setting the usage-amount of the [H] radical polymerization initiator in the radiation-sensitive composition to 0.1 to 30 parts by mass, the surface hardness, adhesion to metal wiring such as a substrate with ITO or molybdenum, and heat resistance (heat transparency) are balanced at a high level. It is possible to form excellent protective films and interlayer insulating films.

The surfactant of component [I] can be added in order to improve the applicability | paintability of a radiation sensitive composition, the reduction of application | coating nonuniformity, and the developability of a radiation irradiation part. As an example of a preferable surfactant, nonionic surfactant, a fluorine-type surfactant, and silicone type surfactant are mentioned.

As a nonionic surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate; (Meth) acrylic acid type copolymers etc. are mentioned. As an example of (meth) acrylic-acid-type copolymers, it is a commercial brand name and a polyflow No. 57, East No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

As the fluorine-based surfactant, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1 Fluoro ethers such as 1,2,2-tetrafluorobutyl) ether and hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether; Sodium perfluorododecylsulfonate; Fluoroalkanes such as 1,1,2,2,8,8,9,9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane; Sodium fluoroalkylbenzenesulfonic acid; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodines; Fluoroalkyl polyoxyethylene ethers; Perfluoroalkyl polyoxyethanols; Perfluoroalkylalkoxylates; Fluorine-based alkyl esters and the like.

Commercially available products of these fluorine-based surfactants include F-Top EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.), Mega Pack F171, 172, 173 (manufactured by Dainippon Inky Co., Ltd.), and Flora FC430, 431 (Sumitomo 3M). Manufactured by Asahi Guard AG710, Saflon S-382, SC-101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), FTX-218 (manufactured by Neosuke Co., Ltd.), etc. Can be mentioned.

As an example of a silicone type surfactant, it is a commercial brand name from SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH8400 FLUID (made by Toray Dow Corning Silicone Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.). Production).

The quantity in the case of using [I] surfactant becomes like this. Preferably it is 0.01-10 mass parts, More preferably, it is 0.05-5 mass parts with respect to 100 mass parts of [A] components. [I] The coating property of a radiation sensitive composition can be optimized by setting the usage-amount of surfactant to 0.01-10 mass parts.

Radiation  Composition

The radiation sensitive composition of this invention is a siloxane polymer of the said [A] component, the polymer which has a repeating unit of the specific structure of the [B] component, a radiation sensitive acid generator or a radiation sensitive base of [C] component It is prepared by mixing a generator and an optional component (such as a dehydrating agent of [D] component). Usually, a radiation sensitive composition is prepared and used in the state which melt | dissolved or disperse | distributed in a suitable solvent preferably. For example, a radiation sensitive composition can be prepared by mixing [A], [B], [C] component, and arbitrary components in a predetermined ratio in a solvent.

As a solvent which can be used for preparation of the said radiation sensitive composition, what melt | dissolves or disperse | distributes each component uniformly and does not react with each component is used suitably. Examples of such solvents include ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, Aromatic hydrocarbons, ketones, esters, etc. are mentioned.

As these solvents,

As ethers, For example, tetrahydrofuran etc .;

As diethylene glycol alkyl ether, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As ethylene glycol alkyl ether acetates, For example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc .;

As propylene glycol monoalkyl ethers, For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc .;

As propylene glycol monoalkyl ether acetates, For example, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, a propylene glycol monopropyl ether acetate, a propylene glycol monobutyl ether acetate, etc .;

As propylene glycol monoalkyl ether propionates, a propylene glycol monomethyl ether propionate, a propylene glycol monoethyl ether propionate, a propylene glycol monopropyl ether propionate, a propylene glycol monobutyl ether propionate, etc. are mentioned, for example. ;

As aromatic hydrocarbons, For example, toluene, xylene, etc .;

As ketones, For example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl- 2-pentanone, etc .;

As esters, for example, methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, methyl hydroxyacetic acid, ethyl hydroxyacetic acid, hydroxyacetic acid butyl, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate propyl, 3-hydroxypropionic acid propyl Butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoic acid, methyl methoxyacetic acid, ethyl methoxyacetic acid, methoxyacetic acid propyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, Ethoxyacetic acid propyl, ethoxyacetic acid butyl, propoxy acetate methyl, ethyl propoxy acetate, Lopoxyacetic acid propyl, butyl propoxyacetic acid, methyl butoxyacetic acid, ethyl butoxyacetate, butoxyacetic acid propyl, butyl butoxyacetic acid, 2-methoxypropionate methyl, 2-methoxypropionic acid propyl, 2-methoxypropionic acid propyl And butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, and the like.

Among these solvents, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, from the viewpoint of excellent solubility or dispersibility, nonreactivity with each component, and ease of coating film formation, Propylene glycol monoalkyl ether acetates, ketones and esters are preferable, and in particular, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, Propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methyl Methyl propionate, 2-hydroxy-2-methylpropy The acid acetate, methyl lactate, ethyl lactate, propyl lactate, butyl, 2-methoxy-propionic acid methyl, 2-methoxy-propionic acid ethyl are preferred. These solvents can be used individually or in mixture.

In addition to the above-mentioned solvents, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, and caproic acid may be further used as necessary. Caprylic acid 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylcellosolve acetate, High boiling point solvents, such as carbitol acetate, can also be used together.

In the case where the radiation-sensitive composition is prepared in a solution or dispersion state, the ratio of components (ie, the total amount of [A], [B] and [C] components, and other optional components) other than the solvent in the liquid is used. Although it can set arbitrarily according to a desired film thickness etc., Preferably it is 5-50 mass%, More preferably, it is 10-40 mass%, More preferably, you may be 15-35 mass%.

Formation of protective film or interlayer insulating film

Next, the method of forming the cured film of a protective film or an interlayer insulation film on a board | substrate using the said radiation sensitive composition is demonstrated. The method includes the following steps in the order described below.

(1) forming the coating film of the radiation sensitive composition of the present invention on a substrate;

(2) irradiating at least a part of the coating film formed in step (1) with radiation;

(3) developing the coating film irradiated with radiation in step (2), and

(4) A step of heating the coating film developed in the step (3).

(One) Radiation  The coating of the composition On a substrate  Forming process

In the process of said (1), after apply | coating the solution or dispersion liquid of the radiation sensitive composition of this invention on a board | substrate, Preferably a solvent is removed by heating (prebaking) a coating surface, and a coating film is formed. Glass, quartz, silicon, resin, etc. are mentioned as an example of the board | substrate which can be used. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, ring-opening polymers of cyclic olefins, and hydrogenated substances thereof.

It does not specifically limit as a coating method of a composition solution or a dispersion liquid, For example, the appropriate method, such as a spray method, a roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, can be employ | adopted. . Among these coating methods, the spin coating method or the slit die coating method is particularly preferable. Although the conditions of prebaking differ also according to the kind, compounding ratio, etc. of each component, Preferably it can be made into about 1 to 10 minutes at 70-120 degreeC.

(2) irradiating at least a part of the coating film with radiation

At the process of said (2), it exposes to at least one part of the formed coating film. In this case, when exposing to a part of coating film, it exposes normally through the photo mask which has a predetermined pattern. As radiation used for exposure, visible light, an ultraviolet-ray, an ultraviolet ray, an electron beam, X-rays, etc. can be used, for example. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet rays of 365 nm is particularly preferable.

The exposure amount in the said process is the value which measured the intensity | strength in the wavelength of 365 nm of radiation with the illuminometer (OAI model 356, OAI Optical Associates Inc. make), Preferably it is 100-10,000 J / m <^2> , Preferably it is 500-6,000 J / m <^2> .

(3) developing process

In the process of said (3), by developing the coating film after exposure, an unnecessary part (non-irradiation part of a radiation) is removed and a predetermined pattern is formed. As a developing solution used for a developing process, the aqueous solution of alkali (basic compound) is preferable. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia; And quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

In addition, an appropriate amount of water-soluble organic solvents and surfactants such as methanol and ethanol can also be added to such an aqueous alkali solution. The concentration of alkali in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining appropriate developability. As the developing method, for example, a suitable method such as a puddle method, a dipping method, a rocking dipping method or a shower method can be used. Although image development time changes with the composition of a radiation sensitive composition, Preferably it is about 10 to 180 second. Subsequent to such a developing process, after performing flowing water washing for 30 to 90 seconds, for example, by air-drying with compressed air or compressed nitrogen, a desired pattern can be formed.

(4) heating process

In the step (4), the condensation reaction of the component [A] (and the component [E]) is promoted and reliably cured by heating the patterned thin film using a heating device such as a hot plate or an oven. Can be obtained. Heating temperature is 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, it can be set as 5 to 30 minutes, for example, when performing a heating process on a hotplate, and 30 to 90 minutes when performing a heating process in an oven. The step baking method etc. which perform two or more heating processes can also be used. In this way, a patterned thin film corresponding to the target protective film or interlayer insulating film can be formed on the surface of the substrate.

Protective film or interlayer insulation film

The film thickness of the protective film or interlayer insulation film thus formed is preferably 0.1 to 8 µm, more preferably 0.1 to 6 µm, still more preferably 0.1 to 4 µm.

The protective film or the interlayer insulating film formed from the radiation-sensitive composition of the present invention, as is clear from the following examples, has excellent properties of transparency, thermal transparency, surface hardness, scratch resistance and crack resistance, and has high resolution. It has a high precision pattern formed of a radiation sensitive composition. Further, the protective film or the interlayer insulating film is excellent in adhesion and crack resistance to metal wiring such as an ITO transparent conductive film and molybdenum even under severe conditions of high temperature and high humidity. Therefore, the said protective film or interlayer insulation film is used suitably for display elements.

(Example)

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

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolyzed condensate of the hydrolyzable silane compound obtained from each synthesis example below were measured by the gel permeation chromatography (GPC) by the following specification.

Device: GPC-101 (Showa Denko KK)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko KK)

Mobile phase: tetrahydrofuran

Siloxane polymer Synthetic example

Synthesis Example 1

25 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, and then 30 mass parts of methyl trimethoxysilanes, 23 mass parts of phenyl trimethoxysilanes, and 0.1 mass part of tetra-i-propoxy aluminum, It heated until solution temperature became 60 degreeC. After solution temperature reached 60 degreeC, 18 mass parts of ion-exchange water was added, it heated until it became 75 degreeC, and it preserve | saved for 3 hours. Subsequently, 28 mass parts of methyl ortho formate was added as a dehydrating agent, and it stirred for 1 hour. Moreover, the solution temperature was 40 degreeC and the evaporation was carried out, maintaining temperature, and the methanol which generate | occur | produced in water and hydrolysis condensation was removed. The hydrolysis-condensation product (A-1) was obtained by the above. Solid content concentration of the hydrolysis-condensation product (A-1) was 40.5 mass%, the number average molecular weight (Mn) of the obtained hydrolysis-condensation product was 1,500, and molecular weight distribution (Mw / Mn) was 2.2.

Synthesis Example 2

25 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, and then 22 mass parts of methyl trimethoxysilanes, 12 mass parts of (gamma)-glycidoxy propyl trimethoxysilane, and 20 mass parts of phenyl trimethoxysilanes And 0.01 mass part of triethylamines were put, and the hydrolysis-condensation product (A-2) was obtained by the method similar to the synthesis example 1. Solid content concentration of the hydrolysis-condensation product (A-2) was 39.8 mass%, the number average molecular weight (Mn) of the obtained hydrolysis-condensation product was 1,300, and molecular weight distribution (Mw / Mn) was 2.2.

Synthesis Example 3

25 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, and then 22 mass parts of methyl trimethoxysilanes, 12 mass parts of 3-methacryloxypropyl trimethoxysilanes, and 20 mass parts of phenyl trimethoxysilanes And 0.5 mass part of oxalic acid was put, and the hydrolysis-condensation product (A-3) was obtained by the method similar to the synthesis example 1. Solid content concentration of the hydrolysis-condensation product (A-3) was 39.8 mass%, the number average molecular weight (Mn) of the obtained hydrolysis-condensation product was 1,200, and molecular weight distribution (Mw / Mn) was 2.5.

Synthesis Example of Copolymer

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. 10 parts by mass of glycidyl methacrylate, 20 parts by mass of styrene, 25 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 3-methacryloxypropyltrimethoxysilane 1 40 mass parts of mass parts and p-isopropenyl phenol (compound represented by said Formula (8)) were put, and after nitrogen-substituting, 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 (B-1). Solid content concentration of the obtained polymer solution was 32.6 mass%. The number average molecular weight of the obtained polymer was 3,300. Moreover, molecular weight distribution (Mw / Mn) was 1.8.

Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. 10 parts by mass of glycidyl methacrylate, 20 parts by mass of styrene, 25 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 3-methacryloxypropyltrimethoxysilane 1 40 mass parts of mass parts and p-vinyl phenol (compound represented by said Formula (8)) were put, and the polymer solution containing a copolymer (B-2) was obtained by the method similar to the synthesis example 4. Solid content concentration of the obtained polymer solution was 30.2 mass%. The number average molecular weight of the obtained polymer was 3,000. In addition, the molecular weight distribution (Mw / Mn) was 1.9.

[Synthesis Example 6]

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. 10 parts by mass of glycidyl methacrylate, 20 parts by mass of styrene, 25 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 3-methacryloxypropyltrimethoxysilane 1 40 mass parts of mass parts and p-hydroxyphenyl methacrylate (compound represented by said Formula (7)) were put, and the polymer solution containing a copolymer (B-3) was obtained by the method similar to the synthesis example 4. Solid content concentration of the obtained polymer solution was 32.2 mass%. The number average molecular weight of the obtained polymer was 3,400. Moreover, molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 7]

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. 10 parts by mass of glycidyl methacrylate, 20 parts by mass of styrene, 25 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 3-methacryloxypropyltrimethoxysilane 1 40 mass parts of mass parts and p-hydroxy methacrylanilide (compound represented by said Formula (5)) were put, and the polymer solution containing a copolymer (B-4) was obtained by the method similar to the synthesis example 4. Solid content concentration of the obtained polymer solution was 32.7 mass%. The number average molecular weight of the obtained polymer was 3,400. Moreover, molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 8]

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. 10 parts by mass of glycidyl methacrylate, 20 parts by mass of styrene, 25 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 3-methacryloxypropyltrimethoxysilane 1 40 mass parts of mass parts and 4-hydroxybenzyl methacrylate (compound represented by said Formula (6)) were put, and the polymer solution containing a copolymer (B-5) was obtained by the method similar to the synthesis example 4. Solid content concentration of the obtained polymer solution was 30.7 mass%. The number average molecular weight of the obtained polymer was 3,200. In addition, the molecular weight distribution (Mw / Mn) was 1.9.

Synthesis Example 9

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. 10 parts by mass of glycidyl methacrylate, 20 parts by mass of styrene, 25 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 3-methacryloxypropyltrimethoxysilane 1 Mass part and 40 mass parts of N- (4-hydroxybenzyl) methacrylamide (compound represented by said formula (4)) were put, and the polymer solution containing a copolymer (B-6) by the method similar to the synthesis example 4 was carried out. Got. Solid content concentration of the obtained polymer solution was 32.0 mass%. The number average molecular weight of the obtained polymer was 3,000. Moreover, molecular weight distribution (Mw / Mn) was 1.8.

Synthesis Example 10

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. Subsequently, 10 mass parts of glycidyl methacrylate, 20 mass parts of styrene, 25 mass parts of N-cyclohexyl maleimide, 1 mass part of 3-methacryloxypropyl trimethoxysilane, and p-isopropenyl phenol (the said 40 mass parts of compounds) represented by Formula (8) were put, and the polymer solution containing a copolymer (B-7) was obtained by the method similar to the synthesis example 4. Solid content concentration of the obtained polymer solution was 30.9 mass%. The number average molecular weight of the obtained polymer was 2,900. Moreover, molecular weight distribution (Mw / Mn) was 1.8.

Synthesis Example 11

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. Subsequently, 10 parts by mass of glycidyl methacrylate, 20 parts by mass of styrene, 25 parts by mass of N-cyclohexylmaleimide, 1 part by mass of 3-methacryloxypropyltrimethoxysilane, and p-vinylphenol (formula ( 40 mass parts of compounds) represented by 8) were put, and the polymer solution containing a copolymer (B-8) was obtained by the method similar to the synthesis example 4. Solid content concentration of the obtained polymer solution was 30.8 mass%. The number average molecular weight of the obtained polymer was 2,800. Moreover, molecular weight distribution (Mw / Mn) was 1.8.

Synthesis Example 12

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. Subsequently, 10 mass parts of glycidyl methacrylate, 20 mass parts of styrene, 25 mass parts of N-cyclohexyl maleimide, 1 mass part of 3-methacryloxypropyl trimethoxysilane, and p-hydroxyphenyl methacrylate (The compound represented by said formula (7)) 40 mass parts was put, and the polymer solution containing a copolymer (B-9) was obtained by the method similar to the synthesis example 4. Solid content concentration of the obtained polymer solution was 32.9 mass%. The number average molecular weight of the obtained polymer was 3,200. Moreover, molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 13]

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. Subsequently, 10 parts by mass of glycidyl methacrylate, 20 parts by mass of styrene, 25 parts by mass of N-cyclohexylmaleimide, 1 part by mass of 3-methacryloxypropyltrimethoxysilane, and p-hydroxymethacrylanilide ( 40 mass parts) of compounds represented by said formula (5) were put, and the polymer solution containing a copolymer (B-10) was obtained by the method similar to the synthesis example 4. Solid content concentration of the obtained polymer solution was 32.9 mass%. The number average molecular weight of the obtained polymer was 3,200. Moreover, molecular weight distribution (Mw / Mn) was 1.8.

[Synthesis Example 14]

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. Subsequently, 10 mass parts of glycidyl methacrylate, 20 mass parts of styrene, 25 mass parts of N-cyclohexyl maleimide, 1 mass part of 3-methacryloxypropyl trimethoxysilane, and 4-hydroxybenzyl methacrylate (The compound represented by said formula (6)) 40 mass parts was put, and the polymer solution containing a copolymer (B-11) was obtained by the method similar to the synthesis example 4. Solid content concentration of the obtained polymer solution was 32.9 mass%. The number average molecular weight of the obtained polymer was 3,100. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

Synthesis Example 15

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. Subsequently, 10 mass parts of glycidyl methacrylate, 20 mass parts of styrene, 25 mass parts of N-cyclohexyl maleimide, 1 mass part of 3-methacryloxypropyl trimethoxysilane, and N- (4-hydroxybenzyl ) 40 mass parts of methacrylamides (compound represented by said Formula (4)) were put, and the polymer solution containing a copolymer (B-12) was obtained by the method similar to the synthesis example 4. Solid content concentration of the obtained polymer solution was 32.0 mass%. The number average molecular weight of the obtained polymer was 3,300. In addition, the molecular weight distribution (Mw / Mn) was 1.9.

Synthesis Example 16

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. 10 parts by mass of glycidyl methacrylate, 20 parts by mass of styrene, 25 parts by mass of n-lauryl methacrylate, 1 part by mass of 3-methacryloxypropyltrimethoxysilane, and p-isopropenylphenol 40 mass parts of compounds) represented by Formula (8) were put, and the polymer solution containing a copolymer (B-13) was obtained by the same method as the synthesis example 4. Solid content concentration of the obtained polymer solution was 31.0 mass%. The number average molecular weight of the obtained polymer was 3,000. In addition, the molecular weight distribution (Mw / Mn) was 1.9.

Synthesis Example 17

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. Subsequently, 10 parts by mass of glycidyl methacrylate, 20 parts by mass of styrene, 25 parts by mass of n-benzyl methacrylate, 1 part by mass of 3-methacryloxypropyltrimethoxysilane, and p-hydroxyphenyl methacrylate ( 40 mass parts) of compounds represented by said formula (7) were put, and the polymer solution containing a copolymer (B-14) was obtained by the method similar to the synthesis example 4. Solid content concentration of the obtained polymer solution was 32.0 mass%. The number average molecular weight of the obtained polymer was 3,300. Moreover, molecular weight distribution (Mw / Mn) was 1.8.

Synthesis Example 18

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. 10 parts by mass of methacrylic acid 3,4-epoxycyclohexyl, 20 parts by mass of styrene, 25 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 3-methacryloxypropyl tree 1 mass part of methoxysilane and 40 mass parts of p-hydroxy methacrylanilide (compound represented by said Formula (5)) were put, and the polymer solution containing a copolymer (B-15) was prepared by the method similar to the synthesis example 4. Got it. Solid content concentration of the obtained polymer solution was 30.0 mass%. The number average molecular weight of the obtained polymer was 3,200. Moreover, molecular weight distribution (Mw / Mn) was 1.8.

Synthesis Example 19

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. Subsequently, 40 mass parts of styrene, 5 mass parts of 3-methacryloxypropyl trimethoxysilane, and 55 mass parts of p-isopropenyl phenols (the compound represented by said formula (8)) were put, and it carried out by the method similar to the synthesis example 4 The polymer solution containing copolymer (B-16) was obtained. Solid content concentration of the obtained polymer solution was 31.0 mass%. The number average molecular weight of the obtained polymer was 3,100. In addition, the molecular weight distribution (Mw / Mn) was 1.9.

Synthesis Example 20

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. Subsequently, 40 mass parts of styrene, 5 mass parts of 3-methacryloxypropyl trimethoxysilane, and 55 mass parts of p-hydroxyphenyl methacrylate (compound represented by said Formula (7)) were put, and it was the same method as the synthesis example 4. The polymer solution containing copolymer (B-17) was obtained. Solid content concentration of the obtained polymer solution was 32.0 mass%. The number average molecular weight of the obtained polymer was 3,300. Moreover, molecular weight distribution (Mw / Mn) was 1.8.

Synthesis Example 21

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. Subsequently, 40 parts by mass of styrene, 5 parts by mass of 3-methacryloxypropyltrimethoxysilane, and 55 parts by mass of p-hydroxymethacrylanilide (compound represented by the formula (5)) were added to the same method as in Synthesis Example 4. This obtained the polymer solution containing copolymer (B-18). Solid content concentration of the obtained polymer solution was 32.0 mass%. The number average molecular weight of the obtained polymer was 3,300. Moreover, molecular weight distribution (Mw / Mn) was 1.8.

Synthesis Example 22

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. Then, 80 mass parts of glycidyl methacrylate and 20 mass parts of styrene were put, and the polymer solution containing a copolymer (B-19) was obtained by the method similar to the synthesis example 4. Solid content concentration of the obtained polymer solution was 32.0 mass%. The number average molecular weight of the obtained polymer was 3,500. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

Synthesis Example 23

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. Subsequently, 79 mass parts of glycidyl methacrylate, 20 mass parts of styrene, and 1 mass part of 3-methacryloxypropyl trimethoxysilane are put, and a copolymer (B-20) is contained by the method similar to the synthesis example 4. A polymer solution was obtained. Solid content concentration of the obtained polymer solution was 28.0 mass%. The number average molecular weight of the obtained polymer was 3,000. In addition, the molecular weight distribution (Mw / Mn) was 1.9.

Synthesis Example 24

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. 34 parts by mass of glycidyl methacrylate, 25 parts by mass of styrene, 35 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, and 3-methacryloxypropyltrimethoxysilane 1 A mass part was put and the polymer solution containing a copolymer (B-21) was obtained by the same method as the synthesis example 4. Solid content concentration of the obtained polymer solution was 32.0 mass%. The number average molecular weight of the obtained polymer was 3,100. In addition, the molecular weight distribution (Mw / Mn) was 1.9.

Synthesis Example 25

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile), 6 parts by mass of 2,4-diphenyl-4-methyl-1-pentene and di 220 parts by mass of ethylene glycol methyl ethyl ether was added. Subsequently, 34 mass parts of glycidyl methacrylate, 25 mass parts of styrene, 35 mass parts of N-cyclohexyl maleimide, and 1 mass part of 3-methacryloxypropyl trimethoxysilane were put into it, and the method similar to the synthesis example 4 was carried out. The polymer solution containing copolymer (B-22) was obtained. Solid content concentration of the obtained polymer solution was 32.0 mass%. The number average molecular weight of the obtained polymer was 3,100. In addition, the molecular weight distribution (Mw / Mn) was 1.9.

Radiation  Preparation of composition and formation of protective film and interlayer insulating film

Example 1

[B] component to the solution (amount equivalent to 100 mass parts (solid content) of hydrolysis-condensation product (A-1)) containing the hydrolysis-condensation product (A-1) obtained by the synthesis example 1 as component [A]. As a solution containing a copolymer (B-1) formed of a monomer containing a compound represented by the above formula (8) as an amount ((B-1) 5 parts by mass (solid content)), [C] as a component ( C-3) 3 parts by mass of 2-nitrobenzylcyclohexylcarbamate, 0.05 parts by mass of 2,4,6-tri (2-pyridyl) -1,3,5-triazine as component [F], [H] 0.1 mass part of silicone type surfactant ("SH8400 FLUID" by Toray Dow Corning Co., Ltd.) was added as a component, propylene glycol monomethyl ether was added so that solid content concentration might be 20 mass%, and the radiation sensitive composition was prepared.

The radiation the composition, using a spinner and then applied to a SiO ₂ Dip a glass substrate to form a coating film and baked 90 ℃, 2 bungan landscape on a hot plate (ITO joined substrate, Mo adhesion in the ITO adhesion evaluation to be described later In the evaluation, a substrate with Mo is used). Next, the ultraviolet-ray was exposed to the obtained coating film by the exposure amount of 5000J / m <^2> . Subsequently, after developing 80 second at 25 degreeC with the 2.38 mass% tetramethylammonium hydroxide aqueous solution, it wash | cleaned for 1 minute with pure water, and also heating in 230 degreeC oven for 60 minutes, and the film thickness of 2.0 micrometers was A protective film was formed. In addition, by adjusting the rotation speed of the spinner at the time of forming the coating film so that the film thickness after heating is 3.0 mu m, the exposure gap (substrate and An interlayer insulating film was formed in the same manner as the above protective film formation except that the distance from the photomask) was exposed at 150 µm.

[Examples 2 to 57 and Comparative Examples 1 to 7]

Except as having described the kind and quantity of each component as Table 1, it carried out similarly to Example 1, the preparation of a radiation sensitive composition, and the formation of a protective film and an interlayer insulation film. In addition, all the numerical values regarding the compounding quantity of each component of Tables 1-3 show a mass part.

Property evaluation

Transparency, thermal transparency, pencil hardness (surface hardness), scratch resistance, crack resistance, and adhesion to a metal wiring such as a substrate or molybdenum with ITO, and a feeling of the protective film formed of Examples 1 to 57 and Comparative Examples 1 to 7 The evaluation method of the resolution (resolution of an interlayer insulation film) of a radioactive composition is demonstrated below. "Resolution" of a radiation sensitive composition gives evaluation of the performance which a composition can form the precise contact hole of an interlayer insulation film, and also gives evaluation as "resolution" of an interlayer insulation film.

(1) Evaluation of transparency of protective film

Light transmittance (%) of wavelength 400-800 nm using a spectrophotometer (150-20 type double beam by Hitachi Seisakusho Co., Ltd.) with respect to the board | substrate which has a protective film formed as mentioned above in each Example and a comparative example. ) Was measured. The minimum value of the light transmittance (%) of wavelength 400-800 nm was shown to Tables 1-3 as evaluation of transparency. When this value is 95% or more, it can be said that the transparency of a protective film is favorable. In the case of the interlayer insulating film, since the film thickness (3.0 µm) was only different from that of the protective film, it was judged that the transparency evaluation of the interlayer insulating film was the same as the evaluation of the transparency of the protective film.

(2) Evaluation of the heat resistance transparency of the protective film

About each board | substrate which has a protective film formed as mentioned above in each Example and a comparative example, it heats at 300 degreeC in clean oven for 30 minutes, and the light transmittance before and behind heating is described in said (1) "evaluation of the transparency of a protective film". Measured in one way. The heat-transparency (%) computed according to the following formula was shown in Tables 1-3. When this value is 5% or less, it can be said that the heat resistance transparency of a protective film is favorable. In the case of the interlayer insulating film, since the thickness (3.0 µm) was only different from that of the protective film, it was judged that the evaluation of the thermal transparency of the interlayer insulating film was the same as the evaluation of the thermal transparency of the protective film.

Heat transparency (%) = light transmittance before heating (%)-light transmittance after heating (%)

(3) Measurement of pencil hardness (surface hardness) of protective film

About the board | substrate which has a protective film formed as mentioned above in each Example and the comparative example, the pencil hardness (surface hardness) of a protective film was measured by the 8.4.1 pencil scraping test of JIS-K-5400-1990, and a result is shown in the table | surface. It showed in 1-3. When this value is 3H or larger, it can be said that the surface hardness of a protective film is favorable. In the case of an interlayer insulating film, since the film thickness (3.0 micrometers) differs only from a protective film, it was judged that evaluation of the pencil hardness of an interlayer insulating film is the same as evaluation of the pencil hardness of a protective film.

(4) Evaluation of the scratch resistance of the protective film

The board | substrate with the protective film formed as mentioned above in each Example and the comparative example was reciprocated 10 times by applying the load of 200g on steel wool # 0000 using the Hakjin type abrasion tester. The situation of abrasion was visually evaluated by the following judgment criteria, and the result was shown to Tables 1-3.

Criteria

◎: no scratch

(Circle): 1-3 flaws arise

△: 4 to 10 scratches are generated

×: 10 or more scratches

If said determination is (double-circle) or (circle), it can be said that it has favorable scratch resistance. In the case of the interlayer insulating film, since the film thickness (3.0 µm) was only different from that of the protective film, the evaluation of the scratch resistance of the interlayer insulating film was judged to be the same as the evaluation of the scratch resistance of the protective film.

(5) Confirmation of crack occurrence (evaluation of crack resistance)

In the Examples and Comparative Examples, the substrate having the protective film formed as described above was left to stand at 23 ° C. for 24 hours, and was the crack generated on the surface of the protective film? A laser microscope (VK-8500 manufactured by Keyence Co., Ltd.) was used. Confirmed using. It evaluated on the following judgment criteria, and the result was shown to Tables 1-3.

Criteria

◎: No crack at all

(Circle): 1-3 cracks exist

△: 4 to 10 cracks present

×: 10 or more cracks

If said determination is (double-circle) or (circle), it can be said that the confirmation result of the presence or absence of a crack is favorable. In the case of the interlayer insulating film, since the film thickness (3.0 µm) was only different from that of the protective film, it was judged that the evaluation of crack resistance of the interlayer insulating film was the same as the evaluation of crack resistance of the protective film.

(6) Evaluation of ITO (Indium Tin Oxide) Adhesiveness and Mo (Molybdenum) Adhesiveness of Protective Film

Except using the substrate with ITO and the substrate with Mo (molybdenum), the protective film was formed as mentioned above in each Example and the comparative example, and the pressure cooker test (120 degreeC, 100% of humidity, 4 hours) was done. Then, the 8.5.3 adhesive checker tape method of JIS-K-5400-1990 was performed, the number of remaining checkerboard eyes was calculated | required in 100 checkerboard eyes, and ITO adhesiveness and Mo adhesiveness of a protective film were evaluated. The results are shown in Tables 1-3. About the board | substrate with an ITO, when the number of the remaining board | substrate out of 100 board | substrate exceeds 90, it can be said that ITO adhesiveness is favorable. In addition, since the Mo adhesion substrate tends to be inferior in adhesion compared with the ITO attachment substrate, Mo adhesion is said to be good with respect to Mo attachment substrate, when the number of remaining board | substrates exceeds 80 pieces in 100 board eyes. Can be. In the case of the interlayer insulating film, since the film thickness (3.0 µm) was only different from that of the protective film, it was judged that the evaluation of ITO adhesiveness and Mo adhesiveness of the interlayer insulating film was the same as the evaluation of ITO adhesiveness and Mo adhesiveness of the protective film.

(7) Evaluation of the resolution (resolution of the interlayer insulating film) of the radiation sensitive composition

In the formation of the interlayer insulating film in each of Examples and Comparative Examples, the resolution can be said to be good as long as the contact hole pattern of 30 µm or less can be resolved. The contact hole pattern size (the minimum size which was resolvable to 20 micrometers-50 micrometers) which was resolvable is shown to Tables 1-3.

In addition, in Table 1, a [C] radiation sensitive acid generator or a radiation sensitive base generator, [E] ethylenically unsaturated compound, the silane compound which has a [F] specific structure, [G] acid diffusion control agent, The abbreviation of [H] radical polymerization initiator and [I] surfactant shows the following, respectively.

C-1: triphenylsulfonium trifluoromethanesulfonate

C-2: 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiopheniumtrifluoromethanesulfonate

C-3: 2-nitrobenzylcyclohexylcarbamate

E-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (trade name: MAX-3510, manufactured by Nippon Kayaku Co., Ltd.)

E-2: pentaerythritol triacrylate (trade name: A-TMM-3LMN, manufactured by Shin-Nakamura Kagaku Kogyo Co., Ltd.)

F-1: 1,4-bis (trimethoxysilylmethyl) benzene

F-2: bis (triethoxysilyl) ethane

F-3: tris- (3-trimethoxysilylpropyl) isocyanurate

G-1: 2,4,6-tri (2-pyridyl) -1,3,5-triazine

H-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl oxime) (brand name: Irgacure OXE02, Chiba Specialty Chemicals Co., Ltd.)

I-1: Silicone type surfactant ("SH8400 FLUID" made by Toray Dow Corning Co., Ltd.)

As is apparent from the results of Tables 1 to 3, the radiation sensitive compositions of Examples 1 to 57 according to the present invention are polymers having a repeating unit having a specific structure in addition to the components [A] and [C]. By including the components, it satisfactorily meets the general requirements such as transparency, heat resistance, pencil hardness (surface hardness), and scratch resistance, and is also suitable for ITO transparent conductive films and molybdenum substrates under severe conditions of high temperature and high humidity. It turned out that the protective film (and interlayer insulation film) which exhibits the outstanding adhesiveness and crack resistance can be formed. Moreover, it turned out that the said radiation sensitive composition expresses sufficient resolution of the grade which can form a contact hole. On the other hand, the protective film (and the interlayer insulation film) formed from the compositions of Comparative Examples 1 to 7, which do not contain the component corresponding to the component [B] of the present invention, is inferior in adhesion to an ITO transparent conductive film or molybdenum substrate, and These compositions did not express sufficient resolution.

The radiation-sensitive composition of the present invention satisfactorily satisfies general requirements such as transparency, heat resistance, and surface hardness, and is also suitable for metal wiring such as ITO transparent conductive films and molybdenum even under strict conditions of high temperature and high humidity. It is possible to form a protective film and an interlayer insulating film exhibiting excellent adhesion and crack resistance. Moreover, the said radiation sensitive composition has negative radiation sensitive properties, and is advantageous in terms of cost. Therefore, the protective film or interlayer insulation film formed in this way can be used suitably especially for a display element.

Claims (9)

[A] siloxane polymer,
[B] a polymer having a repeating unit represented by the following Formula (1),
[C] radiation-sensitive acid generators or radiation-sensitive base generators
A radiation sensitive composition containing:

[In formula (1), R <^1> is a hydrogen atom or a C1-C4 alkyl group, R <^2> -R <^6> is a hydrogen atom, a hydroxyl group, or a C1-C4 alkyl group each independently, B is a single bond, -COO- ^* or -CONH- ^* , m is an integer of 0 to 3, provided that at least one of R ² to R ⁶ is a hydroxyl group, respectively in -COO- ^* or -CONH- ^* Of * bond with (CH ₂ ) _m carbon. The method of claim 1,
The radiation sensitive composition whose [A] siloxane polymer is a hydrolysis-condensation product of the hydrolyzable silane compound represented by following formula (2).

[In formula (2), R <^7> is a C1-C20 non-hydrolyzable organic group, R <^8> is a C1-C4 alkyl group and q is an integer of 0-3.]. The method of claim 2,
(D) A radiation sensitive composition further containing a dehydrating agent. The method of claim 3,
[E] A radiation sensitive composition further containing an ethylenically unsaturated compound. The method according to any one of claims 1 to 4,
[C] A radiation sensitive composition wherein at least one selected from the group consisting of triphenylsulfonate salts and tetrahydrothiophenium salts is used as the radiation sensitive acid generator. The method according to any one of claims 1 to 4,
[C] A radiation sensitive composition wherein at least one selected from the group consisting of 2-nitrobenzylcyclohexylcarbamate and O-carbamoylhydroxyamide is used as the radiation sensitive base generator. The method according to any one of claims 1 to 4,
A radiation sensitive composition used for forming a protective film or an interlayer insulating film of a display element. (1) Process of forming the coating film of the radiation sensitive composition of Claim 7 on a board | substrate,
(2) irradiating at least a part of the coating film formed in step (1) with radiation;
(3) developing the coating film irradiated with radiation in step (2), and
(4) Step of heating the coating film developed in Step (3)
A method of forming a protective film or interlayer insulating film for display element comprising a. The protective film or interlayer insulation film of the display element formed from the radiation sensitive composition of Claim 7.