JP4748323B2 - Radiation-sensitive resin composition, interlayer insulating film and microlens, and production method thereof - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition, an interlayer insulating film and a microlens, and methods for producing them.

In an electronic component such as a thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display element, magnetic head element, integrated circuit element, solid-state imaging element, etc., an interlayer insulation is generally used to insulate between wirings arranged in layers. A membrane is provided. As a material for forming an interlayer insulating film, a material having a small number of steps for obtaining a required pattern shape and having sufficient flatness is preferable, and thus a radiation sensitive resin composition is widely used (patents) Reference 1 and Patent Document 2).
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 further forming a liquid crystal alignment film on the interlayer insulating film. Since the film is exposed to a high temperature condition in the transparent electrode film forming process or exposed to a resist stripping solution used for forming an electrode pattern, sufficient resistance to these is required.
In recent years, TFT-type liquid crystal display elements have been in the trend of larger screens, higher brightness, higher definition, faster response, thinner thickness, etc., and the composition for forming an interlayer insulating film used therefor has high sensitivity. In addition, the interlayer insulating film to be formed is required to have higher performance than ever in terms of low dielectric constant and high transmittance.

On the other hand, a microlens having a lens diameter of about 3 to 100 μm or an optical system material for an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state image sensor, or the like is defined as an optical system material. An array of microlenses is 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 as a lens, or by using the melt-flowed lens pattern as a mask and drying. A method of transferring a lens shape to a base by etching is known. For the formation of the lens pattern, a radiation sensitive resin composition is widely used (see Patent Document 3 and Patent Document 4).

By the way, the element in which the microlens or the microlens array as described above is formed is then applied with a planarizing film and an etching resist film in order to remove various insulating films on the bonding pad which is a wiring forming portion. Exposure and development are performed using a desired mask to remove the etching resist in the bonding pad portion, and then the step is performed to remove the planarizing film and various insulating films by etching to expose the bonding pad portion. Therefore, the microlens or the microlens array needs to have solvent resistance and heat resistance in the flattening film and etching resist coating film forming process and the etching process.
The radiation-sensitive resin composition used to form such a microlens has high sensitivity, and the microlens formed therefrom has a desired radius of curvature, and has high heat resistance and high transmittance. It is required to be a rate.
In addition, the interlayer insulating film and the microlens thus obtained can penetrate between the pattern and the substrate if the development time is slightly longer than the optimum time in the development process when forming them. Therefore, it is necessary to strictly control the development time, 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 the developing time in the developing process during the forming process is longer than a predetermined time. Even if it becomes excessive, the pattern does not peel off and shows good adhesion, and the interlayer insulating film formed therefrom has high heat resistance, high solvent resistance, low dielectric constant, high transmittance, high adhesion On the other hand, when forming a microlens, a good melt shape (desired radius of curvature), high heat resistance, high solvent resistance, and high transmittance are required as a microlens. A radiation-sensitive resin composition that satisfies such requirements has not been known.
JP 2001-354822 A JP 2001-343743 A JP-A-6-18702 JP-A-6-136239

  The present invention has been made based on the above situation. Therefore, an object of the present invention is to provide a pattern shape having high radiation sensitivity, having a development margin capable of forming a good pattern shape even in the development process exceeding the optimum development time, and having excellent adhesion. An object of the present invention is to provide a radiation sensitive composition capable of easily forming a thin film.

  Another object of the present invention is to form an interlayer insulating film having high heat resistance, high solvent resistance, high transmittance, low dielectric constant and high adhesion when used for forming an interlayer insulating film. The object of the present invention is to provide a radiation-sensitive resin composition capable of forming a microlens having a high transmittance and a good melt shape when used for forming a lens.

Still another object of the present invention is to provide a method for 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 and a microlens formed by the method of the present invention.
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 are firstly
[A] (a1) at least one selected from the group of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as “compound (a1)”),
(A2) An unsaturated compound containing at least one of an epoxy group or an oxetanyl group (hereinafter sometimes referred to as “compound (a2)”)
(A3) At least one selected from the group of acryloylmorpholine and methacryloylmorpholine (hereinafter sometimes referred to as “compound (a3)”).
(A4) a copolymer of an unsaturated compound other than (a1), (a2) and (a3) (hereinafter sometimes referred to as “compound (a4)”) (hereinafter referred to as “copolymer [A]”) As well as [B] 1,2-quinonediazide compounds (hereinafter sometimes referred to as “component [B]”).
It achieves by the radiation sensitive resin composition characterized by containing.

Secondly, the objects and advantages of the present invention are:
This is achieved by a method for forming an interlayer insulating film or a microlens, which includes the following steps in the order described below.

(1) The process of forming the coating film of said radiation sensitive composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) Development step, and (4) Heating step.

Third, the objects and advantages of the present invention are
This is achieved by the interlayer insulating film or microlens formed by the above method.

The radiation-sensitive resin composition of the present invention has high radiation sensitivity, has a development margin that can form a good pattern shape even when the optimum development time is exceeded in the development process, and has excellent adhesion. A patterned thin film can be easily formed.
The interlayer insulating film of the present invention formed from the above composition has good adhesion to the substrate, excellent solvent resistance and heat resistance, high transmittance, low dielectric constant, It can be suitably used as an interlayer insulating film for parts.
Further, the microlens of the present invention formed from the upper composition has good adhesion to the substrate, excellent solvent resistance and heat resistance, and has a high transmittance and a good melt shape, It can be suitably used as a microlens for a solid-state image sensor.

Hereinafter, the radiation sensitive resin composition of this invention is explained in full detail.
Copolymer [A]
Copolymer [A] can be produced by radical polymerization of compound (a1), compound (a2), compound (a3) and compound (a4) in the presence of a polymerization initiator in a solvent.
Compound (a1) is at least one selected from the group of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides having radical polymerizability, such as monocarboxylic acids, dicarboxylic acids, dicarboxylic acid anhydrides, and polyvalent carboxylic acids. And mono [(meth) acryloyloxyalkyl] ester, mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, a polycyclic compound having a carboxyl group, and an anhydride thereof.

Specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Examples of dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;
As anhydrides of dicarboxylic acids, for example, anhydrides of the compounds exemplified as the above dicarboxylic acids;
Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl];
Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate;
Examples of the polycyclic compound having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene. 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] And hept-2-ene anhydride.
Of these, monocarboxylic acid and dicarboxylic acid anhydrides are preferably used, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferably used from the viewpoints of copolymerization reactivity, solubility in alkaline aqueous solutions, and availability. . These compounds (a1) are used alone or in combination.

  In the copolymer [A] used in the present invention, the structural unit derived from the compound (a1) is added to the total of repeating units derived from the compounds (a1), (a2), (a3) and (a4). Based on this, the content is preferably 1 to 80% by weight, particularly preferably 5 to 40% by weight. If this structural unit is less than 1% by weight, the adhesion of the resulting interlayer insulating film or microlens tends to be reduced, whereas if the amount of this structural unit exceeds 80% by weight, the radiation sensitive resin composition Storage stability tends to decrease.

The compound (a2) is an unsaturated compound containing either an epoxy group or oxetanyl group having radical polymerizability.
Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and acrylate 3,4. -Epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinyl Examples thereof include benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether. Among these, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. It is preferably used from the viewpoint of increasing the copolymerization reactivity and the heat resistance and surface hardness of the obtained interlayer insulating film or microlens.
Examples of the epoxy group-containing unsaturated compound include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, and 3- (methacryloyl). Oxymethyl) -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- (methacryloyloxyethyl) Oxetane, 3- ( Tacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxyethyl) -2-penta Fluoroethyloxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, And 3- (methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane. These compounds (a2) are used alone or in combination.

  In the copolymer [A] used in the present invention, the structural unit derived from the compound (a2) is added to the total number of repeating units derived from the compounds (a1), (a2), (a3) and (a4). Based on this, the content is preferably 5 to 70% by weight, particularly preferably 10 to 60% by weight. When this structural unit is less than 5% by weight, the heat resistance and curability of the radiation-sensitive resin composition and the surface height tend to decrease. On the other hand, when it exceeds 60% by weight, the radiation-sensitive resin composition is stored. The stability tends to decrease.

Among the compounds (a3), acryloylmorpholine can improve the polymerization conversion by copolymerizing with acrylate among the other unsaturated compounds represented by the compound (a4). Specific examples thereof include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5 .2.1.0 ^2,6 ] decan-8-yl acrylate (hereinafter referred to as “dicyclopentanyl acrylate”), tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl Examples include acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, tetrahydrofurfuryl acrylate, 3-acryloyloxytetrahydrofuran-2-one, and furfuryl acrylate.

  In the copolymer [A] used in the present invention, the structural unit derived from the compound (a3) is added to the total number of repeating units derived from the compounds (a1), (a2), (a3) and (a4). The content is preferably 1 to 50% by weight, particularly preferably 1 to 30% by weight. When this structural unit exceeds 50 weight%, it exists in the tendency for the storage stability of a radiation sensitive resin composition to fall.

  The compound (a4) is not particularly limited as long as it is an unsaturated compound having radical polymerizability. For example, methacrylic acid alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, hydroxy methacrylic acid ester, hydroxyacrylic acid ester, Mention may be made of bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, tetrahydrofuran skeletons, furan skeletons, tetrahydropyran skeletons, unsaturated compounds having a pyran skeleton and other unsaturated compounds.

Examples of methacrylic acid alkyl esters include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, and n-stearyl. Methacrylate, etc .; Examples of cyclic esters of methacrylic acid include, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate (hereinafter, “dicyclopentanyl methacrylate”) Tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl methacrylate, isobornyl methacrylate, etc .; Examples of alkyl alkyl rilates include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, etc .; as cyclic esters of acrylic acid, for example, cyclohexyl Acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (hereinafter referred to as “dicyclopentanyl acrylate”), tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl acrylate, isobornyl acrylate, etc .; acrylic acid aryl ester, for example, phenyl acrylate, benzyl acrylate, etc .; methacrylic acid aryl ester, For example, phenyl methacrylate, benzyl methacrylate, etc .; as unsaturated dicarboxylic acid diesters, for example, diethyl maleate, diethyl fumarate, diethyl itaconate, etc .; as hydroxy methacrylates, for example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3 -Hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethylglycoside, 4-hydroxyphenyl methacrylate, etc .;
Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1]. Hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-carboxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2. 1] Hept-2-ene, 5- (2-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxy Bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2 -Ene, 5,6-di (hydroxymethyl) Cyclo [2.2.1] hept-2-ene, 5,6-di (2-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2. 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [ 2.2.1] Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [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 (hymic acid anhydride), 5-t-butoxycarbonylbicyclo [2. 2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6 -Di (t-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like;

Examples of unsaturated dicarbonylimide derivatives include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, and N-succinimidyl-3. -Maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like;
As unsaturated aromatic compounds, for example, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, etc .; as conjugated dienes, for example, 1,3-butadiene, isoprene, 2 As unsaturated compounds containing a tetrahydrofuran skeleton, for example, tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyl 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, acrylic acid 2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one, etc .; containing tetrahydropyran skeleton Examples of unsaturated compounds include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, and tetrahydropyran 2-methacrylate. 2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, etc .; unsaturated compounds containing a pyran skeleton include, 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, etc .; Examples of the unsaturated compound include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Of these, methacrylic acid alkyl esters, methacrylic acid cyclic alkyl esters, bicyclounsaturated compounds, unsaturated aromatic compounds, and conjugated dienes are preferably used, and in particular, styrene, t-butyl methacrylate, tricyclo [5.2.1.0]. ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3-butadiene, bicyclo [2.2.1] hept-2-ene, tetrahydrofurfuryl (meth) acrylate, Polyethylene glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, furfuryl (Meth) acrylate has copolymerization reactivity and From the viewpoint of solubility in potassium solution. These compounds (a4) are used alone or in combination.

  In the copolymer [A] used in the present invention, the structural unit derived from the compound (a4) is added to the total repeating units derived from the compounds (a1), (a2), (a3) and (a4). Based on this, the content is preferably 10 to 80% by weight, particularly preferably 20 to 70% by weight. When this structural unit is less than 10% by weight, the heat resistance and surface hardness of the resulting interlayer insulating film and microlens tend to be reduced, whereas when the amount of this structural unit exceeds 80% by weight, the radiation sensitive resin The storage stability of the composition tends to decrease.

Preferable specific examples of the copolymer [A] used in the present invention include, for example, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / glycidyl methacrylate / 2-methyl. Cyclohexyl acrylate / N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide / acryloylmorpholine copolymer, methacrylic acid / glycidyl methacrylate / 1- (tetrahydropyran-2-oxy) -butyl-3-ene- 2-one / N-cyclohexylmaleimide / p-methoxystyrene / 3-ethyl-3-methacryloyloxymethyloxetane / N- (3,5-dimethyl-4-hydroxybenzyl) methacrylamide / acryloylmorpholine copolymer, methacrylic acid /Tricyclo[5.2.1.0 ^2,6 ] Decan-8-yl methacrylate / styrene / N-phenylmaleimide / N- (4-hydroxyphenyl) methacrylamide / acryloylmorpholine copolymer, methacrylic acid / glycidyl methacrylate / tricyclo [5.2.1.0 ^2,6 ] Decan-8-yl methacrylate / n-lauryl methacrylate / 3-methacryloyloxytetrahydrofuran-2-one / N- (4-hydroxyphenyl) methacrylamide / acryloylmorpholine copolymer, methacrylic acid / glycidyl methacrylate / styrene / 2 -Methylcyclohexyl acrylate / 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one / 4-hydroxybenzyl methacrylate / acryloylmorpholine copolymer, methacrylic acid / methacrylic acid group Glycidyl / tricyclo [5.2.1.0 ^2,6] decan-8-yl methacrylate / p- methoxystyrene / 4-hydroxybenzyl methacrylate / acryloylmorpholine copolymer, methacrylic acid / tricyclo [5.2.1. 0 ^2,6 ] decan-8-yl methacrylate / glycidyl methacrylate / styrene / p-vinylbenzyl glycidyl ether / tetrahydrofurfuryl methacrylate / 4-hydroxyphenyl methacrylate / acryloyl morpholine copolymer, methacrylic acid / glycidyl methacrylate / N -Cyclohexylmaleimide / α-methyl-p-hydroxystyrene / tetrahydrofurfuryl methacrylate / acryloylmorpholine copolymer, methacrylic acid / glycidyl methacrylate / N-cyclohexylmaleimi Do-3-ethyl-3-methacryloyloxymethyloxetane / 3-methacryloyloxytetrahydrofuran-2-one / tetrahydrofurfuryl methacrylate / 4-hydroxyphenyl methacrylate / acryloylmorpholine copolymer, methacrylic acid / glycidyl methacrylate / 3-ethyl -3-Methacryloyloxymethyloxetane / tetrahydrofurfuryl methacrylate / N-phenylmaleimide / α-methyl-p-hydroxystyrene / acryloylmorpholine copolymer, methacrylic acid / glycidyl methacrylate / 3-ethyl-3-methacryloyloxymethyloxetane / tricyclo [5.2.1.0 ^2,6] decan-8-yl methacrylate / N- cyclohexyl maleimide / n-lauryl methacrylate / alpha-methylcarbamoyl Such -p- hydroxystyrene copolymer / acryloyl morpholine.

The copolymer [A] used in the present invention has a polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”), preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ^{3 to} 5 × 10. ⁴ . If the Mw is less than 2 × 10 ³ , the development margin may not be sufficient, the remaining film ratio of the resulting film may decrease, the pattern shape of the resulting interlayer insulating film or microlens, heat resistance, etc. On the other hand, if it exceeds 1 × 10 ⁵ , the sensitivity may be lowered or the pattern shape may be inferior. The molecular weight distribution (hereinafter referred to as “Mw / Mn”) is preferably 5.0 or less, more preferably 3.0 or less. When Mw / Mn exceeds 5.0, the pattern shape of the obtained interlayer insulating film or microlens may be inferior. The radiation-sensitive resin composition containing the copolymer [A] can easily form a predetermined pattern shape without causing a development residue during development.

[A] The copolymer is, for example, an unsaturated compound (a1), an unsaturated compound (a2), an unsaturated compound (a3), an unsaturated compound (a4) in the presence of a radical polymerization initiator in an appropriate solvent. It can be synthesized by polymerizing under.
Examples of the solvent used for the polymerization include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, and aromatic. There may be mentioned hydrocarbons, ketones, esters and the like.

Specific examples of these solvents include alcohol, methanol, ethanol, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, etc .; ether, tetrahydrofuran, etc .; ethylene glycol ether, ethylene glycol monomethyl ether, ethylene Glycol monoethyl ether, etc .; ethylene glycol alkyl ether acetate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol n-propyl ether acetate, ethylene glycol n-butyl ether acetate, etc .; diethylene glycol alkyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl A Le, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether;
As propylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, etc .; as propylene glycol alkyl ether acetate, propylene glycol methyl ether acetate, propylene Glycol ethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate, etc .; as propylene glycol alkyl ether propionate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol n- Propi Ether propionate, propylene glycol n- butyl ether propionate; aromatic hydrocarbons, toluene, xylene and the like; as ketones, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like;
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Ethyl acetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, 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, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropyl Butyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropion Examples thereof include esters such as propyl acid, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Of these, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable, and diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, and propylene glycol methyl ether acetate are particularly preferable. .

As the polymerization initiator used in the production of the copolymer [A], those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile) Azo compounds such as; benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, organic peroxides such as 1,1′-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.
In the production of the copolymer [A], a molecular weight modifier can be used to adjust the molecular weight. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid; dimethylxanthogen sulfide, Xanthogens such as diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

[B] Component As the 1,2-quinonediazide compound of the [B] component used in the present invention, for example, 1,2-benzoquinone diazide sulfonate, 1,2-naphthoquinonediazide sulfonate, 1,2-benzo Examples thereof include quinone diazide sulfonic acid amide and 1,2-naphthoquinone diazide sulfonic acid amide.

Specific examples thereof include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone azide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfone. Acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2 , 3,4-Trihydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6 -Trihydroxybenzophenone-1,2-naphthoquinone diazi -5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfone 1,2-naphthoquinone diazide sulfonic acid esters of trihydroxybenzophenone such as acid esters, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinone diazide-8-sulfonic acid esters;
2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphtho Quinonediazide-7-sulfonic acid ester, 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1, 2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,3′-tetrahydroxy Benzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,3′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,4′- Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4 '-Tetrahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-8- Sulfonic acid ester, 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2′-tetrahydroxy-4′- Methylbenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3 , 4,2′-Tetrahydroxy-4′-methylbenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester 2,3,4,2′-tetrahydroxy-4′-methylbenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone -1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4 , 4′-Tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide -7-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2-naphtho 1,2-naphthoquinone diazide sulfonic acid ester of tetrahydroxybenzophenone such as quinone diazide-8-sulfonic acid ester;
2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,3,4,2 ′, 6′-penta Of pentahydroxybenzophenone such as hydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,3,4,2 ′, 6′-pentahydroxybenzophenone-1,2-naphthoquinonediazide-8-sulfonic acid ester, etc. 1,2-naphthoquinonediazide sulfonic acid ester;
2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,4, 6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2 -Naphthoquinonediazide-8-sulfonic acid ester, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexa Hydroxybenzophenone-1,2-naphthoquinonediazide-6-sulfonic acid ester, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-7-sulfonic acid ester, 3, 1,2-naphthoquinone diazide sulfonic acid ester of hexahydroxybenzophenone such as 4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinone diazide-8-sulfonic acid ester;

Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis ( 2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2, 4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane -1,2-naphthoquinonediazide-5-sulfonic acid Tellurium, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (p- Hydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1 , 2-Naphthoquinonediazide-5-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide- 7-sulfonic acid ester, tri (p-hydride Kishifeniru) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester,
1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide- 5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1 , 2-Naphthoquinonediazide-7-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-8-sulfonic acid ester, bis (2,3,4-trihydroxy) Phenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) Tan-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (2,3,4- Trihydroxyphenyl) methane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,2- Bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1, -Naphthoquinonediazide-6-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-7-sulfonic acid ester, 2,2-bis (2,3 , 4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-8-sulfonic acid ester,

1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5- Dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane -1,2-naphthoquinonediazide-6-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-7-sulfonic acid Ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinone Azido-8-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfone Acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4, 4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-6-sulfonic acid ester, 4,4 ′-[1 -[4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide 7-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-8-sulfonic acid ester ,
Bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxy Phenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-6-sulfonic acid ester, bis (2,5-Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-7-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenyl Methane-1,2-naphthoquinonediazide-8-sulfonic acid ester 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-4-sulfone Acid ester 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,6,7,5 ′, 6 ′, 7′-hexanol-1,2-naphthoquinonediazide-5 -Sulfonate ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2-naphthoquinonediazide -6-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6 ', 7'-hexanol-1,2- Naphthoquinonediazide-7-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiinde -5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-8-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan -1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid, 2,2, 4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-6-sulfonic acid ester, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1 2,2-naphthoquinonediazide-7-sulfonic acid, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan-1,2-naphthoquinonediazide-8-sulfonic acid, etc. Phenyl) include 1,2-naphthoquinonediazide sulfonic acid esters of alkanoic.
These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

  [B] The usage-amount of a component becomes like this. Preferably it is 5-100 weight part with respect to 100 weight part of copolymers [A], More preferably, it is 10-50 weight part. When this ratio is less than 5 parts by weight, the amount of acid generated by irradiation with radiation is small, so the difference in solubility in an alkaline aqueous solution that is a developer between the irradiated part and the unirradiated part is small, and patterning is difficult. Tend to be. In addition, since the amount of acid involved in the reaction with the copolymer [A] decreases, sufficient heat resistance and solvent resistance may not be obtained. On the other hand, if this ratio exceeds 100 parts by weight, a large amount of unreacted [B] component remains after irradiation for a short time, so that the effect of insolubilization in the alkaline aqueous solution is too high and development is performed. Tend to be difficult

Other Components The radiation-sensitive resin composition of the present invention contains the above-mentioned copolymer [A] and [B] components as essential components, but [C] a thermosensitive acid-generating compound, [ D] A polymerizable compound having at least one ethylenically unsaturated double bond, an epoxy resin other than [E] copolymer [A], [F] a surfactant or [G] an adhesion assistant. Can do.
[C] The heat-sensitive acid generating compound can be used to improve heat resistance and hardness. 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.

Specific examples thereof include alkylsulfonium salts such as 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimony. Dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate, etc .;
Examples of benzylsulfonium salts include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, and benzyl-4-methoxyphenylmethyl. Sulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethyl Sulfonium hexafluorophosphate, etc .;
Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexa Fluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-tert-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4 -Hydroxyphenylsulfonium hexafluorophosphate and the like;
Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethylsulfonium. Hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro Examples thereof include -4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Specific examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p- Benzylbenzothiazonium such as methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate Salt.

Of these, sulfonium salts and benzothiazonium salts are preferably used, particularly 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexanium. Fluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, and 3-benzylbenzothiazolium hexafluoroantimonate are preferably used.
Examples of these commercially available products include Sun-Aid SI-L85, SI-L110, SI-L145, SI-L150, SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.).

  The proportion of component [C] used is preferably 20 parts by weight or less, more preferably 5 parts by weight or less with respect to 100 parts by weight of copolymer [A]. When the amount used exceeds 20 parts by weight, precipitates may be deposited in the coating film forming step, which may hinder the coating film formation.

Examples of the polymerizable compound having at least one ethylenically unsaturated double bond as component [D] (hereinafter sometimes referred to as “component D”) include monofunctional (meth) acrylate, bifunctional ( Preferable examples include (meth) acrylate or tri- or higher functional (meth) acrylate.
Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. And 2-hydroxypropyl phthalate. As these commercial products, for example, Aronix M-101, M-111, M-114 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, TC-120S (above, Nippon Kayaku Co., Ltd.) ) Co., Ltd.), Biscoat 158, 2311 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

  Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate. As these commercial products, for example, Aronix M-210, M-240, M-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (above, Nippon Kayaku) Medicine Co., Ltd.), Biscoat 260, 312 and 335HP (above, Osaka Organic Chemical Industries, Ltd.).

Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like, and as commercially available products thereof, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M-8060 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (Nippon Kayaku Co., Ltd.), screw Over DOO 295, the 300, the 360, the GPT, said 3PA, the 400 (manufactured by Osaka Organic Chemical Industry Ltd.) and the like.
Of these, a tri- or higher functional (meth) acrylate is preferably used, and among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are particularly preferable.

  These monofunctional, bifunctional, or trifunctional or higher (meth) acrylates are used alone or in combination. The proportion of the component [D] used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less with respect to 100 parts by weight of the copolymer [A].

  By including the component [D] at such a ratio, the heat resistance, surface hardness, etc. of the interlayer insulating film or microlens obtained from the radiation-sensitive resin composition of the present invention can be improved. If the amount used exceeds 50 parts by weight, film roughening may occur in the step of forming a coating film of the radiation-sensitive resin composition on the substrate.

  The epoxy resin other than the copolymer [A] as the [E] component (hereinafter sometimes referred to as “E component”) is not limited as long as the compatibility is not affected. Preferably, bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, glycidyl methacrylate ) Polymerized resins and the like can be mentioned. Of these, bisphenol A type epoxy resins, cresol novolac type epoxy resins, glycidyl ester type epoxy resins and the like are particularly preferable.

[E] The use ratio of the component is preferably 30 parts by weight or less with respect to 100 parts by weight of the copolymer [A]. By containing the component [E] at such a ratio, the heat resistance and surface hardness of the protective film or insulating film obtained from the radiation-sensitive resin composition of the present invention can be further improved. When this ratio exceeds 30 parts by weight, the film thickness uniformity of the coating film may be insufficient when a coating film of the radiation sensitive resin composition is formed on the substrate.
The copolymer [A] can also be referred to as an “epoxy resin”, but differs from the component [E] in that it has alkali solubility. [E] component is alkali-insoluble.

  In the radiation sensitive resin composition of the present invention, a surfactant which is the above-mentioned [F] component can be used to further improve the coating property. As the [F] surfactant that can be used here, fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants can be suitably used.

  Specific examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether. , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1 , 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8 , 8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc. Sodium Zensuruhon acid; fluoroalkyl polyoxyethylene ethers; fluoroalkyl ammonium iodide, fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethylene ethanol; can be exemplified fluorine-based alkyl esters; perfluoroalkyl alkoxylates. These commercial products include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183, F178, F191, F191 (and above, Dainippon Ink). Chemical Industries, Ltd.), Fluorad FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.) ), F-top EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.).

  Examples of the silicone surfactant include DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above, Toray Dow Corning) -Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, GE Toshiba Silicone Co., Ltd.) are commercially available. You can list what you have.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Polyoxyethylene aryl ethers such as polyoxyethylene dilaurate, polyoxyethylene dialkyl esters such as polyoxyethylene distearate, etc .; (meth) acrylic acid copolymer polyflow Nos. 57 and 95 (Kyoeisha Chemical Co., Ltd.) ))) Can be used.
These surfactants can be used alone or in combination of two or more.

  These [F] surfactants are preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the copolymer [A]. [F] When the amount of the surfactant used exceeds 5 parts by weight, the coating film may be easily formed when the coating film is formed on the substrate.

  In the radiation-sensitive resin composition of the present invention, an adhesion assistant as the [G] component can also be used in order to improve the adhesion to the substrate. As such [G] adhesion assistant, a functional silane coupling agent is preferably used, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. . Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Such [G] adhesion assistant is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. In the case where the amount of the adhesion assistant exceeds 20 parts by weight, there may be a case where a development residue is likely to occur in the development process.

Radiation-sensitive resin composition The radiation-sensitive resin composition of the present invention is prepared by uniformly mixing the above-mentioned copolymer [A] and [B] components and other components optionally added as described above. Is done. The radiation sensitive resin composition of the present invention is preferably used in a solution state after being dissolved in a suitable solvent. For example, the radiation sensitive resin composition in a solution state can be prepared by mixing the copolymer [A] and [B] components and other optionally added components in a predetermined ratio.

As the solvent used for the preparation of the radiation sensitive resin composition of the present invention, each component of the copolymer A] and [B] components and other components optionally blended is uniformly dissolved, Those that do not react are used.
As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture copolymer [A] mentioned above can be mentioned.

  Among such solvents, alcohol, glycol ether, ethylene glycol alkyl ether acetate, ester and diethylene glycol are preferably used from the viewpoints of solubility of each component, reactivity with each component, ease of film formation, and the like. . Among these, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, Purpylene glycol monomethyl ether acetate, methyl methoxypropionate, and ethyl ethoxypropionate can be particularly preferably used.

  Furthermore, in order to improve the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

  When a high boiling point solvent is used in combination as the solvent of the radiation sensitive resin composition of the present invention, the amount used is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30%, based on the total amount of the solvent. It can be made into weight% or less. If the amount of the high-boiling solvent used exceeds this amount, the coating film thickness uniformity, sensitivity, and residual film rate may decrease.

When the radiation-sensitive resin composition of the present invention is prepared in a solution state, components other than the solvent in the solution (that is, the total of the copolymer [A] and [B] components and other components optionally added) The ratio of (amount) can be arbitrarily set according to the purpose of use, the value of the desired film thickness, etc., but is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and still more preferably 15 to 35% by weight.
The composition solution thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.2 μm.

Formation of Interlayer Insulating Film and Microlens Next, a method for forming the interlayer insulating film and microlens of the present invention using the radiation sensitive resin composition of the present invention will be described. The method for forming an interlayer insulating film or microlens of the present invention includes the following steps in the order described below.
(1) The process of forming the coating film of the radiation sensitive resin composition of this invention on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) Development step, and (4) Heating step.

(1) Step of forming a coating film of the radiation sensitive resin composition of the present invention on a substrate In the step of (1) above, the composition solution of the present invention is applied to the substrate surface, preferably prebaked. To remove the solvent and form a coating film of the radiation-sensitive resin composition.
Examples of the types of substrates that can be used include glass substrates, silicon wafers, and substrates on which various metals are formed.
The method of applying the composition solution is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, or the like is employed. In particular, spin coating and slit die coating are preferred. Prebaking conditions vary depending on the type of each component, the proportion of use, and the like. For example, it can be set at 60 to 110 ° C. for about 30 seconds to 15 minutes.
The thickness of the coating film to be formed is, for example, 3 to 6 μm when the interlayer insulating film is formed, and 0.5 to 3 μm, for example, when the microlens is formed, as the value after pre-baking. preferable.

(2) Step of irradiating at least a part of the coating film In the step (2), the developer is irradiated with radiation through a mask having a predetermined pattern on the formed coating film. The patterning is performed by removing the irradiated portion using the development process. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet rays include KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam.
Among these, ultraviolet rays are preferable, and radiation containing g-line and / or i-line is particularly preferable.
The exposure amount, 50~1,500J / ^{m 2} In the case of forming an interlayer insulating film, in the case of forming a micro-lens is preferably set to 50~2,000J / ^{m 2.}

(3) Development process Examples of the developer used in the development process include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-acid. N-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene An aqueous solution of an alkali (basic compound) such as 1,5-diazabicyclo [4,3,0] -5-nonane can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous alkali solution described above, or various organic solvents that dissolve the composition of the present invention can be used as a developing solution. Furthermore, as a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time at this time varies depending on the composition of the composition, but can be, for example, 30 to 120 seconds.
In addition, the conventionally known radiation-sensitive resin composition has been required to strictly control the development time because the formed pattern peels when the development time exceeds about 20 to 25 seconds from the optimum value. In the case of the radiation-sensitive resin composition of the invention, good pattern formation is possible even when the excess time from the optimum development time is 30 seconds or more, and there is an advantage in product yield.

(4) Heating step (3) Performed as described above (3) After the development step, the patterned thin film is preferably rinsed, for example, by washing with running water, and more preferably irradiated with radiation from a high-pressure mercury lamp or the like. (After post-exposure), the 1,2-quinonediadito compound remaining in the thin film is decomposed, and then the thin film is heated (post-baked) with a heating device such as a hot plate or an oven. Then, the thin film is cured. The exposure amount in the post-exposure step is preferably about 2,000 to 5,000 J / m ² . Moreover, the baking temperature in this hardening process is 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, for example, when performing heat processing on a hotplate, it can be set to 30 to 90 minutes when performing heat processing in oven, for example. At this time, a step baking method or the like in which a heating process is performed twice or more can also be used.
In this way, 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 adhesion, heat resistance, solvent resistance, transparency, and the like, as will be apparent from the examples described later.

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

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

  Synthesis Examples, Examples and Comparative Examples are shown below to describe the present invention more specifically. However, the present invention is not limited to the following examples.

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, 22 parts by weight of methacrylic acid, 23 parts by weight of dicyclopentanyl methacrylate, 5 parts by weight of acryloylmorpholine, 50 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane and 3 parts by weight of α-methylstyrene dimer were charged and the atmosphere was replaced with nitrogen. The stirring was started gently. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-1]. The obtained polymer solution had a solid content concentration of 31.1% by weight, a polymer weight average molecular weight of 17,200, and a molecular weight distribution (ratio of weight average molecular weight / number average molecular weight) of 1.9. . In addition, a weight average molecular weight and a number average molecular weight are polystyrene conversion average molecular weights measured using GPC (Gel permeation chromatography (HLC-8020 manufactured by Tosoh Corporation)).

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 13 parts by weight of methacrylic acid, 50 parts by weight of glycidyl methacrylate, 10 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane, 10 parts by weight of cyclohexylmaleimide, 10 parts by weight of acryloylmorpholine and 7 parts by weight of tetrahydrofurfuryl acrylate were charged. Stirring was started slowly while replacing. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 4 hours to obtain a polymer solution containing the copolymer [A-2]. The obtained polymer solution had a solid content concentration of 32.1% by weight, a weight average molecular weight of 18,200, and a molecular weight distribution of 1.8.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 11 parts by weight of methacrylic acid, 12 parts by weight of cyclohexylmaleimide, 9 parts by weight of α-methyl-p-hydroxystyrene, 50 parts by weight of glycidyl methacrylate, 10 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane, 5 parts by weight of acryloylmorpholine Parts, 3 parts by weight of tetrahydrofurfuryl methacrylate and 3 parts by weight of α-methylstyrene dimer were charged, and the mixture was gently stirred while replacing with nitrogen. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-3]. The resulting polymer solution had a solid content concentration of 32.4% by weight, a weight average molecular weight of 21,200, and a molecular weight distribution of 2.1.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 20 parts by weight of 3-ethyl-3-methacryloyloxymethyloxetane, 30 parts by weight of glycidyl methacrylate, 8 parts by weight of acryloylmorpholine, 12 parts by weight of tetrahydrofurfuryl acrylate and α-methylstyrene Stirring was started gently while charging 4.0 parts by weight of dimer and purging with nitrogen. The temperature of the solution was raised to 70 ° C. and heated at this temperature for 5 hours to obtain a polymer solution containing the copolymer [A-4]. The obtained polymer solution had a solid content concentration of 32.0% by weight, a weight average molecular weight of 20,100, and a molecular weight distribution of 1.9.

Comparative Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 23 parts by weight of methacrylic acid, 47 parts by weight of dicyclopentanyl methacrylate, 20 parts by weight of glycidyl methacrylate and 2.0 parts by weight of α-methylstyrene dimer were charged, and the mixture was gently stirred while replacing with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-1R]. The resulting polymer solution had a solid content concentration of 32.8% by weight, a weight average molecular weight of 24,000, and a molecular weight distribution of 2.3.

Comparative Synthesis Example 2
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether. Subsequently, 25 parts by weight of methacrylic acid, 35 parts by weight of dicyclopentanyl methacrylate, 40 parts by weight of 2-hydroxyethyl methacrylate and 2.0 parts by weight of α-methylstyrene dimer were charged, and gentle stirring was started while replacing with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-2R]. The obtained polymer solution had a solid content concentration of 32.8% by weight, the polymer had a weight average molecular weight of 25,000 and a molecular weight distribution of 2.4.

Example 1
Preparation of radiation sensitive resin composition Polymer solution containing copolymer [A-1] obtained in Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of copolymer [A-1]),
As component [B], 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 Condensation product with sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide -5-sulfonic acid ester) (20 parts by weight) and γ-methacryloxypropyltrimethoxysilane (5 parts by weight) were mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid concentration was 30% by weight. A solution (S-1) of a radiation sensitive resin composition was prepared by filtration through a 5 μm Millipore filter.

Evaluation of interlayer insulation film
(I) Formation of Patterned Thin Film After applying the composition solution (S-1) on a glass substrate using a spinner, the coating film was formed by prebaking on a hot plate at 80 ° C. for 3 minutes.
The coating film obtained above was irradiated with ultraviolet rays having an intensity at 365 nm of 10 mW / cm ² for 15 seconds using a predetermined pattern mask. Next, the film was developed with a 0.5% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute, and then rinsed with pure water for 1 minute. By these operations, unnecessary portions were removed.
The pattern formed above was irradiated with ultraviolet rays having an intensity at 365 nm of 10 mW / cm ² for 30 seconds, and then heated and cured in an oven at 220 ° C. for 60 minutes to obtain a patterned thin film having a thickness of 3 μm.
Further, except that the prebaking temperature was set to 90 ° C. and 100 ° C., the same operation as described above was performed to form three types of patterned thin films having different prebaking temperatures.

(II) Evaluation of resolution In the pattern-like thin film obtained in (I) above, the case where the extraction pattern (5 μm × 5 μm hole) was resolved was evaluated as “◯”, and the case where it was not resolved was evaluated as “X”. The results are shown in Table 1.
(III) Evaluation of heat-resistant dimensional stability In the above (I), the thin film pattern formed at a pre-baking temperature of 80 ° C. was heated in an oven at 220 ° C. for 60 minutes. Table 2 shows the rate of change in film thickness before and after heating. When the dimensional change rate at this time is within 5% before and after heating, the heat-resistant dimensional stability is good, and when the dimensional change rate exceeds 5%, it can be said to be defective.
(IV) Evaluation of Transparency In (I) above, the spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)) was used to measure the transmittance at 400 nm of the patterned thin film formed at a prebake temperature of 80 ° C. And measured for transparency. The results are shown in Table 2. At this time, when the transmittance is 90% or more, the transparency is good, and when the transmittance is less than 90%, the transparency is poor.
(V) Evaluation of heat-resistant discoloration In (I) above, a substrate having a patterned thin film formed at a pre-baking temperature of 80 ° C. is heated in an oven at 250 ° C. for 1 hour, and the change in transmittance of the patterned thin film before and after heating. Was used to evaluate heat discoloration. The evaluation results at this time are shown in Table 2. When the rate of change is less than 5%, the heat discoloration is good, and when it exceeds 5%, it can be said to be defective. The transmittance was determined in the same manner as (VI) transparency evaluation.

(VI) Evaluation of adhesion In (I) above, the adhesion of the patterned thin film formed at a pre-baking temperature of 80 ° C. was evaluated by a cross-cut peel test after a pressure cooker test (120 ° C., humidity 100%, 4 hours). did. The evaluation results at this time are shown in Table 2. The evaluation result was represented by the number of remaining grids out of 100 grids.
(VII) Evaluation of Storage Stability The composition solution was heated in an oven at 40 ° C. for 1 week, and the storage stability was evaluated by the change in viscosity before and after heating. The viscosity change rate at this time is shown in Table 1. When the rate of change is less than 5%, the storage stability is good, and when it is 5% or more, the storage stability is poor.
Evaluation of microlenses
(I) Formation of microlens A 6-inch silicon substrate was spin-coated with the above composition solution (S-1) to a thickness of 2.5 μm, and pre-baked on a hot plate at 70 ° C. for 3 minutes to form a coating film. Formed.
The coating film obtained above was irradiated with ultraviolet rays having an intensity at 436 nm of 10 mW / cm ² using a predetermined pattern mask. Next, after developing with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 25 ° C. for 1 minute, it was rinsed with pure water for 1 minute. By these operations, unnecessary portions were removed and a pattern was formed.
The pattern formed above was irradiated with 200 mJ / cm ^{2 of} ultraviolet light having an intensity of 10 mW / cm ² at 436 nm, then heated at 160 ° C. for 10 minutes, and then further heated at 230 ° C. for 10 minutes to melt-flow the pattern. A lens was formed.

(II) Evaluation of sensitivity Minimum irradiation capable of resolving the space line width of 0.8 μm line and space pattern (10 to 1) of the microlens pattern after melt flow obtained in (I) above. The amount is shown in Table 3. When this value is 100 mJ / cm ² or less, it can be said that the resolution is good and when the sensitivity exceeds 100 mJ / cm ² , the resolution is poor.
(III) Evaluation of transparency A patterned thin film was formed on a glass substrate in the same manner as (I) above.
For a glass substrate on which a microlens pattern after melt flow is formed, the transmittance at 400 nm is measured using a spectrophotometer (150-20 type double beam (manufactured by Hitachi, Ltd.)) to evaluate the transparency. It was. The transmittance at 400 nm at this time is shown in Table 3. When the transmittance is 90 to 100%, the transmittance is good, and when it is less than 90%, the transmittance is poor.

(IV) Evaluation of heat-resistant transparency The glass substrate having the patterned thin film formed in (III) above was heated in an oven at 250 ° C for 1 hour, and the heat-resistant transparency was evaluated by the change in the transmittance of the patterned thin film before and after heating. did. Table 3 shows the change rate of the transmittance at this time. When the rate of change is less than 5%, the heat-resistant transparency is good, and when it exceeds 5%, it can be said to be defective. The transmittance was determined in the same manner as in (III) transparency evaluation.
(V) Evaluation of adhesion The adhesion of the patterned thin film formed in the above (I) was evaluated by a cross-cut peel test after a pressure cooker test (120 ° C., humidity 100%, 4 hours). The evaluation results at this time are shown in Table 3. The evaluation result was represented by the number of remaining grids out of 100 grids.
(VII) Evaluation of solvent resistance A glass substrate having a patterned thin film formed in the same manner as in the above (III) was immersed in isopropyl alcohol at 50 ° C. for 10 minutes, and the change in film thickness was evaluated. Table 3 shows the rate of change at this time. When the rate of change is 0 to 5%, the solvent resistance is good, and when it exceeds 5% and when the film thickness is reduced by dissolution, the solvent resistance can be said to be poor.

Example 2
A polymer solution containing the copolymer [A-2] obtained in Synthesis Example 2 (corresponding to 100 parts by weight (solid content) of the copolymer [A-2]), and
As component [B], 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 Condensation product with sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide -5-sulfonic acid ester) (20 parts by weight) and γ-methacryloxypropyltrimethoxysilane (5 parts by weight) were mixed and dissolved in propylene glycol monomethyl ether acetate to a solid content concentration of 31% by weight. A solution (S-2) of a radiation sensitive resin composition was prepared by filtration through a 5 μm Millipore filter and evaluated. The results are shown in Tables 1-3.

Example 3
A polymer solution containing the copolymer [A-3] obtained in Synthesis Example 3 (corresponding to 100 parts by weight (solid content) of the copolymer [A-3]),
As component [B], 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 Condensation product with sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide 18 parts by weight of -5-sulfonic acid ester) and 5 parts by weight of γ-methacryloxypropyltrimethoxysilane were mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid concentration was 30% by weight. A solution (S-3) of a radiation sensitive resin composition was prepared by filtration through a 5 μm Millipore filter and evaluated. The results are shown in Tables 1-3.

Example 4
A polymer solution containing the copolymer [A-4] obtained in Synthesis Example 4 (corresponding to 100 parts by weight (solid content) of the copolymer [A-4]);
As component [B], 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 Condensation product with sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide -5-sulfonic acid ester) 30 parts by weight, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 5 parts by weight and γ-methacryloxy 5 parts by weight of propyltrimethoxysilane was mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid concentration was 31% by weight. , The solution of the radiation-sensitive resin composition (S-4) was prepared and filtered through a Millipore filter having a pore size 0.5 [mu] m, were evaluated. The results are shown in Tables 1-3.

Comparative Example 1
A polymer solution containing the copolymer [A-1R] obtained in Comparative Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of the copolymer [A-1R]);
As component [B], 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 Condensation product with sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide -5-sulfonic acid ester) (30 parts by weight) and γ-methacryloxypropyltrimethoxysilane (5 parts by weight) were mixed and dissolved in propylene glycol monomethyl ether acetate to a solid content concentration of 31% by weight. A solution (S-1R) of the radiation sensitive resin composition was prepared by filtration through a 5 μm Millipore filter and evaluated. The results are shown in Tables 1-3.

Comparative Example 2
A polymer solution containing the copolymer [A-2R] obtained in Comparative Synthesis Example 1 (corresponding to 100 parts by weight (solid content) of the copolymer [A-2R]),
As component [B], 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 mol) and 1,2-naphthoquinonediazide-5 Condensation product with sulfonic acid chloride (2 mol) (4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide 18 parts by weight of -5-sulfonic acid ester) and 5 parts by weight of γ-methacryloxypropyltrimethoxysilane were mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 31% by weight. A solution (S-2R) of a radiation sensitive resin composition was prepared by filtration through a 5 μm Millipore filter and evaluated. The results are shown in Tables 1-3.

Schematic diagram showing the shape of the microlens

Claims (7)

[A] (a1) at least one selected from the group of unsaturated carboxylic acids and unsaturated carboxylic anhydrides,
(A2) An unsaturated compound containing at least one of an epoxy group or an oxetanyl group (a3) Other than at least one selected from the group of acryloylmorpholine and methacryloylmorpholine (a4) (a1), (a2), (a3) A radiation-sensitive resin composition comprising a copolymer of an unsaturated compound and [B] 1,2-quinonediazide compound. The radiation-sensitive resin composition according to claim 1, which is used for forming an interlayer insulating film. A method for forming an interlayer insulating film, comprising the following steps in the order described below.
(1) The process of forming the coating film of the radiation sensitive resin composition of Claim 1 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) Development step, and (4) Heating step. An interlayer insulating film formed by the method according to claim 3. The radiation-sensitive resin composition according to claim 1, which is used for forming a microlens. A method for forming a microlens comprising the following steps in the order described below.
(1) The process of forming the coating film of the radiation sensitive composition of Claim 1 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) Development step, and (4) Heating step. A microlens formed by the method of claim 6.

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