KR20090013086A - Radiation-sensitive resin composition, interlayer insulation film and microlens, and process for producing them - Google Patents

Abstract

A radiation sensitive resin composition, and a method for preparing an interlayer insulating layer by using the composition are provided to improve solvent resistance, heat resistance and transmittance and to lower dielectric constant. A radiation sensitive resin composition comprises a polymer comprising at least one kind of group selected from a carboxyl group and a carboxylic anhydride group, at least one kind of group selected from an oxylanyl group and an oxetanyl group, and an n-valent group represented by the formula 1; and a 1,2-quinonediazide compound, wherein R^I is a methylene group, or a C2-C10 alkylene or alkylmethylene group; Y is a single bond, -CO-, -O-CO-, or -NHCO-; n is an integer of 2-10; X is a C2-C70 n-valent hydrocarbon group capable of having at least one ether bond, or X is a trivalent group represented by the formula 2 if n is 3; and R^II are independently a methylene group or a C2-C6 alkylene group.

Description

Radiation-sensitive resin composition, interlayer insulating film and microlens, and manufacturing method thereof {RADIATION-SENSITIVE RESIN COMPOSITION, INTERLAYER INSULATION FILM AND MICROLENS, AND PROCESS FOR PRODUCING THEM}

The present invention relates to a radiation-sensitive resin composition, an interlayer insulating film and a microlens, and a manufacturing method thereof.

In an electronic component such as a thin film transistor (hereinafter, referred to as a "TFT") type liquid crystal display element, a magnetic head element, an integrated circuit element, or a solid-state image sensor, an interlayer insulating film is generally provided to insulate between wirings arranged in layers. have. As the material for forming the interlayer insulating film, it is preferable that the number of steps for obtaining the required pattern shape and a sufficient flatness are preferable, so that the radiation-sensitive resin composition is widely used (Japanese Patent Laid-Open No. 2001-354822 and Japanese Patent). See publication 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 a liquid crystal alignment film thereon, so that the interlayer insulating film is subjected to a high temperature condition in the process of forming the transparent electrode film. Since it is exposed or exposed to the peeling liquid of the resist used for pattern formation of an electrode, sufficient tolerance to these is needed.

In recent years, in the TFT type liquid crystal display device, there are trends such as large screen, high brightness, high precision, high speed response, and thinning, and the composition for forming an interlayer insulating film used therein has high sensitivity, and has a low dielectric constant, Higher performance is required than in the prior art in terms of high transmittance.

On the other hand, a microlens having a lens diameter of about 3 to 100 μm or a microlens in which these microlenses are regularly arranged as 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 system material of an optical fiber connector Lens arrays are being used.

To form a microlens or microlens array, a resist pattern corresponding to the lens is formed and then melt-flowed by heat treatment and used as it is, or by dry etching using a melt-flowed lens pattern as a mask. The method of transferring a shape is known. The radiation sensitive resin composition is widely used for formation of these lens patterns (refer Unexamined-Japanese-Patent No. 6-18702 and Unexamined-Japanese-Patent No. 6-136239).

By the way, the element in which the microlens or the microlens array is formed as described above is then coated with a planarization film and an etching resist film to remove various insulating films on the bonding pads, which are wiring forming portions, and exposed and developed using a desired mask. To remove the etching resist of the bonding pad portion, and then to remove the planarization film and various insulating films by etching to expose the bonding pad portion. For this reason, solvent resistance and heat resistance are required for the microlens or the microlens array in the coating film forming step and the etching step of the planarization film and the etching resist.

The radiation sensitive resin composition used to form such a microlens is highly sensitive, and the microlens formed therefrom has a desired radius of curvature, and is required to have high heat resistance and high transmittance.

In the interlayer insulating film and the microlens obtained as described above, when the developing time at the time of forming them is excessively slightly larger than the optimum time, the developing solution penetrates easily between the pattern and the substrate, so that peeling occurs easily. It is necessary to control the time strictly, and there is a problem in terms of product yield.

As described above, in forming the interlayer insulating film and the microlens from the radiation-sensitive resin composition, the composition is required to have high sensitivity, and even when the developing time is excessively larger than the predetermined time in the developing step during the forming step, the pattern is separated. Good heat resistance, high solvent resistance, low dielectric constant, high transmittance, etc. are required for the interlayer insulating film formed therefrom without satisfactory adhesion, and in the case of forming a microlens, a good melt shape (desirable curvature) as a microlens is formed. Radius), high heat resistance, high solvent resistance and high transmittance are required. However, the radiation sensitive resin composition which satisfy | fills these requirements is not known conventionally.

<Start of invention>

This invention is made | formed based on the above circumstances, The objective is to provide the radiation sensitive resin composition which has a high radiation sensitivity and can easily form the patterned thin film excellent in heat resistance.

Another object of the present invention is to form an interlayer insulating film having high heat resistance, high solvent resistance, high transmittance and low dielectric constant when used for forming an interlayer insulating film, and high transmittance and good melt when used for forming a microlens. It is providing the radiation sensitive resin composition which can form the micro lens which has a shape.

Another object of the present invention is to provide a method of forming an interlayer insulating film and a microlens using the radiation-sensitive resin composition.

Still another object of the present invention is to provide an interlayer insulating film having various properties such as high heat resistance, high solvent resistance, low dielectric constant, high permeability, and a good melt shape, and at the same time, various kinds of high heat resistance, high solvent resistance, high transmittance, etc. It is to provide a microlens having characteristics.

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] A polymer having at least one group selected from the group consisting of a carboxyl group and a carboxylic anhydride group, at least one group selected from the group consisting of an oxylanyl group and an oxetanyl group, and an n-valent group represented by the following general formula (1) (Hereinafter referred to as "polymer [A]") and a radiation sensitive resin composition containing the [B] 1,2-quinonediazide compound.

(Wherein R ^I is a methylene group or an alkylene group or alkylmethylene group having 2 to 10 carbon atoms, and Y is a single bond, -CO-, -O-CO- ^* (wherein the bond with "*" is R). Bound to ^I ) or -NHCO- ^* (wherein the bond of "*" is bound to R ^I ), n is an integer from 2 to 10 and X can have one or more ether bonds An n-valent hydrocarbon group having 2 to 70 carbon atoms, or n is 3 and X is a trivalent group represented by the following Chemical Formula 2, wherein "+" represents a bond.)

(In formula, R <^II> is respectively independently a methylene group or a C2-C6 alkylene group, and each "*" shows a bond.)

The objects and advantages of the present invention, secondly

(1) process of forming the coating film of said radiation sensitive resin composition on a board | substrate,

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

(3) developing process, and

(4) heating process

Is achieved by a method for forming an interlayer insulating film or microlens, which comprises in the order described above.

The above object and advantages of the present invention,

It is achieved by an interlayer insulating film or microlens formed by the above method.

The radiation sensitive resin composition of the present invention has high radiation sensitivity and is excellent in development margin, and can easily form a patterned thin film (interlayer insulating film or microlens) having excellent heat resistance.

The interlayer insulating film of the present invention formed from the composition is excellent in solvent resistance and heat resistance, has a high transmittance, has a low dielectric constant, and can be suitably used as an interlayer insulating film of an electronic component.

In addition, the microlens of the present invention formed from the composition is excellent in solvent resistance and heat resistance, has a high transmittance and a good melt shape, and can be suitably used as a microlens of a solid-state imaging device.

Hereinafter, the radiation sensitive resin composition of this invention is explained in full detail.

Polymer [A]

Polymer [A]

At least one group selected from the group consisting of carboxyl groups and carboxylic acid anhydride groups,

At least one group selected from the group consisting of an oxylanyl group and an oxetanyl group, and

It is a polymer which has n-valent group represented by the said Formula (1).

As the alkylene group having 2 to 10 carbon atoms of R ^I in the general formula (1), an alkylene group having 2 to 6 carbon atoms is preferable, and a linear alkylene group having 2 to 6 carbon atoms or a group represented by the following general formula (3) is preferable. As the alkyl methylene group having 2 to 10 carbon atoms of R ^I , a group represented by the following general formula (4) is preferable.

(Wherein, R ^III is a methylene group or a straight chain alkylene group having 2 to 4 carbon atoms, and a bond with “*” is bonded to S)

As Y in the general formula (1), -O-CO- ^* (wherein the bond to which "*" is attached is bonded to R ^I ) is preferable.

As n in the said Formula (1), it is preferable that it is an integer of 2-8, It is more preferable that it is an integer of 2-6 or 8, It is more preferable that it is 2, 3, 4, 6 or 8.

In the above formula (1), when n is 2, for example, a linear or branched alkylene group having 2 to 10 carbon atoms, a divalent group represented by the following formula (5);

As X when n is 3, For example, the trivalent group represented by following formula (6);

As X when n is 4, 6, or 8, the 4, 6, or 8-valent group represented, for example by following General formula (7) is mentioned as a preferable thing, respectively.

(Wherein, R ^IV is a hydrogen atom or a methyl group, m1 is an integer of 1 to 20, and "*" each represents a bond)

(Wherein each "*" represents a bonding hand)

(In formula, m2 is an integer of 0-2, and it shows that "*" is a bond., Respectively.)

The content ratio of at least one group selected from the group consisting of a carboxyl group and a carboxylic anhydride group in the polymer [A] is preferably 0.1 to 10 mmol / g, more preferably 0.5 to 5 mmol / g. The content ratio of at least one group selected from the group consisting of an oxylanyl group and an oxetanyl group is preferably 0.1 to 10 mmol / g, more preferably 1 to 5 mmol / g. The content rate of the n-valent group represented by the said Formula (1) becomes like this. Preferably it is 0.005-1 mmol / g, More preferably, it is 0.01-0.5 mmol / g.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") of the polymer [A] is preferably 2 × 10 ³ to 1 × 10 ⁵ , and more preferably 5 × 10 ³ to 5 × 10 ⁴ . When Mw is less than 2x10 <^{3>, a} developing margin may become enough, the residual film rate etc. of a film obtained may fall, or the pattern shape, heat resistance, etc. of an interlayer insulation film or microlens obtained may fall. On the other hand, when Mw exceeds 1 * 10 < ⁵ >, a sensitivity may fall or a pattern shape may fall. The molecular weight distribution (hereinafter referred to as "Mw / Mn") of the polymer [A] defined as the value obtained by dividing Mw by Mn (number average molecular weight in terms of polystyrene) is preferably 5.0 or less, and more preferably 4.0 or less. to be. When Mw / Mn exceeds 5.0, the pattern shape of the interlayer insulation film or microlens obtained may fall. The radiation sensitive resin composition containing the polymer [A] as described above can easily form a predetermined pattern shape without developing residue when developing.

Polymer [A] can be obtained by any method as long as it is a polymer as described above, but for example

(a1) at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as "compound (a1)"), and

(a2) Unsaturated compounds having at least one group selected from the group consisting of an oxylanyl group and an oxetanyl group (hereinafter referred to as "compound (a2)")

It may be a polymer obtained by radical copolymerization of an unsaturated compound containing a compound in the presence of a compound represented by the following formula (8).

(Wherein, X, Y, R ^I and n are each X, Y, R ^I and n in formula (I) with the consent of the Im)

The compound (a1) is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides having radical polymerizability, for example, anhydrides of monocarboxylic acids, dicarboxylic acids and dicarboxylic acids. And mono [(meth) acryloyloxyalkyl] esters of polyhydric carboxylic acids, mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, polycyclic compounds having carboxyl groups, and anhydrides thereof. .

As these specific examples, As monocarboxylic acid, For example, acrylic acid, methacrylic acid, crotonic acid, etc .;

As the dicarboxylic acid, for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;

As anhydride of dicarboxylic acid, For example, anhydride of the compound illustrated as said dicarboxylic acid;

As mono [(meth) acryloyloxyalkyl] ester of polyhydric carboxylic acid, For example, monosuccinate mono [2- (meth) acryloyloxyethyl], mono phthalate [2- (meth) acryloyloxyethyl ] Etc:

As mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group in both terminal, For example, (omega) -carboxypolycaprolactone mono (meth) acrylate etc .;

As the polycyclic compound having a carboxyl group and anhydrides thereof, for example, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5 -Carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2 .1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like. Each can be mentioned.

Among these, anhydrides of monocarboxylic acid and dicarboxylic acid are preferably used, and acrylic acid, methacrylic acid and maleic anhydride are particularly preferably used in view of copolymerization reactivity, solubility in aqueous alkali solution and availability. These compounds (a1) are used individually or in combination.

The compound (a2) is an unsaturated compound having at least one group selected from the group consisting of an oxylanyl group and an oxetanyl group having radical polymerizability.

As an unsaturated compound which has an oxylanyl group, For example, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha)-n-propyl acrylate, the glycine (alpha)-n-butyl acrylate Cydyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, acrylic acid-3,4-epoxy Cyclohexyl, methacrylic acid-3,4-epoxycyclohexyl, acrylic acid-3,4-epoxycyclohexylmethyl, methacrylic acid-3,4-epoxycyclohexylmethyl, α-ethylacrylic acid-6,7-epoxyheptyl , o-vinylbenzyl-2,3-epoxypropyl ether, m-vinylbenzyl-2,3-epoxypropyl ether, p-vinylbenzyl-2,3-epoxypropyl ether and the like. Of these, methacrylic acid glycidyl, methacrylic acid-3,4-epoxycyclohexylmethyl, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl-2,3-epoxypropyl ether, m-vinyl Benzyl-2,3-epoxypropyl ether, p-vinylbenzyl-2,3-epoxypropyl ether, and the like are preferably used in view of copolymerization reactivity and heat resistance and surface hardness of the resulting interlayer insulating film or microlens.

As an unsaturated compound which has an oxetanyl group, it is 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-methyloxetane, 3- (acryloyloxymethyl), for example. -3-ethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acrylo Yloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluoro Oxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxy Ethyl) -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 Cetane, 3- (2-acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluorojade Cetane, 2- (acryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) -2-methyloxetane, 2- (acryloyloxymethyl) -3-ethyloxetane, 2- ( Acryloyloxymethyl) -2-trifluoromethyloxetane, 2- (acryloyloxymethyl) -2-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -2-phenyloxetane , 2- (acryloyloxymethyl) -2,2-difluorooxetane, 2- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 2- (acryloyloxy Methyl) -2,2,4,4-tetrafluorooxetane, 2- (2-acryloyloxyethyl) oxetane, 2- (2-acryloyloxyethyl) -2-ethyloxetane, 2 -(2-acryloyloxyethyl) -3-ethyloxetane, 2- (2-acryloyloxyethyl) -2-trifluoromethyloxetane, 2- (2-acryloyloxyethyl)- 2-pentafluoroethyl oxetane, 2- (2-acryloyl Oxyethyl) -2-phenyloxetane, 2- (2-acryloyloxyethyl) -2,2-difluorooxetane, 2- (2-acryloyloxyethyl) -2,2,4- Acrylic esters such as trifluorooxetane and 2- (2-acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane;

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-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-tolyluromethyloxetane, 3- ( 2-methacryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane, 3- (2-methac Loyloxyethyl) -2,2,4-trifluoro oxetane, 3- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, 2- (methacrylo) Yloxymethyl) oxetane, 2- (methacryloyloxymethyl) -2-methyloxetane, 2- (methacryloyloxymethyl) -3-ethyloxetane, 2- (methacryloyloxymethyl ) -2-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 2- (methacryloyloxymethyl) -2-phenyloxetane, 3- (Methacryloyloxymethyl) -2,2-difluorooxetane, 2- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 2- (methacryloyloxy Methyl) -2,2,4,4-tetrafluorooxetane, 2- (2-methacryloyloxyethyl) oxetane, 2- (2-methacryloyloxyethyl) -2-ethyloxetane , 2- (2-methacryloyloxyethyl) -3-ethyl oxetane, 2- (2-methacryloyloxyethyl) -2-tolyluromethyloxetane, 2- (2-methacryloyl Oxyethyl) -2-pentafluoroethyloxetane, 2- ( 2-methacryloyloxyethyl) -2-phenyloxetane, 2- (2-methacryloyloxyethyl) -2,2-difluorooxetane, 2- (2-methacryloyloxyethyl Methacrylic acid esters, such as) -2,2,4-trifluorooxetane and 2- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane; have. Among them, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- ( Methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane from the viewpoint of copolymerization reactivity It is preferably used.

These compounds (a2) are used individually or in combination.

Polymer [A] may be a copolymer of an unsaturated compound comprising only compound (a1) and compound (a2), or in addition to compound (a1) and compound (a2) (a3) compound (a1), compound (a2) The copolymer of the unsaturated compound which further contains other unsaturated compounds (henceforth "a compound (a3)") may be sufficient.

The compound (a3) is not particularly limited as long as it is an unsaturated compound having a radical polymerizability of the compound (a1) and the compound (a2) or less. As the compound (a3), for example, methacrylic acid alkyl ester, acrylic acid alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid ester having a hydroxyl group, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated dienes;

Unsaturated compounds having a phenolic hydroxyl group represented by the following formula (I);

Unsaturated compounds having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton or a skeleton represented by the following general formula (II); And

Other unsaturated compounds

Can be mentioned.

[Formula I]

(Wherein R ^I is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² to R ⁶ are the same or different, a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, B is a single bond,- COO- or -CONH-, m is an integer of 0 to 3, provided that at least one of R ² to R ⁶ is a hydroxyl group)

[Formula II]

(Wherein R ⁷ is a hydrogen atom or a methyl group)

As a preferable specific example of a compound (a3), it is methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate as methacrylic acid alkylester, for example. Latex, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate and the like:

As alkyl acrylate, For example, methyl acrylate, isopropyl acrylate, etc .;

As methacrylic acid cyclic alkylester, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, tricyclo [5.2. 1.0 ^2,6 ] decane-8- ^yloxyethyl methacrylate, isoboroyl methacrylate, and the like;

As methacrylic acid ester which has a hydroxyl group, For example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monometha Methacrylate, 2,3-dihydroxypropylmethacrylate, 2-methacryloxyethylglycoside, 4-hydroxyphenylmethacrylate, and the like:

As acrylic acid cyclic alkylester, For example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] Decan-8-yloxyethyl acrylate, isoboroyl acrylate and the like;

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

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

As unsaturated dicarboxylic acid diester, for example, diethyl maleate, diethyl fumarate, diethyl itaconate, etc .:

As the bicyclo unsaturated compound, for example, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [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-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohex Siloxycarbonylbicyclo [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, 5- (2'-hydroxyethyl) bicyclo [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- N, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicycle [2.2.1] hept-2-ene, and 5-hydroxy-5-methyl-bicyclo [2.2.1] hept-2-ene;

As the maleimide compound, for example, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide , N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide Propionate, N- (9-acridinyl) maleimide, and the like;

As an unsaturated aromatic compound, For example, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene etc .;

As the conjugated diene, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like;

As an unsaturated compound which has a phenol skeleton represented by the said Formula (I), For example, the compound etc. which are represented by each of following formula (I-1)-(I-5);

As unsaturated compounds containing a tetrahydrofuran skeleton, for example, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxy Tetrahydrofuran-2-one and the like;

As unsaturated compounds containing a furan skeleton, for example, 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3- En-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, (meth) acrylic acid 2-furan-2-yl-1-methyl-ethylester, 6- (2-furyl) -6-methyl-1-heptene- 3-ones and the like;

As unsaturated compounds containing a tetrahydropyran skeleton, for example (tetrahydropyran-2-yl) methyl (meth) acrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct -1-en-3-one, 2- (meth) acrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one and the like;

As unsaturated compounds containing a pyran skeleton, 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;

Examples of the unsaturated compound containing a skeleton represented by the above formula (II) include polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) mono (meth) acrylate, and the like. ;

As other unsaturated compounds, for example, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 4-acryloyl morpholine, 4-methacryloyl mor Pauline etc. are mentioned, respectively.

[Formula I-1]

Wherein n is an integer of 1 to 3, and the definitions of R ¹ , R ² , R ³ , R ⁴ , R ^5, and R ⁶ are the same as in formula (I).

[Formula I-2]

Wherein the definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as in the above formula (I).

[Formula I-3]

(Wherein n is an integer of 1 to 3, and the definitions of R ¹ , R ² , R ³ , R ⁴ , R ^5, and R ⁶ are the same as those of Formula I).

[Formula I-4]

Wherein the definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as in the above formula (I).

[Formula I-5]

Wherein the definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as in the above formula (I).

Among these, methacrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid cyclic alkyl esters, maleimide compounds, unsaturated aromatic compounds, conjugated dienes;

Phenolic hydroxyl group containing unsaturated compound represented by the said Formula (I);

An unsaturated compound having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton or a skeleton represented by the above formula (II) is preferably used, and in particular, styrene, t-butyl methacrylate, tricyclo [5.2.1.0 ^{2 , 6} ] decane-8-yl methacrylate, lauryl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexyl maleimide, tetrahydrofurfuryl ( Meth) acrylate, polyethyleneglycol mono (meth) acrylate having a repeating number of ethylene units of 2 to 10, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (Meth) acrylamide, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene, 1,3-butadiene, 4-acryloyl morpholine, 4-methacryloyl morpholine , 3- (meth) acryloyloxytetrahydrate Furan-2-one, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one or N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide is copolymerizable and It is especially preferable from a viewpoint of solubility to aqueous alkali solution.

These compounds (a3) are used individually or in combination.

The polymer [A] used in the present invention preferably has a structural unit derived from the compound (a1) based on the sum of the repeating units derived from the compound (a1), (a2) and (a3), preferably 5 to 40 weights. %, Especially preferably, it is 5 to 25 weight%. When this structural unit is less than 5 weight% of a copolymer, it becomes difficult to melt | dissolve in aqueous alkali solution at the time of a developing process, whereas the copolymer exceeding 40 weight% tends to become too high in aqueous alkali solution.

The polymer [A] used in the present invention preferably has a structural unit derived from the compound (a2) based on the sum of the repeating units derived from the compound (a1), (a2) and (a3), preferably 10 to 80 weights. %, Especially preferably, it contains 30 to 80 weight%. When this structural unit is less than 10 weight%, there exists a tendency for the heat resistance, surface hardness, and peeling liquid tolerance of the interlayer insulation film or microlens obtained to fall, and when the quantity of this structural unit exceeds 80 weight%, it is radiation sensitive. There exists a tendency for the storage stability of a resin composition to fall.

The polymer [A] used in the present invention preferably has a structural unit derived from the compound (a3) based on the sum of the repeating units derived from the compound (a1), (a2) and (a3), preferably 10 to 80 weights. %, Especially preferably, it contains 15 to 60 weight%.

As a preferable specific example of the polymer [A] used by this invention, it is a combination of unsaturated compound, for example methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / 4- Acryloyl morpholine / glycidyl methacrylate / styrene, methacrylic acid / glycidyl methacrylate / N-cyclohexyl maleimide / (3-ethyl oxetan-3-yl) methacrylate / alpha- Methyl-p-hydroxystyrene, methacrylic acid / methacrylate glycidyl / N-phenylmaleimide / tetrahydrofurfuryl methacrylate / vinylbenzyl 2,3-epoxypropyl ether, styrene / methacrylic acid / meta Glycylate Glycidyl / N- (4-hydroxyphenyl) methacrylamide / 1,3-butadiene, styrene / methacrylic acid / methacrylic acid glycidyl / (3-ethyloxetan-3-yl) meta Acrylate / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, methacrylic acid / methacrylate glycidyl / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacryl Rate / N-hour Lohexylmaleimide / n-lauryl methacrylate / α-methyl-p-hydroxystyrene, methacrylic acid / methacrylate glycidyl / styrene / 2-methylcyclohexylacrylate / 1- (tetrahydropyran -2-oxy) -butyl-3-en-2-one / 4-hydroxybenzyl methacrylate, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate / methacryl And acid glycidyl / 2-methylcyclohexyl acrylate / N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide.

The polymer [A] is, for example, a mixture containing each of the unsaturated compounds as described above in the presence of a compound represented by the formula (hereinafter referred to as "a polyvalent thiol compound"), preferably in a suitable solvent, It can synthesize | combine by radical polymerization in presence of a polymerization initiator.

The said polyvalent thiol compound is a component which functions as a chain transfer agent at the time of the synthesis of polymer [A].

As said polyhydric thiol compound, the esterified product of a mercaptocarboxylic acid and a polyhydric alcohol, etc. can be used, for example.

As said mercaptocarboxylic acid, For example, thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, 3-mercaptopentanoic acid, etc .;

As a polyhydric alcohol, for example, ethylene glycol, tetraethylene glycol, butanediol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,3,5-tris (2-hydroxyethyl) sia Nurate, sorbitol, etc. are mentioned, respectively.

As a specific example of the preferable polyhydric thiol compound used by this invention, for example, trimethylol propane tris (3-mercapto propionate), pentaerythritol tetrakis (3-mercapto propionate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycorate), 1,4-bis (3-mercaptobutyryloxy ) Butane, pentaerythritol tetrakis (3-mercaptobutylate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H , 3H, 5H) -trione and the like.

The said polyhydric thiol compound can be used individually or in mixture of 2 or more types.

The use ratio of the polyvalent thiol compound in synthesizing the polymer [A] is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, particularly preferably 100 parts by weight of the total unsaturated compound. Preferably from 1.5 to 10 parts by weight. When the use ratio of a polyvalent thiol compound is less than 0.5 weight part, adjustment of sufficient molecular weight may not be able to be performed. On the other hand, when it exceeds 30 weight part, it may become difficult to obtain a high polymerization conversion easily.

As a polymerization initiator used for manufacture of a polymer [A], what is generally known as a radical polymerization initiator can be used. For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2,2'- azobis- (4-methoxy-2, Azo compounds such as 4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide. When using a peroxide as a radical polymerization initiator, it can also be set as a redox type initiator by using a peroxide simultaneously with a reducing agent.

The use ratio of the polymerization initiator is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total unsaturated compound.

As a solvent used for manufacture of the polymer [A], for example, alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether pro Cypionate, aromatic hydrocarbon, ketone, ester, etc. are mentioned.

As these specific examples, as alcohols, for example, methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like:

Tetrahydrofuran and the like as ether:

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

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

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

As the propylene glycol alkyl ether propionate, for example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate and the like:

As propylene glycol alkyl ether acetate, For example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .:

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

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

Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate and hydroxyacetic acid. Methyl, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate, 3-hydroxypropionic acid propyl, 3-hydroxypropionic acid Butyl, 2-hydroxy-3-methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid propyl, butyl acetate, ethoxyacetic acid, ethyl ethoxyacetate, ethoxyacetic acid propyl Butyl oxyacetate, methyl propoxy acetate, ethyl propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate Ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate Ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, 3-methoxy methyl propionate, 3-methoxy ethylpropionate, 3-methoxy propylpropionate, 3-methoxy butyl propionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3-ethoxy propylpropionate, 3 Butyl ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, 3-butoxypropionic acid Butyl, can be given a 3-butoxy-propionic acid propyl, 3-butoxy-propionic acid butyl ester, etc., respectively.

Among these, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether or propylene glycol alkyl ether acetate is preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, and propylene glycol Ethyl ether, propylene glycol methyl ether acetate or methyl 3-methoxypropionate is preferred.

The polymerization temperature is preferably 0 to 150 ° C, more preferably 50 to 120 ° C, and the polymerization time is preferably 10 minutes to 20 hours, more preferably 30 minutes to 6 hours.

As for the polymerization reaction of the unsaturated compound containing the said compound (a1), a compound (a2), and preferably a compound (a3), it is preferable to make the polymerization conversion ratio into 90 weight% or more, and to set it as 93 weight% or more. More preferably, it is still more preferable to set it as 95 weight% or more. Polymerization conversion rate here means the ratio with respect to the total weight of the compound (a1), the compound (a2), and the compound (a3) which were provided for the polymerization reaction of the weight of the polymer [A] obtained by the polymerization reaction, and a polymerization initiator and a chain transfer agent. . The solution containing the polymer [A] obtained by the polymerization reaction by setting the polymerization conversion ratio in the above-described range reduces the film thickness due to heating at the time of forming the coating film even when the solution containing the polymer [A] is used for production of the radiation-sensitive resin composition without purification. It can be made to a minimum, and since the radiation sensitivity of the radiation sensitive resin composition and the heat resistance of the obtained interlayer insulation film or microlens are not impaired, it is preferable.

By carrying out the polymerization reaction of the compound (a1) and the compound (a2) and preferably the unsaturated compound containing the compound (a3) in the presence of a polyvalent thiol compound as described above, it is possible to easily realize the above preferred polymerization conversion rate. It becomes possible. The above excellent effects of the polyvalent thiol compound are the effects first discovered by the inventors of the present invention and the like.

[B] component

[B] component used in this invention is a 1, 2- quinonediazide compound which has a function which produces | generates a carboxylic acid by irradiation of a radiation, and a phenolic compound or an alcoholic compound (henceforth "mother nucleus"), And condensates of 1,2-naphthoquinonediazidesulfonic acid halides can be used.

Examples of the mother core include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother cores.

As these specific examples, it is trihydroxy benzophenone, For example, 2,3,4- trihydroxy benzophenone, 2,4,6- trihydroxy benzophenone etc .;

As tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxy Benzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone and the like;

As pentahydroxy benzophenone, For example, 2,3,4,2 ', 6'- pentahydroxy benzophenone etc .;

As hexahydroxybenzophenone, for example, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxy Benzophenone and the like;

As (polyhydroxyphenyl) alkanes, for example, bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, 1,1,1 -Tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3 -Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] Ethylidene] bisphenol, 4,4 ', 4 "-ethylidedinetrisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3', 3'- Tetramethyl-1,1'-spirobiindene-5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavor Rebound;

As other parent nuclei, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5- Isopropyl-4-hydroxy-2-methyl) phenyl} methyl], 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl ) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene is mentioned.

1,2-naphthoquinone diazide sulfonic acid amide in which the ester bond of the parent nucleus exemplified above is changed to an amide bond, for example, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide 4-sulfonic acid amide and the like are also preferably used.

Among these mother cores, 2,3,4,4'-tetrahydroxybenzophenone, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene ] Bisphenol, 4,4 ', 4 "-ethylidine trisphenol is preferable.

As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable, and specific examples thereof include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1, 2-naphthoquinone diazide-5-sulfonic acid chloride is mentioned. Among them, it is preferable to use 1,2-naphthoquinone diazide-5-sulfonic acid chloride.

In the condensation reaction, 1,2-naphthoquinone diazide sulfonic acid halide corresponding to 30 to 85 mol%, more preferably 50 to 70 mol% of moles of OH groups in the phenolic compound or alcoholic compound is preferably used. It is available.

The condensation reaction can be carried out by a known method.

These [B] components can be used individually or in combination of 2 or more types.

The use ratio of the component [B] is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight based on 100 parts by weight of the polymer [A]. When the ratio of the component (B) is less than 5 parts by weight, the difference in solubility between the irradiated portion and the unirradiated portion of the alkaline aqueous solution serving as the developing solution is small, and patterning may be difficult, resulting in an interlayer insulating film or microlens obtained May have insufficient heat resistance and solvent resistance. On the other hand, when the ratio of component [B] exceeds 100 weight part, the solubility with respect to the said aqueous alkali solution in a radiation part may become inadequate, and it may become difficult to develop.

Other ingredients

The radiation-sensitive resin composition of the present invention contains the above-described polymers [A] and [B] as essential components, but if necessary, [C] a thermosensitive acid-producing compound, [D] at least one ethylenically unsaturated double It may further contain a polymeric compound which has a bond, epoxy resins other than [E] polymer [A], [F] surfactant, [G] adhesion | attachment adjuvant, etc. However, the radiation sensitive resin composition of this invention subtracts the solution containing the polymer [A] obtained by the polymerization reaction of the unsaturated compound containing a compound (a1) and a compound (a2), and preferably a compound (a3). Compounds (a1), compounds (a2) and compounds (a3) other than those remaining in the above solution as polymers (A) remaining in the solution as unreacted unsaturated compounds when provided for the preparation of the radioactive resin composition. It is preferable not to contain 1 or more types of.

The [C] thermosensitive acid generating compound can be used to further improve the heat resistance and hardness of the resulting interlayer insulating film or microlens. Specific examples thereof include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts and phosphonium salts.

Specific examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts, and the like.

As these specific examples, as alkylsulfonium salts, for example, 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxy Carbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, Dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate and the like;

As the benzylsulfonium salt, for example, benzyl-4-hydroxyphenylmethylsulfonium hexafluoro antimonate, 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 .;

As the dibenzylsulfonium salt, for example, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium Hexafluoroantimonate, 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 salt, 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-4- Hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Specific examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-meth Benzyl, such as oxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate A benzothiazonium salt is mentioned.

Among them, sulfonium salts and benzothiazonium salts are preferably used, and 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4 -Acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzyl Benzothiazolium hexafluoroantimonate is preferably used.

As these commercial items, Sunaid 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 component [C] is preferably 20 parts by weight or less, and more preferably 5 parts by weight or less based on 100 parts by weight of the polymer [A]. When this usage-amount exceeds 20 weight part, precipitates may precipitate in a coating film formation process, and it may interfere with coating film formation.

As a polymeric compound which has one or more ethylenically unsaturated double bond which is the said [D] component, For example, monofunctional (meth) acrylate, bifunctional (meth) acrylate, or trifunctional or more (meth) acrylate is used. Preferred is mentioned.

As said monofunctional (meth) acrylate, 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isoboroyl (meth) acrylate, 3-methoxybutyl (meth ) Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, etc. are mentioned. As these commercial items, for example, Aronix M-101, copper M-111, copper M-114 (above, Toagosei Co., Ltd.), KAYARAD TC-110S, copper TC-120S (above, Nippon Kayaku ( Co., Ltd.), Biscot 158, East 2311 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.), 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, bisphenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene diacrylate, and the like. As these commercial items, for example, Aronix M-210, East M-240, East M-6200 (above, Toagosei Co., Ltd.), KAYARAD HDDA, East HX-220, East R-604 (above, Nippon) Manufactured by Kayaku Co., Ltd., Biscot 260, East 312, East 335HP (above, Osaka Yuki Kagaku Kogyo Co., Ltd.), etc. are mentioned.

As said trifunctional or more than (meth) acrylate, a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a tri ((meth) acryloyloxyethyl) phosphate, a pentaeryte, for example Lithol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned, As a commercial item, it is Aronix M-309, copper, for example. M-400, East M-405, East M-450, East M-7100, East M-8030, East M-8060 (above, manufactured by Toa Kosei Co., Ltd.), KAYARAD TMPTA, East DPHA, East DPCA-20, East DPCA-30, East DPCA-60, East DPCA-120 (above, Nippon Kayaku Co., Ltd.), Biscot 295, East 300, East 360, East GPT, East 3PA, East 400 (Over, Yuki Osaka Kagaku Kogyo Co., Ltd.) etc. are mentioned.

Among these, trifunctional or more than (meth) acrylate is preferably used, and trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are particularly preferred. Particularly preferred.

These monofunctional, bifunctional or trifunctional or more (meth) acrylates are used alone or in combination. 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 polymer [A]. The radiation sensitive resin composition of this invention can improve the heat resistance, surface hardness, etc. of the interlayer insulation film or microlens obtained by containing a [D] component in the above-mentioned ratio. When this use ratio exceeds 50 weight part, film roughness may generate | occur | produce in the process of forming the coating film of a radiation sensitive resin composition on a board | substrate.

The epoxy resins other than the polymer [A] which is the above-mentioned [E] component are not limited so long as they do not affect compatibility. Preferably, bisphenol-A epoxy resin, phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, heterocyclic epoxy resin, glyc The resin etc. which co-polymerized the cyl methacrylate are mentioned. Among these, bisphenol-A epoxy resin, cresol novolak-type epoxy resin, glycidyl ester-type epoxy resin, etc. are especially preferable.

The use ratio of the component [E] is preferably 30 parts by weight or less based on 100 parts by weight of the polymer [A]. The radiation sensitive resin composition of this invention can further improve the heat resistance, surface hardness, etc. of the interlayer insulation film obtained by containing [E] component in such a ratio. When this ratio exceeds 30 weight part, when forming the coating film of a radiation sensitive resin composition on a board | substrate, the film thickness uniformity of a coating film may become inadequate.

In addition, although polymer [A] can also be called "epoxy resin," [A] component differs from [E] component in that it has alkali solubility. [E] component is alkali-insoluble.

Surfactant which is the said [F] component can be used in order to improve the coatability of the radiation sensitive resin composition of this invention further. As the [F] surfactant that can be used here, a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant can be preferably used.

Specific examples of the fluorine-based surfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether and 1,1,2,2-tetrafluorooctylhexyl ether , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1 , 1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1, Sodium fluoroalkylbenzenesulfonate, in addition to 2,2,3,3,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane and the like; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodido, fluoroalkylpolyoxyethylene ether, perfluoroalkylpolyoxyethanol; Perfluoro alkyl alkoxylate: A fluorine-type alkyl ester etc. are mentioned. As these commercial items, BM-1000, BM-1100 (above, manufactured by BM Chemisa), Megapack F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471 (or more, DIC ( Co., Ltd.), fluoride FC-170C, FC-171, FC-430, FC-431 (above, Sumitomo 3M Co., Ltd.), Suplon S-112, S-113, S-131, East S-141, East S-145, East S-382, East SC-101, East SC-1 02, East SC-103, East SC-104, East SC-105, East SC-106 (Asahi Glass Ltd.), F-top EF301, copper 303, copper 352 (made by Shin-Akita 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 Silicone (Manufactured by) Ltd., TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials Japan, Ltd.) Can be mentioned.

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 (produced by Kyoeisha 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 with respect to 100 weight part of polymers [A], Preferably it is 5 weight part or less, More preferably, it is used in 0.01-2 weight part. When the usage-amount of [F] surfactant exceeds 5 weight part, when a coating film is formed on a board | substrate, the film roughness of a coating film may arise easily.

The adhesion aid which is the above-mentioned [G] component can be used for the radiation sensitive resin composition of this invention in order to improve the adhesiveness of the interlayer insulation film or microlens obtained with a base body further. As such [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. Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxy Silane, (beta)-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned. Such [G] adhesion aid is preferably used in an amount of 20 parts by weight or less, more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the polymer [A]. [G] When the amount of the adhesive aid exceeds 20 parts by weight, development residues are likely to occur in the development step.

Radiation  Resin composition

The radiation sensitive resin composition of this invention is manufactured by uniformly mixing the above-mentioned polymer [A] and [B] components, and the other components added arbitrarily as mentioned 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 of a solution state can be manufactured by mixing a polymer [A] and a [B] component and the other component added arbitrarily at a predetermined ratio.

As a solvent used for manufacture of the radiation sensitive resin composition of this invention, it is a thing which melt | dissolves each component of the polymer [A] and [B] component, and the other component mix | blended arbitrarily uniformly, and does not react with each component. Is used.

As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture the polymer [A] mentioned above 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, ease of coating film formation, and the like. Among them, 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, di Ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxy propionate, and ethoxy propionate can be used especially preferably.

Moreover, in order to improve the in-plane uniformity of a film thickness simultaneously with the said solvent, you may use a high boiling point solvent together. As a high boiling point solvent which can be used together, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methyl, for example Pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, Diethyl maleate, gamma -butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Among 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 use ratio is with respect to whole quantity of a solvent, Preferably it is 50 weight% or less, More preferably, it is 40 weight% or less, More preferably, 30 It can be made into the weight% or less. When the use ratio of high boiling point solvent exceeds this value, the film thickness uniformity, sensitivity, and residual film ratio of a coating film may be impaired.

When manufacturing the radiation sensitive resin composition of this invention as a solution state, the ratio of components other than the solvent which occupies in a solution (namely, the total amount of a polymer [A] and a [B] component and the other components arbitrarily added) (hereinafter, This value may be arbitrarily set according to the purpose of use, the value of the desired film thickness, and the like, but is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, still more preferably 15 To 35% by weight.

The composition solution thus prepared may be used for use after being filtered using a Millipore filter having a pore size of about 0.2 μm.

Interlayer insulating film, microlens formation

Next, the method of forming the interlayer insulation film and microlens of this invention using the radiation sensitive resin composition of this invention is demonstrated. The method for forming an interlayer insulating film or microlens of the present invention includes the following steps in the order described below.

(1) process of forming the coating film of the radiation sensitive resin composition of this invention on a board | substrate,

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

(3) developing process, and

(4) heating step.

(1) of the present invention Radiation  The coating film of the resin composition On a substrate  Forming process

In the process of said (1), the composition solution of this invention is apply | coated to the surface of a board | substrate, Preferably a solvent is removed by prebaking, and the coating film of a radiation sensitive resin composition is formed.

As a kind of substrate which can be used, a glass substrate, a silicon substrate, and the board | substrate with which various metal was formed in these surfaces are mentioned, for example.

It does not specifically limit as a coating method of a composition solution, For example, the appropriate method, such as the spraying method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, the inkjet method, can be employ | adopted, In particular, the spin coating method and the slit die coating method are preferable. The conditions for prebaking also vary depending on the type of each component, the use ratio, and the like. For example, it can be made into about 30 to 15 minutes at 60-110 degreeC.

As a film thickness of the coating film formed, it is a value after prebaking, for example, when forming an interlayer insulation film, for example, 3-6 micrometers, and forming a microlens, for example, 0.5-3 micrometers is preferable.

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

At the process of said (2), radiation is irradiated to at least one part of the coating film formed as mentioned above. In order to irradiate a part of coating film with radiation, it may be, for example, by a method of irradiating radiation through a mask having a desired pattern.

Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.

Examples of the ultraviolet rays include g-rays (wavelength 436 nm) and i-rays (wavelength 365 nm). As far ultraviolet rays, KrF excimer laser etc. are mentioned, for example. As X-ray, a synchrotron radiation etc. are mentioned, for example. As a charged particle beam, an electron beam etc. are mentioned, for example.

Among these, ultraviolet rays are preferable, and among these, radiation including g-rays and / or i-rays is particularly preferable.

As an exposure amount, it is preferable to set it as 50-1,500 J / m <2> when forming an interlayer insulation film, and 50-2,000 J / m <2> when forming a microlens.

(3) developing process

In the step (3), a patterned coating film (patterned thin film) is obtained by developing the coating film irradiated with radiation as described above using a developing solution to remove the irradiation portion of the radiation.

As a developing solution used for image development processing, 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 Aqueous solutions of alkali (basic compounds) such as] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonane can be used. The pH of the aqueous solution of alkali is preferably 10 to 16, particularly preferably 11 to 15. The aqueous solution which added water-soluble organic solvents, such as methanol and ethanol, and surfactant in an appropriate amount to the aqueous solution of said alkali, or various organic solvents which can melt | dissolve the composition of this invention can also be used as a developing solution.

As the developing method, for example, a suitable method such as a puddle method, a dipping method, a rocking dipping method or a shower method can be used. Although the developing time at this time changes with the composition of the radiation sensitive resin composition of this invention, the composition of the developing solution, and the image development method employ | adopted, it can be set as 30 to 120 second, for example.

(4) heating process

After the (3) developing step carried out as described above, the obtained patterned thin film is preferably rinsed by, for example, running water washing, and preferably irradiated with the entire surface with radiation by a high pressure mercury lamp or the like (after Exposure) to decompose the 1,2-quinonediazite compound remaining in the thin film, and then heat-process (post-baking) the thin film with a suitable heating apparatus such as a hot plate or an oven to obtain the thin film. Curing treatment is performed. The exposure amount in the said post exposure process becomes like this. Preferably it is about 2,000-5,000 J / m <2>. The post-baking temperature in hardening process is 120-250 degreeC, for example. Although post-baking time changes with kinds of a heating apparatus, it can be set as 5 to 30 minutes, for example, when performing a post-baking process on a hot plate, and 30 to 90 minutes when performing a post-baking process in an oven. At this time, the step baking method etc. which perform two or more heating processes can also be used.

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

The interlayer insulating film and the microlens formed as described above are excellent in various properties such as adhesion, heat resistance, solvent resistance and transparency, as is apparent from the examples described later.

Interlayer insulation film

The interlayer insulating film of the present invention formed as described above has good adhesion to a substrate, excellent solvent resistance and heat resistance, high transmittance, low dielectric constant, and can be suitably used as an interlayer insulating film of an electronic component.

Microlenses

The microlens of the present invention formed as described above has good adhesion to a substrate, excellent solvent resistance and heat resistance, has a high transmittance and a good melt shape, and can be suitably used as a microlens of a solid-state imaging device. .

The shape of the microlens of the present invention has a semiconvex lens shape as shown in Fig. 1A.

<Example>

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

Of polymer [A] Synthesis Example

Synthesis Example 1

To the flask equipped with a cooling tube and a stirrer, 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether were added. 15 parts by weight of methacrylic acid, 20 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-ylmethacrylate, 5 parts by weight of 4-acryloyl morpholine, 50 parts by weight of glycidyl methacrylate 10 parts by weight of styrene and 3 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C. and maintained at this temperature for 4 hours, thereby obtaining a polymer solution containing copolymer [A-1].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-1] was 12,000, and molecular weight distribution (Mw / Mn) was 3.0. In addition, the polymer concentration in the polymer solution obtained here was 34.8 weight%.

Synthesis Example 2

8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 172 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. Subsequently, 12 parts by weight of methacrylic acid, 50 parts by weight of glycidyl methacrylate, 3 parts by weight of N-cyclohexylmaleimide, 13 parts by weight of (3-ethyloxetan-3-yl) methacrylate, α-methyl 10 parts by weight of -p-hydroxystyrene and 3 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) were added thereto, followed by nitrogen replacement, followed by gentle stirring. 60 parts by weight of a 20% by weight solution of diethylene glycol ethylmethyl ether of N-cyclohexylmaleimide using a dropping funnel over 40 minutes after the temperature of the solution was raised to 70 ° C. and reached 20 ° C. over 20 minutes. It was dripped in the flask. The polymer solution containing copolymer [A-2] was obtained by holding 70 degreeC for 4 hours after completion | finish of dripping.

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-2] was 10,000, and molecular weight distribution (Mw / Mn) was 2.8. In addition, the polymer concentration in the polymer solution obtained here was 33.1 weight%.

Synthesis Example 3

8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 184 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 15 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 1 part by weight of N-phenylmaleimide, 20 parts by weight of tetrahydrofurfuryl methacrylate, p-vinylbenzyl 2,3-epoxypropyl ether 15 parts by weight and 3 parts by weight of trimethylolpropane tris (3-mercaptopropionate) were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70 ° C., and 20 parts by weight of a 20% by weight solution of diethylene glycol ethylmethyl ether of N-cyclohexylmaleimide was added to the flask at 20 ° C. after reaching 70 ° C. In the same manner, after 40 minutes and 60 minutes, 15 parts by weight of a 20% by weight solution of diethylene glycol ethylmethyl ether of N-cyclohexylmaleimide was added to the flask, and 70 ° C was further added after 60 minutes. By maintaining for 4 hours, a polymer solution containing the copolymer [A-3] was obtained.

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-3] was 9,800, and molecular weight distribution (Mw / Mn) was 2.7. In addition, the polymer concentration in the polymer solution obtained here was 33.4 weight%.

Synthesis Example 4

8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 50 parts by weight of glycidyl methacrylate, 15 parts by weight of N- (4-hydroxyphenyl) methacrylamide, and dipentaerythritol hexakis (3-mer 3 parts by weight of captopropionate) was added to replace the nitrogen, and then 5 parts by weight of 1,3-butadiene was added, and gently stirring was started. The temperature of the solution was raised to 70 ° C. and maintained at this temperature for 5 hours, thereby obtaining a polymer solution containing a copolymer [A-4].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [A-4] was 8,900 and molecular weight distribution (Mw / Mn) was 3.0. In addition, the polymer concentration in the polymer solution obtained here was 32.9 weight%.

Comparative Synthesis Example 1

8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethylmethyl ether were added to a flask equipped with a cooling tube and a stirrer. 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of (3-ethyloxetan-3-yl) methacrylate, tricyclo [5.2.1.0 ^{2, 6} ] 20 parts by weight of decane-8-yl methacrylate and 4 parts by weight of α-methylstyrene dimer were added to replace the nitrogen, followed by gentle stirring. The temperature of the solution was raised to 70 ° C. and maintained at this temperature for 4 hours, thereby obtaining a polymer solution containing copolymer [a-1].

The polystyrene reduced weight average molecular weight (Mw) of the copolymer [a-1] was 7,900, and molecular weight distribution (Mw / Mn) was 2.4. In addition, the polymer concentration in the polymer solution obtained here was 31.6 weight%.

The polymerization conversion rate in each said synthesis example was computed by the following formula from the weight of each component provided to the radical copolymerization, and the polymer concentration of the obtained polymer solution. The results are shown in Table 1 below.

Polymerization Conversion Rate (wt%) = Polymer Concentration (wt%) of Polymer Solution x Total (g) ÷ Total of Charges of Each Component (Including Solvent) ÷ Total (g) x 100

In addition, the polymer concentration (wt%) of the polymer solution is obtained by employing a small amount of the obtained polymer solution in an aluminum dish of which weight is already known and weighing it to obtain the weight of the polymer solution, which is heated on a hot plate at 180 ° C. for 1 hour to obtain a solvent. After removing, the weight was measured again to determine the weight of the polymer, and from these values (weight of polymer ÷ weight of polymer solution x 100).

Example 1

[Manufacture of a radiation sensitive resin composition]

The amount of the solution containing the copolymer [A-1] synthesized in Synthesis Example 1 as the polymer [A], equivalent to 100 parts by weight in terms of the copolymer [A-1] contained therein, [B] 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinone diazide- as components 30 parts by weight of a condensate (B-1) of 5-sulfonic acid chloride (2.0 mol) and 5 parts by weight of γ-glycidoxypropyltrimethoxysilane as the [G] adhesion assistant were mixed so that the solid content concentration was 30% by weight. After adding diethylene glycol ethyl methyl ether, the solution (S-1) of the radiation sensitive resin composition was manufactured by filtering by the membrane filter of 0.2 micrometer of pore diameters.

Examples 2-12 and Comparative Examples 1-3

[Manufacture of a radiation sensitive resin composition]

As the polymer [A] and [B] component, it carried out similarly to Example 1 except having used the thing of the kind shown in following Table 2 by the quantity shown in Table 2, and the solution of a radiation sensitive resin composition (S-2) To (S-12) and (s-1) to (s-3), respectively.

In addition, description of the component [B] in Example 2, 5, 8, 11, and the comparative example 2 shows using 2 types of 1, 2- quinonediazide compounds together, respectively.

Example 13

As the polymer [A], the solution containing the copolymer [A-1] synthesized in Synthesis Example 1 above was used in an amount corresponding to 100 parts by weight (solid content) of the copolymer [A-1] and SH as the [F] surfactant. 0.2 parts by weight of -28 PA (manufactured by Toray Dow Corning Silicone Co., Ltd.) and 5 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesive aid for [G], wherein diethylene glycol ethyl methyl ether and propylene glycol mono Methyl ether acetate was added, and the solvent composition was dissolved so that the solvent composition was diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate = 6/4 (weight ratio) and the solid content concentration was 20% by weight, followed by a membrane filter having a pore diameter of 0.2 µm. By filtration, the solution (S-13) of the radiation sensitive resin composition was produced.

In Table 2, the abbreviation of a component shows the following compounds, respectively.

(B-1): 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphtho Condensate of quinonediazide-5-sulfonic acid chloride (2.0 moles)

(B-2): condensate of 4,4 ', 4 "-ethylidedinetrisphenol (1.0 mol) with 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol)

(B-3): 2,3,4,4'-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonic acid ester (2.44 mol)

(F-1): SH-28PA (Toray Dow Corning Silicone Co., Ltd.)

(G-1): γ-glycidoxypropyltrimethoxysilane

Examples 14-26 and Comparative Examples 4-6

<Performance evaluation as an interlayer insulation film>

The various characteristics as an interlayer insulation film were evaluated as follows using the radiation sensitive resin composition manufactured as mentioned above.

[Evaluation of sensitivity]

For Examples 14 to 25 and Comparative Examples 4 to 6 on the silicon substrate, the composition shown in Table 3 below was applied using a spinner, and then prebaked at 90 ° C. for 2 minutes on a hot plate to obtain a film thickness of 3.0 μm. The coating film of was formed. In Example 26, the coating was carried out by a slit-die coater, and the solvent was removed under a reduced pressure of 0.5 Torr, followed by prebaking at 90 ° C. for 2 minutes on a hot plate to form a coating film having a film thickness of 3.0 μm. After exposure by changing exposure time with Canon PLA-501F exposure machine (ultra-high pressure mercury lamp) through the pattern mask which has a predetermined | prescribed pattern in the obtained coating film, it is tetramethylammonium hydroxide of the density shown in Table 3 as a developing solution. Each of the aqueous solution of axoxide was used, and it developed by the puddle method at 25 degreeC for 80 second. Subsequently, the pattern was formed on a silicon substrate by performing flowing water washing | cleaning for 1 minute with ultrapure water, and then drying. At this time, the minimum exposure amount required in order for the space pattern of 3.0 micrometers line and space (one to one) to melt | dissolve completely was investigated. This value is shown in Table 3 as the sensitivity.

[Evaluation of Development Margin]

For Examples 14 to 25 and Comparative Examples 4 to 6 on the silicon substrate, the composition shown in Table 3 was applied using a spinner, followed by prebaking at 90 ° C. for 2 minutes on a hot plate, and a coating film having a film thickness of 3.0 μm. Formed. In Example 26, the coating was carried out by a slit-die coater, and the solvent was removed under a reduced pressure of 0.5 Torr, followed by prebaking at 90 ° C. for 2 minutes on a hot plate to form a coating film having a film thickness of 3.0 μm. In the "[evaluation of sensitivity]" using the Canon-made PLA-501F exposure machine (ultra high pressure mercury lamp) through the mask which has a pattern of a line and space (1 to 1) of 3.0 micrometers in the obtained coating film, After exposing at the exposure amount corresponding to the value of the measured sensitivity, it developed using the tetramethylammonium hydroxide aqueous solution of the density | concentration shown in Table 3 as a developing solution, respectively, at 25 degreeC, and developing by the puddle method. Subsequently, after flowing water washing for 1 minute with ultrapure water, the pattern was formed on the silicon substrate by drying. At this time, the developing time required for the line width to be 3 m is shown in Table 2 as the optimum developing time. In addition, the time until the line pattern of 3.0 micrometers is peeled off when the image development was continued further from the optimal image development time was measured, and it showed in Table 3 as image development margin. When this value is 30 seconds or more, the development margin can be said to be good.

[Evaluation of Shrinkage at Curing]

On Examples 14 to 25 and Comparative Examples 4 to 6 on the silicon substrate, the composition shown in Table 3 was applied using a spinner, and then prebaked at 90 ° C. for 2 minutes on a hot plate to obtain a film thickness of 3.0 μm. A coating film was formed. In Example 26, the coating was carried out by a slit-die coater, and the solvent was removed under a reduced pressure of 0.5 Torr, followed by prebaking at 90 ° C. for 2 minutes on a hot plate to form a coating film having a film thickness of 3.0 μm. The film thickness (T1) of the coating film obtained here was measured. The obtained coating film was exposed to a cumulative irradiation amount of 3,000 J / m 2 by a Canon PLA-501F exposure machine (ultra-high pressure mercury lamp) without interposing a pattern mask, and the silicon substrate was exposed to 1 at 220 ° C. in a clean oven. After heating for a time to harden a coating film, the film thickness (t1) of this cured film was measured, and the film thickness change rate {| t1-T1 | / T1} x100 [%] by hardening was computed. The results are shown in Table 3. When this value is 10% or less, it can be said that shrinkage | contraction rate at the time of hardening is favorable.

In addition, since the patterning of the film | membrane to form is unnecessary in the evaluation of the shrinkage | contraction rate at the time of hardening, the irradiation process and the image development process were abbreviate | omitted, and only the coating film formation process, the post exposure process, and the heating process were performed for evaluation.

[Evaluation of solvent resistance]

On Examples 14-25 and Comparative Examples 4-6, on the silicon substrate, after apply | coating the composition of Table 3 using a spinner, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film. In Example 26, coating was performed using a slit-die coater, and the solvent was removed under a reduced pressure of 0.5 Torr, followed by prebaking at 90 ° C. for 2 minutes on a hot plate to form a coating film. The obtained coating film was exposed to a cumulative irradiation amount of 3,000 J / m 2 by a Canon PLA-501F exposure machine (ultra high pressure mercury lamp) without interposing a pattern mask, and the silicon substrate was exposed to light at 220 ° C. for 1 hour in a clean oven. Was heated to obtain a cured film having a film thickness of 3.0 mu m. The film thickness (T2) of the cured film obtained here was measured. After the silicon substrate on which the cured film was formed was immersed in dimethyl sulfoxide for 20 minutes at a temperature controlled at 70 ° C., the film thickness t2 of the cured film was measured, and the film thickness change rate by immersion {│t2-T2│ / T2 } × 100 [%] was calculated. The results are shown in Table 3. When this value is 5% or less, it can be said that solvent resistance is favorable.

In addition, since the patterning of the film to form is unnecessary in evaluation of solvent resistance, the irradiation process and the image development process were abbreviate | omitted, and only the coating film formation process, the post-exposure process, and the heating process were performed for evaluation.

[Evaluation of Heat Resistance]

The cured film was formed like the above-mentioned evaluation of solvent resistance, and the film thickness (T3) of the obtained cured film was measured. Subsequently, after further baking the board | substrate which has this cured film in a clean oven at 240 degreeC for 1 hour, the film thickness (t3) of this cured film was measured, and the film thickness change rate by further baking {│t3-T3│ / T3 } × 100 [%] was calculated. The results are shown in Table 3. When this value is 5% or less, heat resistance can be made favorable.

[Evaluation of transparency]

In the evaluation of the above solvent resistance, a cured film was formed on the glass substrate in the same manner except that a glass substrate "Corning 7059 (manufactured by Corning)" was used instead of the silicon substrate. The light transmittance of the glass substrate which has this cured film was measured with the wavelength of 400-800 nm using the spectrophotometer "150-20 type double beam (made by Hitachi Seisakusho)." Table 3 shows the values of the minimum light transmittance at this time. When this value is 90% or more, it can be said that transparency is favorable.

Examples 27-38 and Comparative Examples 7-9

<Evaluation as a micro lens>

Using the radiation sensitive resin composition manufactured as mentioned above, the various characteristics as a micro lens were evaluated as follows. In addition, evaluation of solvent resistance, evaluation of heat resistance, and evaluation of transparency refer to the result in the performance evaluation as the said interlayer insulation film.

[Evaluation of sensitivity]

After apply | coating the composition of Table 4 below using a spinner on a silicon substrate, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 2.0 micrometers in film thicknesses. After exposure by changing exposure time with the Nikon Corporation NSR1755i7A reduction projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a predetermined | prescribed pattern to the obtained coating film, the density shown in Table 4 as a developing solution was performed. The tetramethylammonium hydroxide aqueous solution of was respectively used, and it developed by the puddle method at 25 degreeC for 1 minute. Subsequently, after rinsing with water, the pattern was formed on a silicon substrate by drying. At this time, the minimum exposure amount required for the width of the space pattern of the 0.8 micrometer line and space pattern (1 to 1) to be 0.8 micrometer was investigated. This value is shown in Table 4 as the sensitivity.

[Evaluation of Development Margin]

After apply | coating the composition of Table 3 on a silicon substrate using the spinner, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 2.0 micrometers in film thicknesses. The exposure amount corresponding to the value of the sensitivity measured by said "[evaluation of sensitivity]" with the Nikon Corporation NSR1755i7A reduction projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a predetermined | prescribed pattern in the obtained coating film. After the exposure was carried out, the tetramethylammonium hydroxide aqueous solution of the concentration shown in Table 4 was used as a developing solution, respectively, and the image development time was changed at 25 degreeC, and it developed by the puddle method. Subsequently, the pattern was formed on a silicon substrate by rinsing with water and drying. At this time, the developing time required for the space line width of the 0.8 µm line-and-space pattern (1 to 1) to 0.8 µm is shown in Table 4 as the optimum development time. Moreover, the time (development margin) until peeling of the pattern of 0.8 micrometers in width | variety was further measured from the optimal image development time, and it shows in Table 4 as image development margin.

[Formation of Micro Lens]

After apply | coating the composition of Table 4 on a silicon substrate using the spinner, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film of 2.0 micrometers in film thicknesses. The sensitivity of the sensitivity measured by the "[evaluation of sensitivity]" by the Nikon Co., Ltd. NSR1755i7A reduction projection exposure machine (NA = 0.50, (lambda == 365 nm) through the pattern mask which has a 4.0 micrometer dot and 2.0 micrometer space pattern to the obtained coating film The exposure was performed at an exposure amount corresponding to the value. As a developing solution, the tetramethylammonium hydroxide aqueous solution of the density | concentration described as the developing solution density | concentration in evaluation of the sensitivity of Table 4 was respectively used, and it developed by the puddle method at 25 degreeC for 1 minute. The pattern was then formed on the silicon substrate by rinsing with water and drying. Then, it exposed by the Canon Co., Ltd. product PLA-501F exposure machine (ultra-high pressure mercury lamp) so that accumulated irradiation amount might be 3,000 J / m <2>. Thereafter, the plate was heated at 160 ° C. for 10 minutes and further heated at 230 ° C. for 10 minutes to meltflow the pattern to form microlenses.

Table 4 shows the dimensions (diameter) and the cross-sectional shape of the bottom (surface in contact with the substrate) of the microlenses formed here. The dimension of the microlens bottom portion can be said to be good when it is more than 4.0 micrometers and less than 5.0 micrometers. Moreover, when this dimension becomes 5.0 micrometers or more, it is unpreferable in the state which the adjacent lenses contact. In addition, the cross-sectional shape is good in the case of the semi-convex lens shape as shown in (a) in the schematic diagram shown in FIG. 1, and is bad in the case of a substantially trapezoidal shape as shown in (b).

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

Claims (11)

[A] A polymer having at least one group selected from the group consisting of a carboxyl group and a carboxylic anhydride group, at least one group selected from the group consisting of an oxylanyl group and an oxetanyl group, and an n-valent group represented by the following general formula (1) And [B] 1,2-quinonediazide compound. <Formula 1>

(Wherein R ^I is a methylene group or an alkylene group or alkylmethylene group having 2 to 10 carbon atoms, and Y is a single bond, -CO-, -O-CO- ^* (wherein the bond with "*" is R). Bound to ^I ) or -NHCO- ^* (wherein the bond of "*" is bound to R ^I ), n is an integer from 2 to 10 and X can have one or more ether bonds An n-valent hydrocarbon group having 2 to 70 carbon atoms, or n is 3 and X is a trivalent group represented by the following Chemical Formula 2, and "+" represents a bond.) <Formula 2>

(In formula, R <^II> is respectively independently a methylene group or a C2-C6 alkylene group, and it shows that "*" is a bond., Respectively.) The radiation sensitive resin composition according to claim 1, wherein Y in Formula 1 is -O-CO- ^* , provided that a bond of “*” is bonded to R ^I. [A] (a1) Unsaturated compound having at least one group selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (a2) at least one group selected from the group consisting of an oxylanyl group and an oxetanyl group A radiation-sensitive resin composition comprising a polymer obtained by radical copolymerization of an unsaturated compound containing a compound in the presence of a compound represented by the following formula (8), and a [B] 1,2-quinonediazide compound. <Formula 8> (Wherein, X, Y, R ^I and n are each X, Y, R ^I and n in formula (I) with the consent of the Im) The radiation sensitive resin composition according to claim 3, wherein Y in Formula 8 is -O-CO- ^* , provided that a bond of “*” is bonded to R ^I. The radiation sensitive resin composition of any one of Claims 1-4 for manufacture of an interlayer insulation film. (1) process of forming the coating film of the radiation sensitive resin composition of Claim 5 on a board | substrate, (2) irradiating at least a part of the coating film with radiation; (3) developing process, and (4) heating process The manufacturing method of the interlayer insulation film characterized by including in order as described above. An interlayer insulating film or microlens produced by the method according to claim 6. The radiation sensitive resin composition of any one of Claims 1-4 for microlens manufacture. (1) process of forming the coating film of the radiation sensitive resin composition of Claim 8 on a board | substrate, (2) irradiating at least a part of the coating film with radiation; (3) developing process, and (4) heating process It comprises in the order described above, the manufacturing method of a microlens. The microlens formed by the method of Claim 9. (a1) containing an unsaturated compound having at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (a2) at least one group selected from the group consisting of oxylalanyl groups and oxetanyl groups A method for producing a polymer, wherein the unsaturated compound formed is radically copolymerized in the presence of a compound represented by the following formula (8). <Formula 8>

(Wherein, X, Y, R ^I and n are each X, Y, R ^I and n in formula (I) with the consent of the Im)

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