KR20210125936A - Method for treating radiation-sensitive composition - Google Patents

Abstract

Provided is a method for treating a radiation-sensitive composition, capable of imparting high permeability to a radiation-sensitive composition and suppressing the generation of air bubbles while using an LED light source. The present invention provides the method for treating a radiation-sensitive composition comprising: a resin (A) which is a copolymer of a radically polymerizable compound (a) having an acid group, a radically polymerizable compound (b) having an epoxy group, and another radically polymerizable compound (c) and is soluble in an alkaline aqueous solution; and a radiation-sensitive acid-generating compound (B). The method includes a step (α) of irradiating the radiation-sensitive composition with ultraviolet rays having a main peak wavelength within the range of 375 nm or more and 395 nm or less from an LED element to improve the transmittance of the radiation-sensitive composition.

Description

A method of treating a radiation-sensitive composition {METHOD FOR TREATING RADIATION-SENSITIVE COMPOSITION}

The present invention relates to a method for treating a radiation-sensitive composition, and more particularly, to a bleaching treatment method for improving transmittance of a radiation-sensitive composition.

A display device such as a liquid crystal panel or an organic EL panel is provided with a fine semiconductor element corresponding to each pixel, and as an insulating material (resist material) in the element, a composition exhibiting a property of being sensitive to light (radiation sensitivity) is widely used. is being used

For example, in the manufacturing process of a display device, it is known to improve the light transmittance and durability (heat resistance) of the said pattern by irradiating ultraviolet-ray to the exposed and developed pattern after apply|coating and prebaking a radiation-sensitive composition. have. Thus, the process of improving the transmittance|permeability with respect to visible light by irradiating an ultraviolet-ray with respect to the patterned target film|membrane is called "bleaching process" in some cases. This treatment is caused by decomposing the photosensitive material contained in the radiation-sensitive composition with ultraviolet rays.

For example, in Patent Document 1 below, it is described that a resist pattern is subjected to a bleaching treatment by irradiating an i-ray, that is, an ultraviolet ray having a wavelength of 365 nm.

Japanese Patent Laid-Open No. 2017-037169

Lamps, such as a high-pressure mercury-vapor lamp, are generally used as the light source for bleaching processing. Since there is a description of "i-line" also in the said patent document 1, since a mercury spectrum is assumed, although there is no description on the text, it is understood that use of a high-pressure mercury-vapor lamp is planned.

On the other hand, with the technological progress of a solid-state light source in recent years, examination of the bleaching process using UV-LED is advancing.

However, according to the diligent research of the present inventors, when an LED light source is used for the bleaching process, the problem that the desired transmittance (bleaching ability) cannot be obtained and the problem that foaming occurs inside the radiation-sensitive composition tends to occur could see that

In view of the above problems, the present invention provides a method for treating a radiation-sensitive composition that can provide high transmittance to the radiation-sensitive composition while using an LED light source, and further suppress the generation of air bubbles. aim to

The present invention provides a method for treating a radiation-sensitive composition,

The radiation-sensitive composition,

A radically polymerizable compound (a) having an acid group, a radically polymerizable compound (b) having an epoxy group, and a resin (A) soluble in aqueous alkali solution which is a copolymer of another radically polymerizable compound (c);

having a radiation-sensitive acid-generating compound (B),

A step (α) of improving the transmittance of the radiation-sensitive composition by irradiating the radiation-sensitive composition with ultraviolet rays having a main peak wavelength in the range of 375 nm or more and 395 nm or less from the LED element; do it with

When a bleaching treatment is performed on a film comprising a radiation-sensitive composition, as described above in the section of “Problems to be Solved”, a mercury lamp has conventionally been used. This is because it has been empirically known that a radiation-sensitive acid-generating compound exhibits high photosensitivity to 365 nm (i-ray), which is one of the peak wavelengths of light emitted from a mercury lamp.

The present inventors, from the above findings, first prepare an LED element having a main peak wavelength of around 365 nm, and apply ultraviolet rays emitted from the LED element to a film to be treated (hereinafter, appropriately referred to as "target film") comprising a radiation-sensitive composition. film") and subjected to bleaching treatment. Then, it was confirmed that the transmittance|permeability of the target film|membrane after such a process was lower than a desired value, and satisfactory permeation|transmission performance was not implement|achieved.

In addition, in the above, the expression "near 365 nm" with the main peak wavelength is an LED element having a main peak wavelength of 365 nm, even if it is obtained as an LED element, there is individual difference between the elements, and the main peak wavelength is approximately ±10 nm. This is because an error may occur during manufacturing.

In addition, it was confirmed that some air bubbles were present in the target film after the treatment. Since the target film containing the radiation-sensitive composition functions as an insulating film in a liquid crystal panel or an organic EL panel as described above, when the air bubbles are visually recognized from the light extraction surface side, the display performance of the device It is thought to affect etc.

In contrast, the present inventors prepared an LED element emitting light with a main peak wavelength of 375 nm or more and 395 nm or less, in which the wavelength is intentionally shifted to the longer wavelength side than the i-line (365 nm), and the ultraviolet rays from the LED element are An attempt was made to irradiate the target film. Then, surprisingly, it was found that the transmittance was improved and the amount of bubbles generated in the film could be significantly reduced compared to the case of irradiating the ultraviolet rays from the LED element having a main peak wavelength around 365 nm. This fact is an extremely surprising effect in view of the prior knowledge that radiation-sensitive acid-generating compounds including quinonediazide compounds exhibit high photosensitivity at 365 nm.

In this specification, the "main peak wavelength" refers to the wavelength with the highest light intensity on the spectrum.

The ultraviolet rays may have a half width of 20 nm or less.

By using the LED element emitting ultraviolet rays exhibiting a spectrum having a half maximum width of 20 nm, the light intensity of the 365 nm component contained in the ultraviolet rays can be sufficiently made low with respect to the light intensity of the main peak wavelength. Thereby, the improvement of a transmittance|permeability and suppression of generation|occurrence|production of a bubble are compatible.

The ultraviolet light may have a light intensity at a wavelength of 365 nm that is less than 10% of the light intensity at the main peak wavelength.

The step (α) may be a step of irradiating the radiation-sensitive composition with the ultraviolet rays through a filter that cuts light with a wavelength of 365 nm or less from the LED element.

The radiation-sensitive acid generating compound (B) may be a 1,2-quinonediazide compound.

The proportion of the radiation-sensitive acid-generating compound (B) in the radiation-sensitive composition may be 15 to 30 parts by mass with respect to 100 parts by mass of the resin (A).

The other radically polymerizable compound (c) is a (meth)acrylic acid ester having an alicyclic structure, a (meth)acrylic acid ester having an aromatic ring structure, an aromatic vinyl compound, an N-substituted maleimide compound, and a heterocyclic structure. It is good also as a structural unit derived from at least 1 sort(s) of monomer chosen from the group which consists of vinyl compounds.

In the compound constituting the resin, (meth)acrylic acid ester having an alicyclic structure, (meth)acrylic acid ester having an aromatic ring structure, an aromatic vinyl compound, an N-substituted maleimide compound, or a vinyl compound having a heterocyclic structure, etc. By including a cyclic structure, the effect|action which suppresses foaming at the time of ultraviolet irradiation can be heightened.

The said resin (A) is good also as a thing containing the structural unit containing a crosslinkable group. According to such a structure, the effect|action which suppresses foaming at the time of ultraviolet irradiation can further be heightened.

In addition, the treatment method of the radiation-sensitive composition,

A step (β1) of forming an underlying film;

a step (β2) of applying the radiation-sensitive composition to the upper layer of the base film formed by the step (β1);

After the step (β2), a step (β3) of sequentially performing each treatment of prebaking, exposure, and development on the radiation-sensitive composition;

The step (α) may be performed after the step (β3).

According to the above method, it is possible to improve transmittance with respect to a patterned insulating film formed in, for example, a display device.

According to the method of this invention, generation|occurrence|production of the bubble in a film|membrane is suppressed while providing high transmittance|permeability with respect to the target film|membrane which consists of a radiation-sensitive composition while using an LED light source.

1 is a view schematically showing one step of a method for treating a radiation-sensitive composition according to the present invention.
Fig. 2 is a diagram showing an example of the spectrum of ultraviolet rays emitted from the LED element.
Fig. 3 is a diagram in which the spectrum of ultraviolet rays having main peak wavelengths of 365 nm, 385 nm and 405 nm is superimposed.
4 is another view schematically showing one step of the method for treating the radiation-sensitive composition according to the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows typically one process of the processing method of the radiation-sensitive composition which concerns on this invention. However, FIG. 1 is schematically illustrated to the last, and the actual dimensional ratio and the dimensional ratio on the drawing do not necessarily coincide.

The film to be processed (hereinafter, referred to as "target film 1") is laminated on the upper layer of the layer 2 and subjected to a patterning process. The target film 1 comprises a material (radiation-sensitive composition) exhibiting radiation sensitivity. A detailed description of the material is given below. In addition, the layer 2 corresponds to "underlying film".

The target film 1 is irradiated with ultraviolet rays L1 having a main peak wavelength of 375 nm or more and 395 nm or less from the light source 3 on which the LED element 4 is mounted (corresponding to the step (α)). 2 : shows an example of the spectrum of the ultraviolet-ray L1. The spectrum shown in FIG. 2 corresponds to the case where the LED element 4 is an element emitting an ultraviolet ray L1 having a main peak wavelength of 385 nm. In the spectrum shown in FIG. 2, the full width at half maximum (dλ) is 13 nm. Moreover, it is preferable that the half width (dλ) is 20 nm or less.

The LED element 4 is realized by including, for example, an active layer having a well layer made of InGaN or AlInGaN and a barrier layer made of InGaN or AlInGaN having a lower In composition ratio than that of GaN or the well layer.

By irradiating the target film 1 with the ultraviolet L1 having a main peak wavelength of 375 nm or more and 395 nm or less, the transmittance of the target film 1 is improved and the generation of bubbles in the target film 1 is suppressed. This point will be described later with reference to Examples.

Next, the material of the target film 1 will be described.

The target film 1 contains a radiation-sensitive composition. This radiation-sensitive composition contains a resin (A) and a radiation-sensitive acid generating compound (B), and contains other compounding agents (C) as needed.

《Resin (A)》

Resin (A) has an alkali-soluble group, Preferably it consists of a material which shows the property of hardening by heating. Such resin (A) is obtained by radical copolymerizing the radically polymerizable compound (a) which has an acidic radical, and the radically polymerizable compound (b) which has an epoxy group together with another radically polymerizable compound (c) in a solvent.

As a specific example of the radically polymerizable compound (a) which has an acidic radical,

As a monomer which comprises the structural unit which has a carboxy group, For example, unsaturated monocarboxylic acids, such as (meth)acrylic acid crotonic acid and 4-vinyl benzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid;

Examples of the monomer constituting the structural unit having a sulfonic acid group include vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, (meth)acryloyloxyethylsulfonic acid and the like;

As a monomer constituting the structural unit having a phenolic hydroxyl group, for example, 4-hydroxystyrene, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, hydroxyphenyl (meth)acryl rate etc. are mentioned, respectively. Moreover, maleimide can be used as a monomer.

Examples of the radically polymerizable compound (b) having an epoxy group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2- (3,4-epoxycyclohexyl)ethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, (3-methyloxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl) (meth)acrylate, (oxetan-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate etc. are mentioned. In addition, in this specification, it is also called "epoxy group" including oxiranyl group and oxetanyl group.

When obtaining the resin (A) (hereinafter, referred to as "copolymer (I)"), a binary system of the radically polymerizable compound (a) having an acid group and (b) having an epoxy group In the radical polymerization in , a radically polymerizable compound having an epoxy group and an acid group reacts during a polymerization reaction, crosslinking may occur, and the polymerization system may be gelled.

Then, in order to obtain a copolymer (I), it is appropriate to use another radically polymerizable compound (c) as a 3rd component, and to suppress reaction with the radically polymerizable compound which has an epoxy group and an acidic radical. As such other radically polymerizable compound (c), (meth)acrylic acid alkyl ester, (meth)acrylic acid cycloalkyl ester, (meth)acrylic acid aromatic ester, aromatic vinyl compound, N-substituted maleimide compound, heterocyclic-containing vinyl compound, A conjugated diene compound, a nitrogen-containing vinyl compound, an unsaturated dicarboxylic acid dialkyl ester compound, etc. are mentioned.

As a specific example of another radically polymerizable compound (c),

As (meth)acrylic acid alkyl ester, (meth)acrylate methyl, (meth)acrylate, (meth)acrylic acid n-propyl, (meth)acrylic acid isopropyl, (meth)acrylate butyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid n-lauryl, (meth)acrylic acid n-stearyl and the like;

As (meth)acrylic acid ester having an alicyclic structure, (meth)acrylic acid cyclohexyl, (meth)acrylic acid 2-methylcyclohexyl, (meth)acrylic acid dicyclopentanyl, (meth)acrylic acid tricyclo[5.2.1.0 ^2,5 ]Decan-8-yloxyethyl, (meth)acrylic acid isoboronyl, etc.;

As (meth)acrylic acid ester which has an aromatic ring structure, (meth)acrylic acid phenyl, (meth)acrylic acid benzyl, etc.;

As the aromatic vinyl compound, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-t-butyl-2 -Methylstyrene, divinylbenzene, trivinylbenzene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethyl styrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, diphenylethylene, vinylnaphthalene, vinylpyridine, etc.;

As the N-substituted maleimide compound, N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4 -Ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, N-adamantylmaleimide, N-phenylmaleimide Mid, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-benzylmaleimide mide, N-naphthyl maleimide, and the like;

As a vinyl compound having a heterocyclic structure, (meth)acrylic acid tetrahydrofurfuryl, (meth)acrylic acid tetrahydropyranyl, (meth)acrylic acid 5-ethyl-1,3-dioxan-5-ylmethyl, (meth) 5-methyl-1,3-dioxan-5-ylmethyl acrylate, (meth)acrylic acid (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl, 2-(meth)acrylo yloxymethyl-1,4,6-trioxaspiro [4,6] undecane, (meth)acrylic acid (γ-butyrolacton-2-yl), (meth)acrylic acid glycerin carbonate, (meth)acrylic acid (γ -lactam-2-yl), N-(meth)acryloyloxyethylhexahydrophthalimide, etc.;

As the conjugated diene compound, 1,3-butadiene, isoprene, etc.;

As a nitrogen-containing vinyl compound, (meth)acrylonitrile, (meth)acrylamide, etc.;

Examples of the unsaturated dicarboxylic acid dialkyl ester compound include diethyl itaconic acid and the like. Moreover, as another monomer, in addition to the above, monomers, such as vinyl chloride, vinylidene chloride, and vinyl acetate, are mentioned, for example.

Another radically polymerizable compound (c) is from the viewpoint of controlling the glass transition temperature of the polymer component and suppressing the melt flow at the time of thermosetting, among them, (meth)acrylic acid alkyl ester, (meth)acrylic acid having an alicyclic structure It is a structural unit derived from at least one monomer selected from the group consisting of esters, (meth)acrylic acid esters having an aromatic ring structure, aromatic vinyl compounds, N-substituted maleimide compounds, and vinyl compounds having a heterocyclic structure. desirable.

Moreover, the copolymerization ratio of the radically polymerizable compound (a) which has an acidic radical of copolymer (I) becomes like this. Preferably it is 5-40 mass %, Especially preferably, it is 10-30 mass %. When it is less than 5 mass %, since the copolymer obtained becomes difficult to melt|dissolve in aqueous alkali solution, it is easy to generate|occur|produce an undeveloped part, and it is difficult to make sufficient pattern. Conversely, when it exceeds 40 mass %, the solubility of the obtained copolymer in aqueous alkali solution becomes too large, and it becomes difficult to prevent the dissolution of a radiation-irradiated part, ie, film|membrane decrease phenomenon.

The copolymerization ratio of the radically polymerizable compound (b) having an epoxy group in the copolymer (I) is preferably 10 to 70 mass%, particularly preferably 20 to 50 mass%. When it is less than 10% by mass, the reaction with the acid generated by irradiating the radically polymerizable compound (a) or the radiation-sensitive acid-generating compound (B) having an acid group with radiation hardly proceeds sufficiently, and the heat resistance of the pattern obtained from the composition is sufficient. It becomes difficult to become Moreover, when it exceeds 70 mass %, it will become easy to generate|occur|produce a problem in the storage stability of copolymer (I).

The copolymerization ratio of another radically polymerizable compound (c) of a copolymer (I) becomes like this. Preferably it is 10-70 mass %, Especially preferably, it is 30-50 mass %. If it is less than 10 mass %, gelation will become easy to occur during a polymerization reaction. Moreover, when it exceeds 70 mass %, since the quantity of the radically polymerizable compound (b) which has an epoxy group and the radically polymerizable compound (a) which has an acidic group becomes relatively small, the solubility of the resin with respect to aqueous alkali solution decreases, The heat resistance of the pattern obtained from the composition may become insufficient.

As a solvent used when superposing|polymerizing copolymer (I), For example, Alcohol, such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether; cellosolve esters such as methyl cellosolve acetate; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; In addition, aromatic hydrocarbons, ketones, esters, etc. are mentioned.

As a polymerization catalyst in radical polymerization, a normal radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile) ), azo compounds such as 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); and organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate and 1,1-bis-(t-butylperoxy)cyclohexane, and hydrogen peroxide. When using a peroxide as a radical polymerization initiator, it is good also as a redox type initiator by combining a reducing agent.

The molecular weight of the above copolymer (I) and its distribution are not particularly limited as long as the solution of the radiation-sensitive composition forming the target film 1 can be uniformly applied.

《Radiation sensitive acid generating compound (B)》

The radiation-sensitive acid-generating compound (B) is a compound that generates an acid when irradiated with light. As an example, the radiation-sensitive acid generating compound is a quinonediazide compound (B1). The quinonediazide compound (B1) is composed of a compound having one or more phenolic hydroxyl groups and 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid. It is an ester compound.

More specifically, the quinonediazide compound (B1) is 1,2-benzoquinonediazidesulfonic acid ester, 1,2-naphthoquinonediazidesulfonic acid ester, 1,2-benzoquinonediazidesulfonic acid amide and 1,2-quinonediazide compounds such as 1,2-naphthoquinonediazidesulfonic acid amide.

Among these, the quinonediazide compound (B1) is a compound having good transparency in the visible region of 400 to 800 nm after irradiation with radiation, for example, 2,3,4-trihydroxybenzophenone, 2,3, 4,4'-tetrahydroxybenzophenone, 3'-methoxy-2,3,4,4'-tetrahydroxybenzophenone, 2,2',5,5'-tetramethyl-2',4, 4'-trihydroxytriphenylmethane, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol and 2,4,4- 1,2-benzoquinonediazide-4-sulfonic acid esters such as trimethyl-2',4',7-trihydroxy-2-phenylflavan, 1,2-naphthoquinonediazide-4-sulfonic acid Preferred examples include esters or 1,2-naphthoquinonediazide-5-sulfonic acid esters.

A quinonediazide compound (B1) may be used individually by 1 type, and may use 2 or more types together.

In addition, the radiation-sensitive acid generating compound (B) is not limited to a quinonediazide compound (B1), as long as it is a compound which produces|generates an acid by irradiating light, Another acid generator (B2) may be sufficient. Examples of the acid generator (B2) include an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid compound, a sulfonimide compound, and a diazomethane compound.

The addition amount of the radiation-sensitive acid generating compound (B) is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, particularly preferably 15 to 100 parts by mass of the resin (A). 30 parts by mass. If it is less than 5 parts by mass, the amount of acid produced by absorbing light is small, so there is no difference in solubility in aqueous alkali solution before and after light irradiation, patterning becomes difficult, and the epoxy group of the copolymer (I) Also in the reaction, since the amount of the acid involved is reduced, there is a possibility that a problem may arise in the heat resistance of the pattern obtained from the composition. In addition, when it exceeds 100 parts by mass, most of the added radiation-sensitive acid-generating compound still remains in its form after a short period of irradiation. have.

In particular, by setting the amount of the radiation-sensitive acid generating compound (B) to be added within the range of 15 to 30 parts by mass with respect to 100 parts by weight of the resin (A), the effect of suppressing the amount of bubbles generated after the step (α) is performed is enhanced. can

《Other compounding agents (C)》

From a viewpoint of improving the hardness and heat resistance of the target film 1, it is also possible to use together the (meth)acrylic compound, an epoxy compound, etc. which are shown below.

A (meth)acrylic compound is used in order to improve the hardness, heat resistance, etc. of the coating film formed by superposing|polymerizing by (meth)acrylic compound itself at the time of final heating. As a (meth)acrylic compound, monofunctional (meth)acrylate, bifunctional (meth)acrylate, and trifunctional or more than trifunctional (meth)acrylate are mentioned. The epoxy compound is used in order to adjust the reaction point with the above-mentioned copolymer (I) and the acid produced|generated from the radiation-sensitive acid-generating compound by irradiation at the time of final heating.

Examples of the epoxy compound include bisphenol A epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, heterocyclic An epoxy resin etc. are mentioned. Among these, a phenol novolak-type epoxy resin, a cresol novolak-type epoxy resin, a cyclic aliphatic epoxy resin, and a glycidyl ester-type epoxy resin are preferable from the point of being hard to color even after heat processing.

As a compounding agent (C), you may contain a crosslinkable compound. The crosslinkable compound is, for example, an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure), a methylol group, a vinyl group, a (meth)acryloyl group, a cyclic carbonate group, etc. compounds having a crosslinkable group of

Among the crosslinkable groups, an oxiranyl group (epoxy group), oxetanyl group, methylol group, and combinations thereof are preferable, an oxiranyl group and an oxetanyl group are more preferable, and an oxiranyl group is still more preferable.

As the compounding agent (C), a surfactant may be included. As surfactant, a fluorine-type surfactant, silicone type surfactant, and other surfactant can be used, for example.

The radiation-sensitive composition contained in the target film 1 can be easily prepared by uniformly mixing each component described above. Upon mixing, it is provided for use in the form of a solution, usually dissolved in a suitable solvent. As the solvent to be used, a solvent that can uniformly dissolve the copolymer (I) and the radiation-sensitive acid-generating compound (B) and does not react with each component is used.

As such a solvent, For example, alcohols, such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone; Ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate and esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl acetate, and butyl acetate.

Further, N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether , dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-buty High boiling point solvents, such as lolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate, can also be added.

Among these solvents, from the viewpoint of solubility, reactivity with each component, and easy formation of a coating film, glycol ethers such as ethylene glycol monoethyl ether; ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; esters such as ethyl 2-hydroxypropionate; diethylene glycols such as diethylene glycol monomethyl ether and diethylene glycol methyl ethyl ether; Propylene glycol alkyl ether acetates, such as propylene glycol methyl ether acetate, are suitable.

In addition, in the preparation of the composition solution, for example, a solution of the copolymer (I), a solution of a radiation-sensitive acid generating compound, and a solution of other compounding agents are separately prepared, and these solutions are prepared immediately before use. It can also be mixed in proportions. The composition solution prepared as mentioned above can also be used for use, after filtering using the membrane filter etc. with a pore diameter of 0.2 micrometer.

When producing the target film 1, a desired coating film is formed by applying the above-described composition solution to a predetermined substrate surface (the upper surface of the layer 2 in FIG. 1) and removing the solvent by heating. The coating method to the substrate surface is not particularly limited, and for example, various methods such as a spray method, a roll coating method, and a spin coating method can be adopted.

Although the heating conditions of the coating film of a radiation-sensitive composition change with the kind of each component, a compounding ratio, etc., it is about 5 to 15 minutes at 70-90 degreeC normally. Next, the obtained coating film is irradiated with ultraviolet rays through a mask of a predetermined pattern, then developed using a developer, and unnecessary portions are removed to form a pattern. 1, the coating film (target film 1) after patterning is shown.

Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethyl Amine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo(5.4.0)-7-undecene, 1,5 Aqueous solutions of alkalis such as -diazabicyclo(4.3.0)-5-nonane can be used. Also, 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 may be used as a developing solution.

The development time is usually 30 to 180 seconds, and the development method may be any of a liquid accumulation method, a dipping method, and the like. After image development, an unnecessary part can be removed and a pattern can be formed by performing running water washing|cleaning for 30 to 90 second and air-drying with compressed air or compressed nitrogen. Then, for example, by irradiating an ultraviolet-ray, the acid-generating compound remaining in the pattern which is an unexposed part is changed into an acid. In addition, using a heating device such as a hot plate or oven, at a predetermined temperature, for example, 150 to 250 ° C. for a predetermined time, for example, 5 to 30 minutes on a hot plate, 30 to 90 minutes if in an oven, By heat-treating, the target film 1 excellent in heat resistance, transparency, hardness, etc. can be obtained.

[Example]

Next, the present invention will be more specifically described by way of examples, but the present invention is not limited by these examples. In addition, below, unless otherwise indicated, a part shows "mass part".

[Synthesis Example 1] (Synthesis of Copolymer (I-1))

Into a flask equipped with a cooling tube and a stirrer, 10 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate (PGMEA) were placed. Then, 15 parts of methacrylic acid, 20 parts of glycidyl methacrylate, 15 parts of 3,4-epoxycyclohexylmethyl methacrylate, and 50 parts of styrene are put, and after nitrogen substitution, the temperature of the solution is lowered while stirring slowly. The polymer solution containing the copolymer (I-1) which is an alkali-soluble resin was obtained by raising to 70 degreeC, and holding this temperature for 5 hours and superposing|polymerizing. The obtained polymer was reprecipitated in hexane and purified by filtration and vacuum drying. The copolymer (I-1) was dissolved in PGMEA to obtain a polymer concentration of 30% by mass solution. The weight average molecular weight (Mw) of this copolymer (I-1) was 10,000, and the weight average molecular weight (Mw)/number average molecular weight (Mn) was 2.3.

[Synthesis Examples 2 to 4] (Synthesis of copolymers (I-2) to (I-4))

Polymer solutions each containing copolymers (I-2) to (I-4) were obtained in the same manner as in Synthesis Example 1 except that each component of the type and compounding amount (parts by mass) shown in Table 1 was used. In Table 1, "-" represents that the corresponding component is not used.

The meaning of each symbol in Table 1 is as follows.

MA: methacrylic acid

GMA: glycidyl methacrylate

ST: Styrene

M-100:3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100 manufactured by Daicel Co., Ltd.)

DCM: dicyclofentanyl methacrylic acid

CHMI:N-Cyclohexylmaleimide

PMI:N-phenylmaleimide

PIPE:p-isopropenylphenol

OXMA: (3-ethyloxetan-3-yl)methyl methacrylate

[Ingredients of the radiation-sensitive composition]

The copolymer (I) (resin (A)), the radiation-sensitive acid-generating compound (B), and the organic solvent (C) as other compounding agents used in the preparation of the radiation-sensitive compositions of Examples and Comparative Examples are shown below.

<Copolymer (I)>

Copolymer I-1 to I-4: Copolymers (I-1) to (I-4) synthesized in Synthesis Examples 1-4

<Radiation-sensitive acid-generating compound (B)>

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

B-2: Condensate of 1,1,1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol)

<Organic solvent (C)>

C-1: diethylene glycol methyl ethyl ether (EDM)

C-2: propylene glycol monomethyl ether acetate (PGMEA)

[evaluation]

A target film 1 was prepared using the radiation-sensitive compositions of Examples and Comparative Examples, and the following items were evaluated.

<Example 1>

30 parts of a radiation-sensitive acid generating compound (B-1) was mixed with the 30 mass % density|concentration polymer solution containing copolymer (I-1) based on 100 parts of copolymer (I-1). Further, the obtained mixture was dissolved in an organic solvent (C-1) so that the concentration of all components other than the solvent was 30% by mass, and then filtered through a membrane filter having a pore diameter of 0.2 µm to prepare a radiation-sensitive composition.

<Examples 2 to 9, Comparative Examples 1 to 4>

Except having used each component of the kind shown in following Table 2, it operated similarly to Example 1, and the radiation-sensitive composition of Examples 2-9 and Comparative Examples 1-4 was prepared.

<Evaluation of bubbles>

On a silicon substrate, the radiation-sensitive compositions of Examples and Comparative Examples shown in Table 2 below were applied using a spinner, and then prebaked on a hot plate at 90° C. for 2 minutes to form a coating film having a thickness of 6.0 µm. Then, it developed by the liquid accumulation method in 23 degreeC for 60 second in the tetramethylammonium hydroxide aqueous solution of 2.38 mass % density|concentration.

Then, after performing 1 minute running-water washing with ultrapure water, drying was performed, and the board|substrate for foam evaluation which simulated the target film|membrane 1 was created. About this board|substrate for evaluation, the ultraviolet-ray L1 of the wavelength described in Table 2 was irradiated from the light source 3 which mounted the LED element 4 at the illumination intensity of 2000 mW/cm<^2> , and exposure amount 600mJ/cm<^2>.

After irradiating the ultraviolet-ray (L1), 6 steps of visual evaluation were performed about the bubble on the coating-film surface based on the following reference|standard.

(Evaluation standard)

0… The occurrence of air bubbles could not be confirmed.

One… Bubbles were partially confirmed at the end of the coating film.

2… Bubbles were confirmed all over the edge of the coating film.

3… Bubbles were partially confirmed in the central part of the coating film.

4… In the central part of the coating film, air bubbles were confirmed all over.

5… In the central part of the coating film, while bubbles were confirmed all over, the defect generate|occur|produced in a part of the coating film.

Further, as described above, since the coating film is applied by spin coating, the edge of the substrate for evaluation is slightly thicker than the central portion. Since bubbles are more likely to occur as the film thickness is thicker, it can be judged that the occurrence of bubbles in the central portion of the coating film, which is a region having a relatively thin film thickness, is a situation in which bubbles are more likely to occur.

<Evaluation of transmittance>

On a glass substrate ("Corning 7059" by Corning), the radiation-sensitive compositions of Examples and Comparative Examples shown in Table 2 below were applied using a spinner, and then pre-baked on a hot plate at 90° C. for 2 minutes to have a film thickness of 3.0 A coating film of μm or a film thickness of 6.0 μm was formed. Then, it developed by the liquid accumulation method in 23 degreeC for 60 second in the tetramethylammonium hydroxide aqueous solution of 2.38 mass % density|concentration.

Next, after performing running water washing|cleaning for 1 minute with ultrapure water, it dried and created the board|substrate for evaluation in which the cured film which simulated the target film 1 was formed. About this board|substrate for evaluation, the ultraviolet-ray L1 of the wavelength described in Table 2 was irradiated from the light source 3 in which the LED element 4 was mounted at the illumination intensity of 2000 mW/cm<^2> , and exposure amount 600mJ/cm<^2>. Then, it heated at 230 degreeC for 30 minutes. This heating is performed for the purpose of accelerating the crosslinking reaction (curing) of the crosslinking component present in the target film 1 .

With respect to the substrate for evaluation, a spectrophotometer (“150-20 double beam” manufactured by Hitachi, Ltd.) was used to measure the light transmittance in a wavelength range of 400 nm to 800 nm, and for each glass substrate evaluation substrate, a wavelength of 400 nm to 800 nm The lowest value of the light transmittance in the range (also referred to as the lowest light transmittance) was evaluated.

Moreover, the same evaluation was performed about the board|substrate for evaluation produced by the same method with the film thickness of a coating film being 6.0 micrometers using the radiation-sensitive composition of the Example and the comparative example shown in following Table 2.

In addition, the transmittance before ultraviolet (L1) irradiation of the evaluation substrate manufactured with the coating film thickness of 3.0 µm was 70%, and the ultraviolet (UV) light ( L1) The transmittance|permeability in before irradiation was 52 %.

Table 2 shows the evaluation results of the radiation-sensitive compositions of Examples 1 to 9 and Comparative Examples 1 to 4, and the target film 1 produced using the composition.

Fig. 3 is a diagram in which spectra of ultraviolet rays L1 having main peak wavelengths of 365 nm, 385 nm and 405 nm emitted from the light source 3 used in each Example or Comparative Example are superimposed. In the example, the ultraviolet L1 was irradiated to the substrate for evaluation from the light source 3 mounted with the LED element 4 having a main peak wavelength of 385 nm. Moreover, in the comparative example, separately from the light source 3 used in the Example, the light source 3 which mounted the LED element 4 whose main peak wavelength is 365 nm, or the light source 3 which mounted the LED element 4 of 405 nm ( 3) was prepared, and the ultraviolet-ray L1 was irradiated with respect to the board|substrate for evaluation from each light source 3.

According to Table 2, comparing Example 1, Comparative Example 1, and Comparative Example 2, in which the radiation-sensitive composition is formed of the same material composition, the main peak wavelength is 365 nm or 405 nm ultraviolet (L1) irradiated Compared to the case (Comparative Example 1, Comparative Example 2), when the ultraviolet L1 having a main peak wavelength of 385 nm is irradiated (Example 1), regardless of the film thickness of the target film 1, the transmittance is high, It turns out that foaming in a film|membrane is suppressed.

Similarly, according to Table 2, comparing Example 3, Comparative Example 3, and Comparative Example 4, in which the radiation-sensitive composition is formed with the same material composition, the ultraviolet (L1) having a main peak wavelength of 365 nm or 405 nm is Compared to the irradiated case (Comparative Example 1, Comparative Example 2), when the ultraviolet L1 having a main peak wavelength of 385 nm was irradiated (Example 1), regardless of the film thickness of the target film 1, the transmittance was high, and it turns out that foaming in a film|membrane is suppressed.

Further, in any one of Examples 1 to 9, which were prepared by appropriately changing the composition of the radiation-sensitive composition, the main peak wavelength was irradiated with ultraviolet (L1) of 385 nm, so that the film thickness of the target film 1 was correlated. It turns out that the transmittance|permeability is high and foaming in a film|membrane is suppressed.

In addition, the generation of bubbles in the target film 1 by irradiating the target film 1 containing the radiation-sensitive composition with ultraviolet rays L1, for example, the reaction of the following formula (1) occurs, , it is thought to originate from the generation of nitrogen gas. The following formula (1) shows the reaction when the naphthoquinonediazide compound constituting the radiation-sensitive acid generating compound (B) is irradiated with ultraviolet rays (L1) (indicated by hν in the formula (1) below). .

The reaction of the formula (1) is likely to occur when the naphthoquinonediazide compound is irradiated with ultraviolet rays of a wavelength showing high photosensitivity. That is, in the present invention, by intentionally irradiating the target film 1 containing the radiation-sensitive acid-generating compound (B) with ultraviolet rays (L1) in a wavelength band in which the photosensitivity is slightly lowered, the reaction of the formula (1) is It is considered that the progress is slowed down, thereby reducing the production rate of nitrogen gas. And, according to the results in Table 2, it was confirmed that the transmittance of the target film 1 was improved even when irradiated with ultraviolet light L1 in a wavelength band where the photosensitivity slightly decreased, here, the main peak wavelength is 385 nm.

In addition, as described above in the section of "Means for Solving Problems", the LED element 4 has individual differences within ±10 nm with respect to the main peak wavelength depending on the precision at the time of manufacture or the environment at the time of use. It is thought to exist. In view of the above circumstances, by irradiating the target film 1 with ultraviolet rays L1 having a main peak wavelength in the range of 375 nm or more and 395 nm or less from the LED element 4, the transmittance of the target film 1 is similar to that of each embodiment. It turns out that improvement and suppression of foaming are compatible.

[Separate embodiment]

As shown in FIG. 4 , the light source 3 is equipped with a filter 5 that cuts light with a wavelength of 365 nm or less, and the ultraviolet L1 emitted from the LED element 4 is emitted by the filter 5 with a wavelength The light of 365 nm or less may be irradiated to the target film 1 in a cut state. The filter 5 is constituted of, for example, a dielectric multilayer film.

1: target film
2: Layer (lower layer of target film)
3: light source
4: LED element
5: filter
L1: Ultraviolet

Claims (21)

A method of treating a radiation-sensitive composition comprising:
The radiation-sensitive composition,
A radically polymerizable compound (a) having an acid group, a radically polymerizable compound (b) having an epoxy group, and a resin (A) soluble in aqueous alkali solution which is a copolymer of another radically polymerizable compound (c);
having a radiation-sensitive acid-generating compound (B),
A step (α) of improving the transmittance of the radiation-sensitive composition by irradiating the radiation-sensitive composition with ultraviolet rays having a main peak wavelength in the range of 375 nm or more and 395 nm or less from the LED element; A method of treating a radiation-sensitive composition comprising: The method according to claim 1,
The ultraviolet rays have a half maximum width of 20 nm or less. The method according to claim 1,
The ultraviolet light has a light intensity at a wavelength of 365 nm that is less than 10% of the light intensity at the main peak wavelength. 3. The method according to claim 2,
The ultraviolet light has a light intensity at a wavelength of 365 nm that is less than 10% of the light intensity at the main peak wavelength. 4. The method according to claim 3,
The said process (α) is a process of irradiating the said ultraviolet-ray to the said radiation-sensitive composition through a filter which cuts the light of wavelength 365nm or less from the said LED element, The treatment method of the radiation-sensitive composition characterized by the above-mentioned. 5. The method according to claim 4,
The said process (α) is a process of irradiating the said ultraviolet-ray to the said radiation-sensitive composition through a filter which cuts the light of wavelength 365nm or less from the said LED element, The treatment method of the radiation-sensitive composition characterized by the above-mentioned. 7. The method according to any one of claims 1 to 6,
The radiation-sensitive acid-generating compound (B) is a 1,2-quinonediazide compound. 7. The method according to any one of claims 1 to 6,
The proportion of the radiation-sensitive acid-generating compound (B) in the radiation-sensitive composition is 15 to 30 parts by mass with respect to 100 parts by mass of the resin (A). 7. The method according to any one of claims 1 to 6,
The other radically polymerizable compound (c) is a (meth)acrylic acid ester having an alicyclic structure, a (meth)acrylic acid ester having an aromatic ring structure, an aromatic vinyl compound, an N-substituted maleimide compound, and a heterocyclic structure. A method for treating a radiation-sensitive composition, characterized in that it is a structural unit derived from at least one monomer selected from the group consisting of vinyl compounds. 7. The method according to any one of claims 1 to 6,
A step (β1) of forming an underlying film;
a step (β2) of applying the radiation-sensitive composition to the upper layer of the base film formed by the step (β1);
After the step (β2), a step (β3) of sequentially performing each treatment of prebaking, exposure, and development on the radiation-sensitive composition;
The method for treating a radiation-sensitive composition, wherein the step (α) is performed after the step (β3). 8. The method of claim 7,
The proportion of the radiation-sensitive acid-generating compound (B) in the radiation-sensitive composition is 15 to 30 parts by mass with respect to 100 parts by mass of the resin (A). 12. The method of claim 11,
The other radically polymerizable compound (c) is a (meth)acrylic acid ester having an alicyclic structure, a (meth)acrylic acid ester having an aromatic ring structure, an aromatic vinyl compound, an N-substituted maleimide compound, and a heterocyclic structure. A method for treating a radiation-sensitive composition, characterized in that it is a structural unit derived from at least one monomer selected from the group consisting of vinyl compounds. 13. The method of claim 12,
a step (β1) of forming an underlying film;
a step (β2) of applying the radiation-sensitive composition to the upper layer of the base film formed by the step (β1);
After the step (β2), a step (β3) of sequentially performing each treatment of prebaking, exposure, and development on the radiation-sensitive composition;
The method for treating a radiation-sensitive composition, wherein the step (α) is performed after the step (β3). 8. The method of claim 7,
The other radically polymerizable compound (c) is a (meth)acrylic acid ester having an alicyclic structure, a (meth)acrylic acid ester having an aromatic ring structure, an aromatic vinyl compound, an N-substituted maleimide compound, and a heterocyclic structure. A method for treating a radiation-sensitive composition, characterized in that it is a structural unit derived from at least one monomer selected from the group consisting of vinyl compounds. 15. The method of claim 14,
a step (β1) of forming an underlying film;
a step (β2) of applying the radiation-sensitive composition to the upper layer of the base film formed by the step (β1);
After the step (β2), a step (β3) of sequentially performing each treatment of prebaking, exposure, and development on the radiation-sensitive composition;
The method for treating a radiation-sensitive composition, wherein the step (α) is performed after the step (β3). 9. The method of claim 8,
The other radically polymerizable compound (c) is a (meth)acrylic acid ester having an alicyclic structure, a (meth)acrylic acid ester having an aromatic ring structure, an aromatic vinyl compound, an N-substituted maleimide compound, and a heterocyclic structure. A method for treating a radiation-sensitive composition, characterized in that it is a structural unit derived from at least one monomer selected from the group consisting of vinyl compounds. 8. The method of claim 7,
a step (β1) of forming an underlying film;
a step (β2) of applying the radiation-sensitive composition to the upper layer of the base film formed by the step (β1);
After the step (β2), a step (β3) of sequentially performing each treatment of prebaking, exposure, and development on the radiation-sensitive composition;
The method for treating a radiation-sensitive composition, wherein the step (α) is performed after the step (β3). 18. The method of claim 17,
The proportion of the radiation-sensitive acid-generating compound (B) in the radiation-sensitive composition is 15 to 30 parts by mass with respect to 100 parts by mass of the resin (A). 9. The method of claim 8,
a step (β1) of forming an underlying film;
a step (β2) of applying the radiation-sensitive composition to the upper layer of the base film formed by the step (β1);
After the step (β2), a step (β3) of sequentially performing each treatment of prebaking, exposure, and development on the radiation-sensitive composition;
The method for treating a radiation-sensitive composition, wherein the step (α) is performed after the step (β3). 17. The method of claim 16,
a step (β1) of forming an underlying film;
a step (β2) of applying the radiation-sensitive composition to the upper layer of the base film formed by the step (β1);
After the step (β2), a step (β3) of sequentially performing each treatment of prebaking, exposure, and development on the radiation-sensitive composition;
The method for treating a radiation-sensitive composition, wherein the step (α) is performed after the step (β3). 10. The method of claim 9,
a step (β1) of forming an underlying film;
a step (β2) of applying the radiation-sensitive composition to the upper layer of the base film formed by the step (β1);
After the step (β2), a step (β3) of sequentially performing each treatment of prebaking, exposure, and development on the radiation-sensitive composition;
The method for treating a radiation-sensitive composition, wherein the step (α) is performed after the step (β3).

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