KR101289223B1 - Radiation Sensitive Resin Composition, and Formation of Interlayer Insulating Film and Microlens - Google Patents

Abstract

The present invention contains a copolymer of a compound having a structure having an ether bond such as unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, oxetane compound and tetrahydrofuran structure and a 1,2-quinonediazide compound. A radiation sensitive resin composition used for forming a microlens and an interlayer insulating film is provided.

Radiation-sensitive resin composition, interlayer insulating film, microlens

Description

Radiation Sensitive Resin Composition, and Formation of Interlayer Insulating Film and Microlens

1 is a schematic diagram of a microlens cross-sectional shape.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2001-354822

[Patent Document 2] Japanese Patent Application Laid-Open No. 2001-343743

[Patent Document 3] Japanese Unexamined Patent Publication No. 6-18702

[Patent Document 4] Japanese Unexamined Patent Publication No. 6-136239

[Patent Document 5] Japanese Patent Application Laid-Open No. 2001-330953

The present invention relates in particular to a radiation sensitive resin composition useful for the formation of an interlayer insulating film and microlens, an interlayer insulating film and microlens formed of the radiation sensitive resin composition, and a method of forming the interlayer insulating film and microlens.

Electronic components such as thin film transistors (hereinafter referred to as "TFT") type liquid crystal display elements, magnetic head elements, integrated circuit elements, and solid-state image pickup elements are generally provided with an interlayer insulating film for insulating between wirings arranged in layers. . As the material for forming the interlayer insulating film, since the number of steps for obtaining the required pattern shape is small, and it is preferable to have sufficient flatness, the radiation-sensitive resin composition is widely used (Japanese Patent Laid-Open No. 2001-354822). And Japanese Patent Laid-Open No. 2001-343743.

Among the electronic components, for example, a TFT type liquid crystal display element is manufactured through a process of forming a transparent electrode film on the interlayer insulating film and forming a liquid crystal alignment film thereon, so that the interlayer insulating film is subjected to a high temperature condition in the step of forming the transparent electrode film. Since it is exposed or exposed to the stripping solution of the resist used for pattern formation of an electrode, sufficient resistance to these is needed.

In addition, recently, in the TFT type liquid crystal display device, large screen, high brightness, high precision, high-speed response, and thinning are progressing, and due to the request for yield in the process, a highly sensitive radiation-sensitive resin composition used for forming an interlayer insulation film In addition, the interlayer insulating film to be formed is required to have higher performance than the conventional one in view of low dielectric constant, high light transmittance, and the like.

On the other hand, as an optical material of an imaging optical system of an on-chip color filter such as a facsimile, an electronic copier, a solid-state imaging device, or an optical fiber connector, a microlens having a lens diameter of about 3 to 100 μm in diameter or a microlens array in which it is arranged regularly It is used.

As a method of forming a microlens, a patterned thin film corresponding to a lens is formed, and then heated and melted to be used as a lens as it is, or a lens is formed by dry etching using a melt-flowed lens pattern as a mask. And a method for transferring the same is known. The radiation sensitive resin composition is also widely used for formation of such a lens pattern (refer Unexamined-Japanese-Patent No. 6-18702 and Unexamined-Japanese-Patent No. 6-136239).

In addition, the radiation sensitive resin composition used to form the lens pattern is required that the microlenses formed with high sensitivity and high sensitivity have a desired radius of curvature and have high heat resistance and high light transmittance.

In addition, the device in which the microlens is formed as described above is coated with a planarization film and an etching resist to remove various insulating films on the bonding pad, which is a wiring forming portion, and irradiated with radiation through a desired photomask, followed by developing and bonding. After removing the etching resist of the pad portion, the planarizing film and various insulating films are removed by etching to expose the bonding pad portion. Therefore, the microlenses require solvent resistance, heat resistance, and the like in the coating film forming step and the etching step of the planarization film and the etching resist.

On the other hand, in the interlayer insulating film and the microlens obtained as described above, when the developing time is more than the optimum time in the developing step in forming them, the developer easily penetrates between the pattern and the substrate, and peeling occurs easily. In order to avoid the problem, it is necessary to strictly control the development time, which is problematic in terms of yield and productivity of the product.

Moreover, in order to improve the heat resistance and surface hardness of an interlayer insulation film and a microlens, the proposal which adds antimony fluoride as a heat sensitive acid generator was made to the radiation sensitive resin composition which is a raw material (Japanese Patent Laid-Open No. 2001-330953). In the case of such a radiation sensitive resin composition, the problem of the toxicity by an antimony type compound is pointed out.

Thus, in the radiation sensitive resin composition used for formation of an interlayer insulation film or a microlens, high sensitivity is required, and in the developing step, it is required that no pattern peeling occurs even when the developing time is more than a predetermined time. In addition, the formed interlayer insulating film requires high heat resistance, high solvent resistance, low dielectric constant, high light transmittance, and the like, while forming a microlens, in addition to a good melt shape (desirable curvature radius) as a microlens, high heat resistance, Although high solvent resistance, high light transmittance, etc. are required, the radiation sensitive resin composition which can satisfy such various requirements fully and does not have a problem also in safety is not known conventionally.

<Start of invention>

The present invention has been made on the basis of the above circumstances, and the first object of the present invention is not a safety problem, and is excellent in sensitivity, resolution, storage stability as a solution, and the like, and still exceeds the optimum developing time in the developing step. It is providing the radiation sensitive resin composition which has a favorable image development margin which can form a favorable pattern shape.

The 2nd object of this invention is to provide the method of forming the interlayer insulation film which combines the outstanding solvent resistance, heat resistance, light transmittance, adhesiveness, etc. using the said radiation sensitive resin composition.

Further, a third object of the present invention is to provide a method for forming a microlens having excellent melt shape, having excellent solvent resistance, heat resistance, light transmittance, adhesiveness, and the like by using the radiation-sensitive resin composition described above. There is.

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

According to the present invention, the above objects and advantages of the present invention,

[A] (a1) at least one compound selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides,

(a2) at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), and

(a3) Unsaturated compound having at least one structure selected from the group consisting of a tetrahydrofuran structure, a furan structure, a tetrahydropyran structure, a pyran structure and a structure represented by the following formula (3) in a molecule:

&Lt; / RTI &gt;

[B] 1,2-quinonediazide compound

It is achieved by the radiation sensitive resin composition characterized by including the following.

(Wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ independently of each other are a hydrogen atom) , A fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6.

Wherein R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ And n is the same as defined in Formula 1).

(In formula, R <^6> is a hydrogen atom or a methyl group, m is an integer of 2-10.)

The above objects and advantages of the present invention are secondly achieved by a method for forming an interlayer insulating film, which comprises the following steps in the order described below.

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

(B) irradiating at least a portion of said film with radiation,

(C) developing the film after irradiation, and

(D) A step of heating the film after development.

The above objects and advantages of the present invention are achieved by a method of forming a microlens, which comprises the following steps in the order described below.

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

(B) irradiating at least a portion of said film with radiation,

(C) developing the film after irradiation, and

(D) A step of heating the film after development.

BEST MODE FOR CARRYING OUT THE INVENTION [

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

[A] copolymer

[A] copolymer contained in the radiation sensitive resin composition of this invention is 1 or more types chosen from (a1) unsaturated carboxylic acid and unsaturated carboxylic anhydride (henceforth "unsaturated compound (a1)"). , (a2) at least one selected from the group consisting of a compound represented by the formula (1) and a compound represented by the formula (2) (hereinafter referred to as an "unsaturated compound (a2)"), and (a3) in a molecule Air of an unsaturated compound having one or more structures selected from the group consisting of furan structure, furan structure, tetrahydropyran structure, pyran structure and structure represented by the above formula (hereinafter referred to as &quot; unsaturated compound (a3) &quot;) It is coalescing.

As an unsaturated compound (a1), a monocarboxylic acid compound, a dicarboxylic acid compound, the acid anhydride of dicarboxylic acid, the mono [(meth) acryloyloxyalkyl] ester of polyhydric carboxylic acid, both terminal, for example Mono (meth) acrylate etc. of the polymer which has a carboxyl group and a hydroxyl group are mentioned.

Examples of the monocarboxylic acid compound include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid and the like;

As said dicarboxylic acid compound, For example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .;

As an acid anhydride of the said dicarboxylic acid, For example, acid anhydride etc. of the said dicarboxylic acid compound;

As mono [(meth) acryloyloxyalkyl] ester of the said polyhydric carboxylic acid, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), etc .;

As mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group in the said both terminal, ω-carboxypolycaprolactone monoacrylate, the ω-carboxypolycaprolactone monomethacrylate, etc. are mentioned, respectively.

Among these unsaturated compounds (a1), acrylic acid, methacrylic acid, maleic anhydride and the like are preferred in terms of copolymerization reactivity, solubility in aqueous alkali solution and availability.

The said unsaturated compound (a1) can be used independently and can also use 2 or more types together.

In the polymer (A), the content of the repeating unit derived from the (a1) unsaturated compound is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, particularly preferably 15 to 40% by weight. By setting it as the content rate of this range, the solubility with respect to the alkaline developing solution of the composition obtained can be controlled to a more appropriate range.

An unsaturated compound (a2) is 1 or more types of compounds chosen from the group which consists of a compound represented by following formula (1), and the compound represented by following formula (2).

&Lt; Formula 1 >

(Wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ independently of one another are hydrogen An atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6.

<Formula 2>

Wherein R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ And n has the same meaning as defined in Formula 1 above.)

In the above formulas (1) and (2), examples of the alkyl group having 1 to 4 carbon atoms of R, R ¹ , R ² , R ³ , R ^4, and R ⁵ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, etc. are mentioned.

Moreover, as a C6-C20 aryl group of R <^2> , R <^3> , R <^4> and R <^5> , a phenyl group, a toluyl group, etc. are mentioned, for example. Moreover, as a C1-C4 perfluoroalkyl group of R <^2> , R <^3> , R <^4> and R <^{5>, it} is a trifluoromethyl group, pentafluoroethyl group, heptafluoro-n-propyl group, heptafluoro, for example. -i-propyl group, nonafluoro-n-butyl group, nonafluoro-i-butyl group, nonafluoro-sec-butyl group, nonafluoro-t-butyl group, etc. are mentioned.

As a compound represented by the said Formula (1), for example, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl)- 3-ethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyl Oxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorojade Cetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl ) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2-trifluoromethyloxetane, 3- ( 2-acryloyloxyethyl) -2-pentafluoroethyl oxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) -2, 2-difluoro Oxetane, 3- (2-acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluoro Acrylic esters such as oxetane;

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-methacryloyloxy Ethyl) -2,2-difluorooxetane, 3- (2-meth (Methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, etc., Esters, and the like.

As a compound represented by the said Formula (2), for example, 2- (acryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) -2-methyloxetane, 2- (acryloyloxymethyl)- 3-methyloxetane, 2- (acryloyloxymethyl) -4-methyloxetane, 2- (acryloyloxymethyl) -2-trifluoromethyloxetane, 2- (acryloyloxymethyl) 3-trifluoromethyloxetane, 2- (acryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 2- (Acryloyloxymethyl) -3-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -4-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -2-phenylox Cetane, 2- (acryloyloxymethyl) -3-phenyloxetane, 2- (acryloyloxymethyl) -4-phenyloxetane, 2- (acryloyloxymethyl) -2,3-difluoro Rooxetane, 2- (acryloyloxymethyl) -2,4-difluorooxetane, 2- (acryloyloxymethyl) -3,3-diflu Oroxoxane, 2- (acryloyloxymethyl) -3,4-difluorooxetane, 2- (acryloyloxymethyl) -4,4-difluorooxetane, 2- (acryloyl Oxymethyl-3,3,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,4,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,3 , 4,4-tetrafluorooxetane,

2- (2-acryloyloxyethyl) oxetane, 2- [2- (2-methyloxetanyl)] ethyl methacrylate, 2- [2- (3-methyloxetanyl)] ethyl methacryl Late, 2- (acryloyloxyethyl) -2-methyloxetane, 2- (2-acryloyloxyethyl) -4-methyloxetane, 2- (2-acryloyloxyethyl) -2- Trifluoromethyloxetane, 2- (2-acryloyloxyethyl) -3-trifluoromethyloxetane, 2- (2-acryloyloxyethyl) -4-trifluoromethyloxetane, 2 -(2-acryloyloxyethyl) -2-pentafluoroethyl oxetane, 2- (2-acryloyloxyethyl) -3-pentafluoroethyl oxetane, 2- (2-acryloyloxy Ethyl) -4-pentafluoroethyloxetane, 2- (2-acryloyloxyethyl) -2-phenyloxetane, 2- (2-acryloyloxyethyl) -3-phenyloxetane, 2- (2-acryloyloxyethyl) -4-phenyloxetane, 2- (2-acryloyloxyethyl) -2,3-difluorooxetane, 2- (2-acryloyloxyethyl)- 2,4-difluorooxetane, 2- (2-acryloyl jade Ethyl) -3,3-difluorooxetane, 2- (2-acryloyloxyethyl) -3,4-difluorooxetane, 2- (2-acryloyloxyethyl) -4,4 -Difluorooxetane, 2- (2-acryloyloxyethyl) -3,3,4-trifluorooxetane, 2- (2-acryloyloxyethyl) -3,4,4-tri Acrylic esters such as fluorooxetane and 2- (2-acryloyloxyethyl) -3,3,4,4-tetrafluorooxetane;

2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -2-methyloxetane, 2- (methacryloyloxymethyl) -3-methyloxetane, 2- ( Methacryloyloxymethyl) -4-methyloxetane, 2- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -3-trifluoro Methyl oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -2-pentafluoroethyl oxetane, 2- (methacrylo) Yloxymethyl) -3-pentafluoroethyl oxetane, 2- (methacryloyloxymethyl) -4-pentafluoroethyl oxetane, 2- (methacryloyloxymethyl) -2-phenyloxetane , 2- (methacryloyloxymethyl) -3-phenyloxetane, 2- (methacryloyloxymethyl) -4-phenyloxetane, 2- (methacryloyloxymethyl) -2,3- Difluorooxetane, 2- (methacryloyloxymethyl) -2,4-difluorooxetane, 2- (methacryloyloxy methyl) -3,3-difluorooxetane, 2- ( Methacryloyloxymethyl) -3,4-difluorooxetane, 2- (methacryloyloxymethyl) -4,4-difluorooxetane, 2- (methacryloyloxymethyl)- 3,3,4-trifluorooxetane, 2- (methacryloyloxymethyl) -3,4,4-trifluorooxetane, 2- (methacryloyloxymethyl) -3,3, 4,4-tetrafluorooxetane,

2- (2-methacryloyloxyethyl) oxetane, 2- [2- (2-methyloxetanyl)] ethyl methacrylate, 2- [2- (3-methyloxetanyl)] ethyl meth Acrylate, 2- (2-methacryloyloxyethyl) -2-methyloxetane, 2- (2-methacryloyloxyethyl) -4-methyloxetane, 2- (2-methacryloyl Oxyethyl) -2-trifluoromethyloxetane, 2- (2-methacryloyloxyethyl) -3-trifluoromethyloxetane, 2- (2-methacryloyloxyethyl) -4- Trifluoromethyloxetane, 2- (2-methacryloyloxyethyl) -2-pentafluoroethyl oxetane, 2- (2-methacryloyloxyethyl) -3-pentafluoroethyl oxetane , 2- (2-methacryloyloxyethyl) -4-pentafluoroethyloxetane, 2- (2-methacryloyloxyethyl) -2-phenyloxetane, 2- (2-methacrylo Yloxyethyl) -3-phenyloxetane, 2- (2-methacryloyloxyethyl) -4-phenyloxetane, 2- (2-methacryloyloxyethyl) -2,3-difluoro Oxetane, 2- (2-methacryloyloxyethyl) -2,4-dip Oroxoxane, 2- (2-methacryloyloxyethyl) -3,3-difluorooxetane, 2- (2-methacryloyloxyethyl) -3,4-difluorooxetane, 2- (2-methacryloyloxyethyl) -4,4-difluorooxetane, 2- (2-methacryloyloxyethyl) -3,3,4-trifluorooxetane, 2- (2-methacryloyloxyethyl) -3,4,4-trifluorooxetane, 2- (2-methacryloyloxyethyl) -3,3,4,4-tetrafluorooxetane, etc. And methacrylic acid esters thereof.

Among these unsaturated compounds (a2), 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2- Trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4- It is preferable at the point that the developing margin of the radiation sensitive resin composition from which trifluoromethyl oxetane etc. are obtained is wide, and the chemical-resistance of the interlayer insulation film and microlenses obtained is improved.

These unsaturated compounds (a2) can be used independently and can also use 2 or more types together.

The content of the structural unit derived from the unsaturated compound (a2) in the copolymer (A) is preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight. By setting it as content of this range, the balance of the storage stability of a composition and the heat resistance of the obtained interlayer insulation film or microlens becomes more excellent.

The unsaturated compound (a3) is an unsaturated compound having at least one structure selected from the group consisting of a tetrahydrofuran structure, a furan structure, a tetrahydropyran structure, a pyran structure and a structure represented by the following formula (3) in a molecule.

<Formula 3>

(Wherein R ⁶ is hydrogen or a methyl group, m is an integer from 2 to 10.)

As an example of an unsaturated compound (a3), it is an unsaturated compound which has a tetrahydrofuran structure, for example, tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy- propionic acid tetrahydrofurfuryl ester, (meth) acrylic acid Tetrahydrofuran-3-yl ester and the like;

As an unsaturated compound having a furan structure, for example, 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-yl-hex-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethylester, 6- (2-furyl) -6-methyl-1-hepten-3-one Etc;

As an unsaturated compound having a tetrahydropyran structure, for example, (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1- En-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 having a pyran structure, for example, 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone, 4- (1,5-dioxa-6 -Oxo-7-octenyl) -6-methyl-2-pyrone and the like;

As an unsaturated compound which has a structure represented by said Formula (3), the compound etc. which are represented by each of following formula (4)-6 can be illustrated, respectively.

(In formulas 4 to 6, R ⁷ is independently a hydrogen atom or a methyl group, a is independently an integer of 2 to 10 in formulas 4 and 5, and a is an integer of 3 to 10 in formula 6).

Among these, tetrahydrofurfuryl (meth) acrylate, (meth) acrylic acid tetrahydrofuran-3-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, furfuryl ( Meth) acrylate, the compound represented by the said Formula (4), etc. are used preferably from a viewpoint of expanding development margin. These may be used independently and may be used in combination of 2 or more type.

The content of the repeating unit derived from the unsaturated compound (a3) in the copolymer (A) is preferably 3 to 50% by weight, more preferably 5 to 40% by weight. By setting it as content of this range, the developability of a composition can be improved more.

[A] The polymer is optionally different from the unsaturated compounds (a1), (a2) and (a3) in addition to the repeating units derived from the unsaturated compounds (a1), (a2) and (a3). The repeating unit derived from another olefin unsaturated compound (henceforth "unsaturated compound (a4)") may be contained. The unsaturated compound (a4) is not particularly limited as long as it can be copolymerized with the above-mentioned unsaturated compounds (a1), (a2) and (a3), but is, for example, an alkyl acrylate, a methacrylic acid alkyl ester or a cyclic alkyl ester of acrylic acid. Cyclic alkyl esters of methacrylic acid, acrylic aryl esters, methacrylic acid aryl esters, unsaturated dicarboxylic acid diesters, hydroxyalkyl acrylates, hydroxyalkyl methacrylates, bicyclounsaturated compounds, unsaturated dicarbonyls Mid derivatives, styrene and derivatives thereof, and other unsaturated compounds may be mentioned.

As said acrylic acid alkyl ester, For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, etc .;

As said methacrylic acid alkyl ester, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t Butyl methacrylate and the like;

Examples of the cyclic alkyl esters of acrylic acid include cyclohexyl acrylate, 2-methylcyclohexyl acrylate and tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate (hereinafter referred to as "dicyclopentanyl acrylate". 2-dicyclopentanyloxyethyl acrylate, isoboroyl acrylate and the like;

Examples of the cyclic alkyl ester of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate and tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate (hereinafter, " Dicyclopentanyl methacrylate "), 2-dicyclopentanyloxyethyl methacrylate, isoboroyl methacrylate, etc .;

As said acrylic acid aryl ester, For example, phenyl acrylate, benzyl acrylate;

As said methacrylic acid aryl ester, For example, phenyl methacrylate, benzyl methacrylate;

As said unsaturated dicarboxylic acid diester, For example, diethyl maleate, diethyl fumarate, diethyl itaconic acid;

As said hydroxyalkyl acrylate, for example, hydroxymethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate Latex, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethylglycoside and the like;

As said hydroxyalkyl methacrylate, For example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc .;

As said bicyclo unsaturated compound, it is bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethyl bicyclo [2.2.1] hept, for example. 2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-carboxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] Hept-2-ene, 5- (2-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [ 2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2 -Ene, 5,6-di (2-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6 -Diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2. 1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene , 5-cyclohexyloxy Carbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2.2. 1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like;

As said unsaturated dicarbonyl imide derivative, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimidyl-3- maleimide benzoate, N-succinimidyl, for example 4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like;

As said styrene and its derivatives, For example, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, m-vinyl toluene, p-vinyl toluene, p-methoxy styrene etc .;

Examples of the other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl- 1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4 acrylic acid Epoxybutyl, methacrylic acid 3,4-epoxybutyl, α-ethylacrylic acid 3,4-epoxybutyl, acrylic acid 6,7-epoxyheptyl, methacrylic acid 6,7-epoxyheptyl, α-ethyl acrylic acid 6,7 -Epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, and the like.

Among these unsaturated compounds (a4), t-butyl methacrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl methacrylate, bicyclo [2.2.1] hept-2-ene, N-phenylmaleimide, N -Cyclohexylmaleimide, styrene, p-methoxystyrene, 1,3-butadiene, glycidyl methacrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycy Cidyl ether and the like are preferable in view of copolymerization reactivity and solubility in an aqueous alkali solution of the obtained [A] copolymer.

The said unsaturated compound (a4) may be used independently and may use 2 or more types together.

The content of the structural unit derived from the unsaturated compound (a4) in the copolymer (A) is preferably 80% by weight or less, more preferably 10 to 80% by weight, particularly preferably 20 to 70% by weight. By setting it as content of this range, the storage stability of the composition obtained and the solubility to alkaline developing solution can be controlled to a more appropriate range.

As a preferable [A] copolymer in this invention, More specifically,

At least one unsaturated compound (a1) selected from the group consisting of acrylic acid, methacrylic acid and maleic anhydride,

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, With 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane and 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane At least one unsaturated compound (a2) selected from the group consisting of:

Tetrahydrofurfuryl (meth) acrylate, (meth) acrylic acid tetrahydrofuran-3-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, furfuryl (meth) At least one unsaturated compound (a3) selected from the group consisting of acrylates and compounds represented by formula (4),

t-butyl methacrylate, 2-methylcyclohexyl acrylate, dicyclopentanyl methacrylate, bicyclo [2.2.1] hept-2-ene, N-phenylmaleimide, N-cyclohexyl maleimide, styrene, selected from the group consisting of p-methoxy styrene, 1,3-butadiene, glycidyl methacrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether The copolymer with 1 or more types of unsaturated compounds (a4) which are mentioned can be illustrated.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of the copolymer (A) is preferably 1 × 10 ³ to 5 × 10 ⁵ , more preferably 3 × 10 ³ to 3 × 10 ⁵ , further preferably Preferably 5 × 10 ³ to 1 × 10 ⁵ .

The molecular weight distribution defined by the ratio (Mw / Mn) of the Mw of the [A] copolymer and the polystyrene reduced number average molecular weight (hereinafter referred to as "Mn") is preferably 5.0 or less, and more preferably 1.0 to 3.0. to be.

The radiation sensitive resin composition containing the [A] copolymer having Mw and Mw / Mn can form a pattern of a predetermined shape very easily without causing development residue or film reduction during development.

The copolymer (A) has at least one of a carboxyl group and a carboxylic anhydride group and an oxetane ring structure, and has suitable solubility in aqueous alkali solution, and can be easily cured by heating without using a special curing agent. . Moreover, the radiation sensitive resin composition containing the [A] copolymer can easily form a film of a predetermined pattern without causing development residue or film reduction during development.

[A] copolymer may be used independently and may use 2 or more types together.

Such copolymers [A] include, for example, unsaturated compounds (a1), unsaturated compounds (a2) and unsaturated compounds (a3), and optionally unsaturated compounds (a4) in the presence of a radical polymerization initiator in a suitable solvent. It can synthesize | combine by superposing | polymerizing.

Examples of the solvent used for the polymerization include alcohols, ethers, ethylene glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol ethers, propylene glycol ethers, propylene glycol alkyl ether acetates, propylene glycol alkyl ether propionates and aromatic hydrocarbons. , Ketones, esters and the like.

As said alcohol, For example, methanol, ethanol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol;

Ethers such as tetrahydrofuran;

As ethylene glycol ether, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc .;

As ethylene glycol alkyl ether acetate, For example, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol n-propyl ether acetate, ethylene glycol n-butyl ether acetate, etc .;

As diethylene glycol 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 propylene glycol ether, For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, etc .;

Examples of propylene glycol alkyl ether acetates include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate, and the like;

Examples of the propylene glycol alkyl ether propionate include propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol n-propyl ether propionate, propylene glycol n-butyl ether propionate, and the like;

As an aromatic hydrocarbon, For example, toluene, xylene, etc .;

Methyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like as the ketone;

As the ester, for example, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid n-propyl, hydroxyacetic acid n-butyl, methyl lactate, lactic acid Ethyl, lactic acid n-propyl, lactic acid n-butyl, 3-hydroxypropionic acid methyl, 3-hydroxypropionic acid ethyl, 3-hydroxypropionic acid n-propyl, 3-hydroxypropionic acid n-butyl, 2-hydroxy-2 Methyl methyl propionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoic acid, methyl methoxyacetic acid, methoxyacetic acid ethyl, methoxyacetic acid n-propyl, methoxyacetic acid n- Butyl, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxyacetic acid n-propyl, ethoxyacetic acid n-butyl, n-propoxyacetic acid methyl, n-propoxyacetic acid ethyl, n-propoxyacetic acid n-prop , n-propoxyacetic acid n-butyl, n-butoxyacetic acid methyl, n-butoxyacetic acid ethyl, n-butoxyacetic acid n-propyl, n-butoxyacetic acid n-butyl, 2-methoxypropionate, 2 Ethyl methoxypropionate, 2-methoxypropionic acid n-propyl, 2-methoxypropionic acid n-butyl, 2-ethoxypropionic acid methyl, 2-ethoxypropionic acid ethyl, 2-ethoxypropionic acid n-propyl, 2-e N-butyl oxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionic acid, n-butyl 2-n-propoxypropionate, 2-n- Methyl butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxy propionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid n-propyl, 3-methoxypropionic acid n-butyl, 3-ethoxypropionic acid methyl, 3-ethoxypropion Ethyl, 3-ethoxypropionic acid n-propyl, 3-ethoxypropionic acid n-butyl, 3-n-propoxypropionic acid methyl, 3-n-propoxypropionic acid ethyl, 3-n-propoxypropionic acid n-propyl, 3 -n-propoxypropionate n-butyl, 3-n-butoxypropionate methyl, 3-n-butoxypropionate ethyl, 3-n-butoxypropionic acid n-propyl, 3-n-butoxypropionic acid n-butyl, etc. Each can be mentioned.

Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol ether, propylene glycol ether, propylene glycol alkyl ether acetate and the like are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, and propylene Preference is given to glycol methylether acetate.

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

Moreover, as a radical polymerization initiator used for the said superposition | polymerization, for example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2,2 ' Azo compounds such as -azobis- (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, and 1,1'-bis- (t-butylperoxy) cyclohexane; Hydrogen peroxide and the like. When using a peroxide as a radical polymerization initiator, it can also be used with a reducing agent as a redox type initiator.

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

In addition, in the said superposition | polymerization, in order to adjust the molecular weight of a [A] copolymer, a molecular weight modifier can be used.

Specific examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; Xanthogens, such as dimethyl xanthogen sulfide and di-i-propyl xanthogen disulfide, tert-pinolene, (alpha) -methylstyrene dimer, etc. are mentioned.

These molecular weight modifiers can be used individually or in combination of 2 or more types.

[B] 1,2-quinonediazide compound

[B] 1,2-quinonediazide compound contained in the radiation sensitive resin composition of this invention is a 1,2-quinonediazide compound which generate | occur | produces an acid by irradiation, For example, 1,2-benzoquinone Diazide sulfonic acid ester, 1,2-naphthoquinone diazide sulfonic acid ester, 1,2-benzoquinone diazide sulfonic acid amide, 1,2-naphthoquinone diazide sulfonic acid amide, etc. are mentioned.

As said 1,2-naphthoquinone diazide sulfonic acid ester, For example, the 1, 2- naphthoquinone diazide sulfonic acid ester of trihydroxy benzophenone, and the 1, 2- naphthoquinone diazide of tetrahydroxy benzophenone Sulfonic acid ester, 1,2-naphthoquinone diazide sulfonic acid ester of pentahydroxybenzophenone, 1,2-naphthoquinone diazide sulfonic acid ester of hexahydroxy benzophenone, and other (polyhydroxyphenyl) alkanes 1 And 2-naphthoquinone diazide sulfonic acid ester. Moreover, as the specific example, it is a 1, 2- naphthoquinone diazide sulfonic-acid ester of trihydroxy benzophenone, for example, 2,3, 4- trihydroxy benzophenone-1, 2- naphthoquinone azide-4- Sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonedia Zide-6-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-7-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2- Naphthoquinone diazide-8-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone- 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,4,6-trihydrate Roxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,4,6- Li-hydroxy benzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester and the like;

As 1,2-naphthoquinone diazide sulfonic-acid ester of tetrahydroxy benzophenone, it is 2,2 ', 4,4'- tetrahydroxy benzophenone- 1,2- naphthoquinone diazide-4-, for example. Sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone- 1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,2' , 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonedia Zide-4-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzo Phenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide -7-sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone -1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3, 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide -7-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester,

2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4 ' -Methylbenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide- 6-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,2'-tetra Hydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2- Naphthoquinone diazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone diazide-5-sulfonic acid ester, 2,3 , 4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-meth To oxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid And 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinone diazide-8-sulfonic acid ester.

As the 1,2-naphthoquinone diazide sulfonic acid ester of the pentahydroxybenzophenone, for example, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinone diazide 4-sulfonic acid ester, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2', 6 '-Pentahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,2', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide -7-sulfonic acid ester, 2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinone diazide-8-sulfonic acid ester and the like;

As 1,2-naphthoquinone diazide sulfonic-acid ester of the said hexahydroxy benzophenone, it is 2,4,6,3 ', 4', 5'-hexahydroxy benzophenone-1,2-naphtho, for example. Quinonediazide-4-sulfonic acid ester, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6 , 3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,4,6,3 ', 4', 5'-hexahydroxybenzo Phenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-8- Sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,3 ', 4' , 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2- Naphthoquinonediazide-6-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2- Neoplasm? Diazide-7-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexa-hydroxy benzophenone-1, 2-naphthoquinonediazide-8-sulfonic acid ester and the like;

As 1,2-naphthoquinone diazide sulfonic-acid ester of the said other (polyhydroxyphenyl) alkane, it is bis (2, 4- dihydroxy phenyl) methane- 1, 2- naphthoquinone diazide-, for example. 4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2- Naphthoquinonediazide-6-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,4-dihydroxyphenyl Methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, bis (4-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (4-hydroxyphenyl Methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (4-hydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (4-hydroxyphenyl Methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (4 -Hydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, tris (4-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, tris (4 -Hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, tris (4-hydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, tris (4 -Hydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, tris (4-hydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester,

1,1,1-tris (4-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl) ethane-1,2 Naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-7-sulfonic acid ester, 1,1,1-tris (4-hydroxyphenyl) ethane-1,2-naphthoquinonediazide- 8-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane- 1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (2,3 , 4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide - 8-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3,4 -Trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonedia Zide-6-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,2-bis (2,3 , 4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-8-sulfonic acid ester,

1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2 , 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxy Phenyl) -3-phenylpropane-1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1 , 2-naphthoquinonediazide-7-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide- 8-sulfonic acid ester, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4 Sulfonic acid ester, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-5- Sulfonic acid ester, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] Sphenol-1,2-naphthoquinonediazide-6-sulfonic acid ester, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] Bisphenol-1,2-naphthoquinonediazide-7-sulfonic acid ester, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol -1,2-naphthoquinonediazide-8-sulfonic acid ester,

Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl ) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2- Naphthoquinone diazide-6-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinone diazide-7-sulfonic acid ester, bis ( 2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-8-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1, 1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'- Tetramethyl-1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinone Diazide-6-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1, 2-naphthoquinonediazide-7-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'- Hexanol-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide- 4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl- 7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,2,4-trimethyl-7,2', 4'-trihydroxyflavan -1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-8- Sulfonic acid esters and the like.

As said 1, 2- benzoquinone diazide sulfonic-acid ester, the compound which changed the 1, 2- naphthoquinone in said each 1, 2- naphthoquinone diazide sulfonic-acid ester to 1, 2- benzoquinone is mentioned. .

As said 1, 2- naphthoquinone diazide sulfonic-acid amide, the compound which replaced the sulfonic acid ester in each said 1, 2- naphthoquinone diazide sulfonic-acid ester with sulfonic acid amide is mentioned.

As said 1, 2- benzoquinone diazide sulfonic-acid amide, the 1, 2- naphthoquinone in said each 1, 2- naphthoquinone diazide sulfonic-acid ester is mentioned, and the sulfonic acid ester is sulfonic acid The compound which replaced with amide is mentioned.

Of these 1,2-quinonediazide compounds, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3 -Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester or bis (2,5-dimethyl-4-hydroxyphenyl) Preference is given to 2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid esters.

The 1,2-quinonediazide compounds may be used alone or in combination of two or more thereof.

The use ratio of the 1, 2- quinonediazide compound in the radiation sensitive resin composition of this invention becomes like this. Preferably it is 5-100 weight part, More preferably, it is 10-50 weight part with respect to 100 weight part of [A] copolymers. It is wealth. By setting it as the usage ratio of this range, the balance of pattern formation property, developability, and the heat resistance and solvent resistance of the interlayer insulation film and microlenses obtained are more favorable.

Other components

The radiation sensitive resin composition of this invention contains the above-mentioned copolymer [A] and [B] components as an essential component, and [C] a thermosensitive acid production compound and [D] one or more ethylene as needed. It may contain a polymeric compound which has a sex unsaturated double bond, [E] epoxy resin, [F] surfactant, or [G] adhesion | attachment adjuvant.

The [C] thermosensitive acid generating compound can be used to improve the heat resistance and hardness of the interlayer insulating film and microlens to be formed. As the specific example, onium salts, such as a sulfonium salt, a benzothiazonium salt, an ammonium salt, a phosphonium salt, are mentioned, for example.

[C] As the thermosensitive acid-producing compound, sulfonium salts and benzothiazonium salts are preferably used among them.

Specific examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts, and the like, and specific examples thereof include alkylacefonium salts, for example, 4-acetophenyldimethylsulfonium hexafluoro. Antimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsul Phonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate and the like;

As the benzylsulfonium salt, for example, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexa Fluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro- 4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, etc .;

Examples of dibenzylsulfonium salts include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium Dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3- Methyl-4-hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate and the like;

As the substituted benzylsulfonium salts, for example, p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p -Chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl- Hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Of these [C] thermosensitive acid-forming compounds, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethyl Sulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoro Antimonates are preferably used.

As these commercial items, Sunide SI-L85, SI-L110, SI-L145, SI-L150, SI-L160 (manufactured by Sanshin Kagaku Kogyo Co., Ltd.) and the like can be given.

The use ratio of the [C] thermosensitive acid generating compound is preferably 20 parts by weight or less, more preferably 0.01 to 20 parts by weight, still more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the [A] copolymer. to be. By setting it as the usage-amount of this range, the heat resistance and hardness of the interlayer insulation film and microlens which are formed can be improved more, without impairing the film formation property of a composition.

Examples of the polymerizable compound having one or more ethylenically unsaturated double bonds [D] (hereinafter also referred to as "[D] component") include monofunctional (meth) acrylate, bifunctional (meth) acrylate, or the like. Trifunctional or more than (meth) acrylate is mentioned preferably.

As said monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboroyl (meth) acrylate, 3-methoxybutyl (meth), for example Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, etc. are mentioned. As these commercial items, for example, Alonics M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), Kayarad TC-110S, TC-120S (above, Nippon Kayaku) Co., Ltd.), biscoat 158, 2311 (above, Osaka Kagaku Kogyo Co., Ltd. product), etc. are mentioned.

As said bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxy ethanol fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, etc. are mentioned. As these commercial items, for example, Alonics M-210, M-240, M-6200 (above, Toagosei Co., Ltd.), Kayarard HDDA, HX-220, R-604 (above, Nippon Kayaku ( Co., Ltd.), biscoat 260, 312, 335HP (above, Osaka Kagaku Kogyo Co., Ltd. product) etc. are mentioned.

As said trifunctional or more than (meth) acrylate, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. Examples of the commercially available product include Alonics M-309 and M-400. , M-405, M-450, M-7100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.), Kayarard TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA -120 (above, manufactured by Nippon Kayaku Co., Ltd.), biscot 295, 300, 360, GPT, 3PA, 400 (above, manufactured by Osaka Yuka Kagaku Kogyo Co., Ltd.), and the like.

Of these, trifunctional or higher (meth) acrylates are preferably used, and trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate are particularly preferred. desirable.

These monofunctional, bifunctional or trifunctional or more (meth) acrylates may be used alone, or may be used in combination of two or more thereof.

The use ratio of the component [D] is preferably 50 parts by weight or less, and more preferably 30 parts by weight or less based on 100 parts by weight of the [A] copolymer.

By containing [D] component in such a ratio, the heat resistance, surface hardness, etc. of the interlayer insulation film or microlens obtained can be improved more, without affecting the film formation property of a composition.

The above-mentioned [E] epoxy resin is not limited as long as there is no influence on compatibility, but preferably bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, cyclic aliphatic epoxy resin and glycidyl ester The epoxy resin, the glycidyl amine epoxy resin, the heterocyclic epoxy resin, and the resin which co-polymerized glycidyl methacrylate etc. are mentioned. Among these, bisphenol A epoxy resin, cresol novolak-type epoxy resin, glycidyl ester type epoxy resin, etc. are mentioned.

The use ratio of the epoxy resin (E) is preferably 30 parts by weight or less based on 100 parts by weight of the [A] copolymer. By containing [E] component in such a ratio, the heat resistance, surface hardness, etc. of the obtained interlayer insulation film or microlens can be further improved, without impairing the film formation property of composition, especially the uniformity of film thickness.

In addition, when an epoxy group containing monomer is used as a copolymerization monomer of [A] copolymer, although [A] copolymer can also be called "epoxy resin," [A] copolymer is alkali-insoluble in that it has alkali solubility. [E] It is different from an epoxy resin.

As said [F] surfactant, a fluorine-type surfactant, a silicone type surfactant, and a nonionic surfactant can be used preferably.

As a specific example of a fluorine-type surfactant, For example, 1,1,2,2- tetrafluorooctyl (1,1,2,2- tetrafluoro propyl) ether, 1,1,2,2- tetrafluoro octyl Hexyl ether, octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonic acid, 1, Sodium fluoroalkylbenzenesulfonate, in addition to 1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane and the like; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodide, fluoroalkylpolyoxyethylene ether, perfluoroalkylpolyoxyethanol; Perfluoroalkyl alkoxylates; Fluorine-based alkyl esters and the like.

As these commercial items, BM-1000, BM-1100 (above, BM Chemie Co., Ltd.), Megapack F142D, F172, F173, F183, F178, F191, F471 (above, Dai Nippon Ink Chemical Industries, Ltd.) Manufactured), Florad FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), Supron S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF301, 303, 352 Kasei Co., Ltd.) etc. are mentioned.

As said silicone type surfactant, For example, DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above, Toray Dow Corning What is marketed under brand names, such as a silicone company make, TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba Silicone Co., Ltd. make) Can be.

As said 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; Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate;

(Meth) acrylic-acid copolymer polyflow No. 57, 95 (made by Kyoesha Chemical Co., Ltd.), etc. can be used.

These surfactant can be used individually or in combination of 2 or more types.

These [F] surfactant is used preferably with 5 weight part or less, More preferably, it is 2 weight part or less with respect to 100 weight part of [A] copolymers.

As said [G] adhesion | attachment adjuvant, a functional silane coupling agent is used preferably, for example, The silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, is mentioned especially. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanatepropyl triethoxysilane, γ-glycidoxypropyl trimethoxy Silane, β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, and the like. Such [G] adhesion aid is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the [A] copolymer.

Sensitizing radiation property  Resin composition

The radiation sensitive resin composition of this invention is manufactured by mixing uniformly the above-mentioned [A] copolymer, the [B] 1,2-quinonediazide compound, and the other components which can be arbitrarily added above. The radiation-sensitive resin composition of the present invention is preferably dissolved in a suitable solvent and used in a solution state. For example, the radiation-sensitive resin composition in a solution state is prepared by mixing the [A] copolymer and the [B] 1,2-quinonediazide compound and other components optionally added in a predetermined ratio in a suitable solvent. can do.

As a solvent used for manufacture of the radiation sensitive resin composition of this invention, each component of the [A] copolymer, the [B] 1,2-quinonediazide compound, and the other components arbitrarily mix | blended is melt | dissolved uniformly, Those that do not react with the ingredients are used.

As such a solvent, the same thing as what was illustrated as a solvent which can be used at the time of superposition | polymerization for manufacturing the above-mentioned [A] copolymer is mentioned.

Among these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycol are preferably used in view of solubility of each component, reactivity with each component, and ease of film formation. Among these, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene Glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate and ethyl ethoxypropionate can be particularly preferably used.

Moreover, in order to raise the in-plane uniformity of a film thickness with the said solvent, you may use together a high boiling point solvent. As a high boiling point solvent which can be used together, it is N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpi, for example. Ralidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, male Acid diethyl, gamma -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

When using a high boiling point solvent together as a solvent of the radiation sensitive resin composition of this invention, the usage-amount can be 50 weight% or less with respect to solvent whole quantity, Preferably it is 40 weight% or less, More preferably, it is 30 weight% or less. . By setting it as the usage-amount in this range, the film thickness uniformity (in-plane uniformity) of a film can be improved more, without impairing the sensitivity and residual film rate of a composition.

When preparing the radiation sensitive resin composition of this invention as a solution state, components other than the solvent which occupy in a solution (namely, [A] copolymer and [B] 1,2-quinonediazide compound, and the other optionally added Although the ratio of the total amount of components) can be arbitrarily set according to the purpose of use, the value of a desired film thickness, etc., Preferably it is 5-80 weight%, More preferable solid content concentration changes with a film formation method. As solid content concentration at the time of employ | adopting a coating method for film formation, 15-35 weight% is preferable, and 50-70 weight% is preferable as solid content concentration when employing a dry film method for film formation.

The composition solution thus prepared may be used after being filtered using a Millipore filter having a pore size of about 0.2 to 0.5 μm or the like.

The radiation sensitive resin composition of this invention can be used especially suitably for formation of an interlayer insulation film and a microlens.

Method of forming interlayer insulating film and microlens

The method for forming an interlayer insulating film and the method for forming a microlens of the present invention include the following steps in the order described below.

(A) Process of forming the film of radiation sensitive resin composition on a board | substrate

(B) irradiating at least a portion of the coating with radiation

(C) Process of developing the film after exposure

(D) step of heating the film after development

Hereinafter, each of these steps will be described.

(A) Process of forming the film of radiation sensitive resin composition on a board | substrate

This process is a process of forming the film of a radiation sensitive resin composition by apply | coating or transferring the radiation sensitive resin composition of this invention to the board | substrate surface. When the radiation sensitive resin composition of this invention contains a solvent, a film can be formed by apply | coating or transferring a composition which is a solution phase to the surface of a board | substrate, and then prebaking and removing a solvent.

As a board | substrate which can be used, a glass substrate, a silicon wafer, the board | substrate which provided various metal films on these surfaces, etc. are mentioned, for example.

It does not specifically limit as a coating method, For example, the spraying method, the roll coating method, the rotary coating method (spin coating method), the slit die coating method, the bar coating method, the inkjet coating method, etc. can be employ | adopted, and especially a spin The coating method and the slit die coating method are preferable.

As a transfer method, the dry film method is mentioned, for example.

When the dry film method is employed when forming a film of the radiation sensitive resin composition on a substrate, the dry film is a sense comprising the radiation sensitive resin composition of the present invention on a base film, preferably a flexible base film. It is a thing formed by laminating | stacking a radiation layer (henceforth "a radiation sensitive dry film").

The radiation-sensitive dry film can be formed by laminating a radiation-sensitive layer by applying the radiation-sensitive resin composition of the present invention as a liquid composition, preferably on a base film and then drying.

As a base film of a radiation sensitive dry film, a synthetic resin film, such as a polyethylene terephthalate (PET) film, polyethylene, a polypropylene, polycarbonate, polyvinyl chloride, can be used, for example. The thickness of the base film is suitably in the range of 15 to 125 占 퐉.

Although it does not specifically limit as a coating method at the time of laminating | stacking a radiation sensitive layer on a base film, For example, the appropriate method, such as an applicator coating method, a bar coating method, a roll coating method, a curtain flow coating method, can be employ | adopted.

Although the conditions of the said prebaking differ according to the kind, usage ratio, etc. of each component, it can be made into about 30 second-15 minutes at 60-110 degreeC, for example.

As for the film thickness of the film formed, when forming an interlayer insulation film, about 3-6 micrometers is preferable, and when forming a microlens, for example, about 0.5-3 micrometers is preferable. In addition, the said film thickness should be understood as a value after solvent removal, when the radiation sensitive resin composition of this invention contains a solvent.

(B) A step of irradiating radiation (hereinafter referred to as "exposure") at least a part of the film

In this process, it exposes to at least one part of the formed film. When exposing only a part of the said film, it exposes normally through the photomask which has a predetermined pattern.

Examples of the radiation used for exposure include ultraviolet rays such as g-ray (wavelength 436 nm) and i-rays (365 nm), far-ultraviolet rays such as KrF excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams. Etc., and ultraviolet rays are preferable among these, and especially the radiation which contains g line | wire and / or i line | wire is preferable.

As an exposure amount, when forming an interlayer insulation film, for example, about 50-3,000 J / m <^2> , and when forming a microlens, about 50-5,000 J / m <^2> is preferable, for example.

(C) Process of developing the film after exposure

In this process, a predetermined pattern is formed by developing the film after exposure and removing an exposure part.

As a developing solution used for image development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine , Triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0 Alkali (basic compound) aqueous solutions such as] -7-undecene and 1,5-diazabicyclo [4,3,0] -5-nonene are preferred, but the film of the radiation-sensitive resin composition may be dissolved in some cases. Various organic solvents can also be used.

Moreover, an appropriate amount of water-soluble organic solvents and surfactants, such as methanol and ethanol, can also be added to the said aqueous alkali solution.

As a developing method, appropriate methods, such as a puddle method, the dipping method, the oscillation dipping method, the shower method, can be employ | adopted.

Although developing time changes with kinds, usage ratios, etc. of each component, it can be made into about 30 to 120 second, for example.

In addition, in the conventionally known radiation-sensitive resin composition, when the developing time exceeds about 20 to 25 seconds from the optimum time, since the peeling occurs in the formed pattern, it was necessary to strictly control the developing time, but the radiation-sensitive resin composition of the present invention In this case, even if the excess time from the optimum developing time is 30 seconds or more, good pattern formation is possible, which is very advantageous in terms of product yield and productivity.

(D) step of heating the film after development

In this step, the film on which the predetermined pattern is formed is preferably washed, for example, by running water, and more preferably, the radiation remaining such as a high-pressure mercury lamp is exposed to the entire surface (after exposure), thereby remaining in the coating film. After decomposing the 1,2-quinonediazide compound, the coating film is cured by heat treatment (post-baking) with a heating apparatus such as a hot plate or an oven. In addition, when forming a microlens, the formed pattern is melt-flowed by post-baking, and it is set as a predetermined shape.

The exposure amount in the post exposure is preferably about 2,000 to 5,000 J / m ² .

In addition, the heating temperature in post-baking is about 120-250 degreeC, for example. The heating time varies depending on the type of heating device, but may be, for example, about 5 to 30 minutes on a hot plate and, for example, about 30 to 90 minutes in an oven. At this time, the step baking method etc. which perform two or more heat processings can also be employ | adopted.

In this way, a patterned thin film corresponding to the target interlayer insulating film or microlens can be formed on the substrate surface.

Interlayer Insulator and Micro Lens

The interlayer insulating film and the microlens of the present invention are each preferably formed from the radiation-sensitive resin composition of the present invention as described above.

The interlayer insulating film of this invention can be used very favorably for electronic components, such as a TFT type liquid crystal display element, a magnetic head element, an integrated circuit element, and a solid-state image sensor.

In addition, the microlens of the present invention has a semiconvex lens shape having a good shape. The microlens of the present invention and the microlens array regularly arranged therewith can be very preferably used as an optical system material of an imaging optical system or an optical fiber connector of an on-chip color filter such as a facsimile, an electronic copier, a solid-state imaging device, and the like.

As described above, the radiation-sensitive resin composition of the present invention has excellent sensitivity and resolution, is excellent in storage stability as a composition solution, and has good development margins that can still form a good pattern shape even when the optimum development time is exceeded in the development process. In particular, it can be used very preferably as microlenses, such as an interlayer insulation film and a solid-state image sensor of various electronic components.

Further, according to the method for forming the interlayer insulating film and the method for forming the microlens of the present invention, even if the developing time exceeds the optimum developing time, a good pattern can be formed, and the interlayer insulating film and the microlens having the above excellent characteristics can be easily formed. .

The interlayer insulating film of the present invention has excellent solvent resistance, heat resistance, light transmittance, adhesiveness, and the like, and has a low dielectric constant.

In addition, the microlenses of the present invention have excellent solvent resistance, heat resistance, light transmittance, adhesiveness, and the like, and have a good melt shape.

<Examples>

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to a following example.

Synthesis of Copolymer

&Lt; Synthesis Example 1 &

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol methyl ether acetate were added. Then, 22 parts by weight of methacrylic acid, 28 parts by weight of dicyclopentanyl methacrylate, 40 parts by weight of 3- (methacryloyloxymethyl) -2-phenyloxetane, 10 parts by weight of tetrahydrofurfuryl methacrylate, and After adding 1.5 parts by weight of α-methylstyrene dimer, the solution was slowly stirred while replacing with nitrogen to raise the temperature of the solution to 70 ° C. and maintained at this temperature for 4 hours to polymerize (A solid content concentration of 33.8 weight). %) Was obtained.

Mw of the obtained [A] copolymer was 14,000 and Mw / Mn was 2.1. In addition, Mw and Mn are polystyrene conversion average molecular weights measured using GPC (gel permeation chromatography) (HLC-8020 by Tosoh Corporation). This [A] copolymer is called "copolymer (A-1)."

&Lt; Synthesis Example 2 &

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol methyl ether acetate were added. Subsequently, 5 parts by weight of styrene, 11 parts by weight of methacrylic acid, 45 parts by weight of 3- (methacryloyloxymethyl) -3-ethyloxetane, 5 parts by weight of styrene, 10 parts by weight of tetrahydrofurfuryl methacrylate, and After 1.5 parts by weight of α-methylstyrene dimer was added, the mixture was slowly stirred with nitrogen substitution to raise the temperature of the solution to 70 ° C., and maintained at this temperature for 4 hours to polymerize (A solid content concentration of 32.8 weight). %) Was obtained.

Mw of the obtained [A] copolymer was 22,000 and Mw / Mn was 2.1. This [A] copolymer is called "copolymer (A-2)."

&Lt; Synthesis Example 3 &

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 150 parts by weight of propylene glycol methyl ether acetate were added. Subsequently, 5 parts by weight of styrene, 25 parts by weight of methacrylic acid, 20 parts by weight of N-cyclohexylmaleimide, 35 parts by weight of 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, and Chemical Formula 4 15 parts by weight of the compound represented by (the average value of a in the formula is 2.2) and 1.5 parts by weight of α-methylstyrene dimer were added, and slowly stirring was started while replacing with nitrogen to raise the temperature of the solution to 70 ° C. The solution (solid content concentration 32.7 weight%) of the [A] copolymer was obtained by hold | maintaining and polymerizing for 4 hours.

Mw of the obtained [A] copolymer was 18,500 and Mw / Mn was 2.2. This [A] copolymer is called "copolymer (A-3)."

&Lt; Synthesis Example 4 &

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol methyl ether acetate were added. Then, 20 parts by weight of styrene, 10 parts by weight of methacrylic acid, 50 parts by weight of 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 20 parts by weight of tetrahydrofurfuryl methacrylate and α- After adding 2.0 parts by weight of methyl styrene dimer, stirring was started slowly while replacing with nitrogen to raise the temperature of the solution to 70 ° C., and the polymerization was carried out by maintaining the temperature for 5 hours (solid content concentration of 32.0 wt%). Got.

Mw of the obtained [A] copolymer was 16,500 and Mw / Mn was 1.7. This [A] copolymer is called "copolymer (A-4)."

<Comparative Synthesis Example 1>

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added. Subsequently, 23 parts by weight of methacrylic acid, 47 parts by weight of dicyclopentanyl methacrylate, 20 parts by weight of glycidyl methacrylate, and 2.0 parts by weight of α-methylstyrene dimer were added thereto, followed by slowly stirring with nitrogen substitution to start the solution. The temperature was raised to 70 ° C., and this solution was maintained for 5 hours to obtain a solution of a copolymer (solid content concentration of 32.8 wt%).

Mw of the obtained copolymer was 24,000 and Mw / Mn was 2.3. This copolymer is called "copolymer (a-1)".

&Lt; Comparative Synthesis Example 2 &

In a flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol methyl ether acetate were added. Subsequently, 22 parts by weight of methacrylic acid, 28 parts by weight of dicyclopentanyl methacrylate, 40 parts by weight of 3- (methacryloyloxymethyl) -2-phenyloxetane, 10 parts by weight of styrene and α-methylstyrene dimer 1.5 After adding a weight part, stirring was started slowly with nitrogen substitution, and the temperature of the solution was raised to 70 ° C, and the temperature was maintained for 4 hours to polymerize to obtain a solution (solid content concentration of 31.8 wt%) of the (A) copolymer.

Mw of the obtained copolymer was 18,000 and Mw / Mn was 2.01. This copolymer is called "copolymer (a-2)."

Sensitizing radiation property  Preparation and Evaluation of Resin Compositions

&Lt; Example 1 >

An amount corresponding to 100 parts by weight of the solution containing the copolymer (A-1) obtained in Synthesis Example 1 as the component [A] in terms of the copolymer (A-1), and 4,4'- as the component [B]. 30 parts by weight of [1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, [C] 1 part by weight of triphenylsulfonium trifluoromethanesulfonate as a component, and 5 parts by weight of γ-methacryloyloxypropyl trimethoxysilane as other components to give a solid content of 30% by weight of propylene glycol methyl ether acetate After dissolving in, it filtered by the Millipore filter of 0.2 micrometer of pore diameters, and the composition (S-1) was prepared.

Evaluation of Preservation Stability

A part of composition (S-1) prepared above was taken, it sealed in the glass screw tube, it heated in the oven of 40 degreeC for 1 week, and the change rate of the viscosity before and behind heating was measured. The results are shown in Table 1 below. Here, storage stability is favorable when a viscosity change rate is 0 to +5%.

Evaluation of developing margin

After applying the composition (S-1) on a plurality of silicon substrates respectively using a spinner, a film was formed by prebaking on a hot plate at 90 ° C. for 2 minutes. The intensity | strength in wavelength 365nm is 80 using Canon's PLA-501F exposure machine (ultra high pressure mercury lamp) through the mask which has a pattern of a line and space (10: 1) of 3.0 micrometers in the obtained film | membrane. After irradiating the ultraviolet-ray which is W / m <^2> for 40 second, it developed by the puddle method by changing the developing time for every board | substrate at 25 degreeC using the tetramethylammonium hydroxide aqueous solution of 0.4 weight% of concentration as a developing solution. Subsequently, flowing water was washed with ultrapure water for 1 minute and dried to form a pattern having a thickness of 3.0 mu m on the wafer. At this time, the minimum development time required for the line line width to be 3.0 µm is shown in Table 1 as the optimum development time. Moreover, when developing further from the optimal developing time, the time until the line-pattern of 3.0 micrometers was peeled off was measured, and it shows in Table 1 as a developing margin. When this value is 30 seconds or more, the development margin can be said to be good.

I. Evaluation as an interlayer insulating film

(1) evaluation of resolution

Formation of patterned thin film

After apply | coating composition (S-1) on a glass substrate using a spinner, it prebaked for 3 minutes on the 80 degreeC hotplate, and formed the film.

Subsequently, the obtained film was irradiated with the ultraviolet-ray whose intensity | strength is 100 W / m <^2> at wavelength 365nm for 15 second through the photomask of a predetermined pattern. Then, after developing for 1 minute at 25 degreeC with 0.5 weight% of tetramethylammonium hydroxide aqueous solution, the unnecessary part was removed by washing with pure water for 1 minute, and the pattern was formed.

Subsequently, after irradiating the formed pattern with the ultraviolet-ray whose intensity | strength is 100 W / m <^2> in wavelength 365nm for 30 second, the pattern-form thin film of 3.0 micrometers of film thicknesses was obtained by heating (post-baking) for 60 minutes in 220 degreeC oven. In addition, except having made the prebaking temperature into 90 degreeC or 100 degreeC, the same operation as the above was performed and the total three types of patterned thin films from which the prebaking temperature differs were obtained.

Resolution evaluation

"(Circle)" and the case where it was not resolved were evaluated as "x" for the case where the separation pattern (5 micrometer x 5 micrometer hole) resolved with respect to the obtained patterned thin film. The results are shown in Table 2 below.

(2) Evaluation of heat resistance dimensional stability

In "-formation of the patterned thin film" of said "(1) resolution evaluation" WHEREIN: The film thickness before and after baking for 60 minutes in the oven of 220 degreeC is measured about the pattern formed at the prebaking temperature of 80 degreeC. It was. The results are shown in Table 2. Here, when the rate of change of the film thickness is within ± 5%, it can be said that the heat-resistant dimensional stability is good.

(3) evaluation of transparency

After apply | coating composition (S-1) on a glass substrate using a spinner, it prebaked for 3 minutes on the 80 degreeC hotplate, and formed the film.

Next, the ultraviolet-ray whose intensity | strength is 100 W / m <^2> in wavelength 365nm was irradiated to the whole surface of the obtained film for 30 second. Subsequently, a film having a thickness of 3.0 µm was obtained by heating (post-baking) for 60 minutes in an oven at 220 ° C.

A glass substrate of the same kind as that used for the substrate on the reference side using a spectrophotometer (150-20 type double beam (manufactured by Hitachi Seisakusho Co., Ltd.)) for a light transmittance having a wavelength of 400 nm of the film obtained above. It measured and installed.The result is shown in Table 2. Here, when a transmittance | permeability is 90% or more, transparency can be said to be favorable.

(4) evaluation of heat discoloration resistance

After heating the board | substrate which has the film measured by said "(3) transparency evaluation" in 250 degreeC oven for 1 hour, the light transmittance of wavelength 400nm was measured similarly to "(3) transparency evaluation". The transmittance change rate before and after heating is shown in Table 2. Here, it can be said that heat discoloration resistance is favorable when the change rate of transmittance | permeability is less than 5%.

(5) Evaluation of adhesion

A film having a film thickness of 3.0 µm was obtained in the same manner as the front end portion of the above "(3) Evaluation of transparency". After placing the board | substrate which has this film | membrane in pressure kiln of temperature 120 degreeC, and humidity 100% for 4 hours, the board | substrate graduation peeling test was done according to JIS-K5400. Table 2 shows the number of remaining checkerboard ticks among the 100 checkerboard ticks at this time.

II. Evaluation as a microlens

(1) Evaluation of sensitivity

After the composition (S-1) was applied onto the plurality of silicon substrates using a spinner so that the film thickness after removal of the solvent was 2.5 μm, respectively, the substrate was prebaked for 3 minutes on a hot plate at 70 ° C. to form a plurality of substrates having a film. It was.

Subsequently, after exposing varying the exposure amount for every board | substrate through the mask which has a line-and-space pattern (10: 1) of 0.8 micrometers of line | wire widths in the obtained film, it is 25 degreeC by 2.38 weight% of tetramethylammonium hydroxide aqueous solution. The patterned thin film was obtained by developing for 1 minute at and washing with pure water for 1 minute.

The said several board | substrate was observed under the microscope, and the minimum exposure amount which can resolve the space line width (0.08 micrometer) was investigated. The results are shown in Table 3 below. When this value is 1,000 J / m <^2> or less, it can be said that a sensitivity is favorable.

(2) Evaluation of transparency

After apply | coating composition (S-1) on a glass substrate using a spinner, it prebaked for 3 minutes on the 70 degreeC hotplate, and formed the film.

Next, the ultraviolet-ray whose intensity | strength is 100 W / m <^2> in wavelength 365nm was irradiated to the whole surface of the obtained film for 30 second. Subsequently, the film | membrane of 2.5 micrometers in thickness was obtained by heating (postbaking) for 60 minutes in 160 degreeC oven.

The light transmittance of the wavelength of 400 nm of the film | membrane obtained above is measured using the spectrophotometer (150-20 type double beam (made by Hitachi Seisakusho Co., Ltd.), and installing the same kind of glass substrate as what was used for the board | substrate to the reference side. The result is shown in Table 3. Here, when the transmittance | permeability is 90% or more, it can be said that transparency is favorable.

(3) Evaluation of heat discoloration resistance

After heating the board | substrate which has the film measured by said "(2) transparency evaluation" in 250 degreeC oven for 1 hour, the light transmittance of wavelength 400nm was measured similarly to "(2) transparency evaluation". Table 3 shows the change in transmittance before and after heating. Here, it can be said that heat discoloration resistance is favorable when the change rate of transmittance | permeability is less than 5%.

(4) Evaluation of solvent resistance

The film | membrane of 2.5 micrometers of film thicknesses was obtained like the shear part of said "(2) transparency evaluation". The board | substrate which has this film was immersed in 50 degreeC isopropanol for 10 minutes, and the film thickness change rate before and behind immersion was measured. The results are shown in Table 3. Solvent resistance is favorable for this value being 0 to +5%.

(5) Evaluation of adhesion

Except having used the silicon substrate instead of the glass substrate, it carried out similarly to the front-end part of said "(2) transparency evaluation", and obtained the film of 2.5 micrometers in thickness. After placing the board | substrate which has this film | membrane in pressure kiln of temperature 120 degreeC, and humidity 100% for 4 hours, the board | substrate graduation peeling test was done according to JIS-K5400. Table 3 shows the number of remaining checkerboard ticks among the 100 checkerboard ticks at this time.

(6) Evaluation of microlens shape

The composition (S-1) was applied onto a plurality of silicon substrates using a spinner so as to have a film thickness of 2.5 μm after solvent removal, and then prebaked for 3 minutes on a 70 ° C. hot plate to form a substrate having a film.

Subsequently, the obtained film was exposed at an exposure amount of 3,000 J / m ² using a Nikon Corporation NSR1755i7A reduced projection exposure machine (NA = 0.50, lambda = 365 nm) through a pattern mask having a 4.0 μm dot 2.0 μm space pattern. Then, it developed by the puddle method at 25 degreeC with the aqueous solution of tetramethylammonium hydroxide of concentration 1.1weight%. Subsequently, it was washed with water and then dried to form a pattern on the wafer. Then, it exposed so that the cumulative irradiation amount might be 3,000 J / m <^2> by Canon's PLA-501F exposure machine (ultra high pressure mercury lamp). Thereafter, the plate was heated at 160 ° C. for 10 minutes and then heated at 230 ° C. for 10 minutes to melt-flow the pattern to form a microlens.

Table 3 shows the dimensions (diameter) and the cross-sectional shape of the bottom portion of the formed microlens (surface contacting the substrate). It can be said that it is favorable when the dimension of a microlens bottom part is more than 4.0 micrometers and less than 5.0 micrometers. Moreover, when this dimension becomes 5.0 micrometers or more, adjacent lenses will contact and it is unpreferable. In addition, the cross-sectional shape is good when it is a semi-convex lens shape like (a) in the schematic diagram shown in FIG. 1, and it is bad when it is almost trapezoid shape like (b).

<Examples 2 to 4, Comparative Example 1>

The compositions were prepared and evaluated in the same manner as in Example 1 except that the solutions containing the copolymers shown in Table 1 were used instead of the solutions containing the copolymer (A-1), respectively. The results are shown in Tables 1 to 3.

Comparative Example 2

4,4 '-[1- as an amount equivalent to 100 parts by weight of the solution containing the copolymer (a-2) obtained in Comparative Synthesis Example 2 in terms of copolymer (a-2). 30 parts by weight of {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, γ- as other components 5 parts by weight of methacryloyloxypropyl trimethoxysilane were mixed, dissolved in propylene glycol methyl ether acetate so that the solid content concentration was 30% by weight, and then filtered with a Millipore filter having a pore size of 0.5 µm to prepare a composition.

It evaluated like Example 1 except having used the said composition instead of composition (S-1). The evaluation results are shown in Tables 1-3. In Comparative Example 2, when the microlenses were formed, the adjacent lenses were in contact with each other, so that the cross-sectional shape of the microlenses could not be evaluated.

According to the present invention, a copolymer of a compound having a structure having an ether bond such as unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, oxetane compound and tetrahydrofuran structure and 1,2-quinonediazide compound The radiation sensitive resin composition which is excellent in the sensitivity, the resolution, storage stability, image development margin, etc. which are used for formation of a microlens and an interlayer insulation film can be provided.

Claims (8)

[A] (a1) at least one compound selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides, (a2) at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2), and (a3) Unsaturated compound having at least one structure selected from the group consisting of a tetrahydrofuran structure, a furan structure, a tetrahydropyran structure, a pyran structure and a structure represented by the following formula (3) in a molecule: &Lt; / RTI &gt; [B] 1,2-quinonediazide compound A radiation-sensitive resin composition comprising a. &Lt; Formula 1 >

(Wherein R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ independently of each other are a hydrogen atom) , A fluorine atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6. <Formula 2>

Wherein R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ And n is the same as defined in Formula 1). <Formula 3>

(In formula, R <^6> is a hydrogen atom or a methyl group, m is an integer of 2-10.) The olefinic unsaturated compound according to claim 1, wherein the copolymer (A) is different from the components (a1), (a2) and (a3), and (a1), (a2) and (a3). It is a copolymer of phosphorus (a4) component, The said (a4) component is acrylic acid alkyl ester, methacrylic acid alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid aryl ester, methacrylic acid aryl ester, unsaturated dicarboxylic acid diester, and hydroxy Alkyl acrylates, hydroxyalkyl methacrylates, bicyclo unsaturated compounds, unsaturated dicarbonylimide derivatives, styrene and derivatives thereof, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacryl Amide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl Glycidyl acrylate, Glycidyl α-butyl acrylate, 3,4-epoxy butyl acrylate, 3,4-epoxy butyl methacrylate, 3,4-epoxy butyl acrylate, 6,7- acrylic acid Epoxyheptyl, methacrylic acid 6,7-epoxyheptyl, α-ethylacrylic acid 6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether A radiation sensitive resin composition which is at least one compound selected from the group consisting of. The radiation sensitive resin composition according to claim 1 or 2, which is used for forming an interlayer insulating film. (A) a step of forming a coating film of the radiation sensitive resin composition according to claim 1 on a substrate, (B) irradiating at least a portion of said film with radiation, (C) developing the film after irradiation, and (D) step of heating the film after development The method of forming an interlayer insulating film comprising the above in the order described above. The interlayer insulation film formed from the radiation sensitive resin composition of Claim 1. The radiation sensitive resin composition according to claim 1 or 2, which is used for forming a microlens. (A) a step of forming a coating film of the radiation sensitive resin composition according to claim 1 on a substrate, (B) irradiating at least a portion of said film with radiation, (C) developing the film after irradiation, and (D) step of heating the film after development Method for forming a microlens, characterized in that it comprises in the order described above. The microlens formed from the radiation sensitive resin composition of Claim 1.

Images