JP4950735B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition used for a photoresist for manufacturing a semiconductor, and more specifically, a coating having excellent alkali solubility, excellent developability, and excellent transparency, heat resistance, and chemical resistance. The present invention relates to a negative photosensitive resin composition from which a film can be obtained.

Conventionally, a metaparacresol novolak resin is used for a photoresist for microfabrication used in the manufacture of semiconductors, and polyhydroxystyrene, an alicyclic acrylic resin, and the like are used with the recent miniaturization. Also, vinyl ester resins, acrylic resins, and the like are used for mounting semiconductor elements on printed boards and forming metal wiring.
Recently, various methods for forming a pattern using these photolithography techniques and curing it by heating to use as a permanent coating have been studied mainly in the display field. In this case, various properties such as transparency, heat resistance, chemical resistance, and electrical insulation as a permanent coating are required.

Examples of resins used for chemically amplified positive photoresists include polyhydroxystyrene resins, acrylic resins, and novolak resins in which phenolic hydroxyl groups are protected with a protecting group that is eliminated by an acid. Yes. (For example, see Patent Documents 1 to 3)
In order to increase the sensitivity and resolution of a photoresist, light transmittance for exposure, heat resistance to prevent pattern deformation due to heat generated during dry etching, and alkali solubility among others are required. . However, these resins did not satisfy the light transmittance, alkali solubility, and heat resistance simultaneously and sufficiently.
In addition, in recent years, chemically amplified positive photoresists using these resins have been studied not only for photolithography using excimer laser but also for photolithography using conventional g-line and i-line, There is a need for higher sensitivity and higher resolution.

The present inventors have proposed a polymer having an N-substituted acrylamide unit as a new material for photoresist (see Patent Document 4). However, although this polymer is excellent in light transmittance, alkali solubility, and heat resistance, it is not sufficiently soluble in an ester solvent, the type of solvent to be used is limited, and the heat discoloration resistance of the coating film is also low. It was not sufficient, and it was required to be a material having transparency and usable as a permanent coating film.
As an improvement of this polymer, the present inventors have further proposed a polymer having a structural unit of hydroxyphenyl methacrylate (see Patent Document 2). Compared to the above polymer, this polymer has improved solubility in ester solvents and improved heat discoloration of the coating film, but the alkali solubility may be insufficient, and the improvement desired.

JP 2004-109959 A JP 2004-126605 A JP 2004-115724 A JP 2003-73424 A JP 2006-111802 A

  In view of the present situation, the object of the present invention is a photosensitive resin composition, particularly a negative, which has a good alkali solubility, an excellent developability, and a coating film having excellent transparency, heat resistance and chemical resistance. It is providing a type photosensitive resin composition.

  As a result of intensive studies to achieve the above object, the present inventor has found that a polymer having an acrylamide or acrylate containing an aromatic carboxylic acid group as a constituent unit and a radical polymerizable having an unsaturated double bond. It has been found that the above object can be achieved by using a composition containing a compound. The present invention has been completed based on such findings.

That is, the present invention provides the following photosensitive resin composition.
1. The polymer [A] containing the structural unit (a1) represented by the following general formula (1) and / or the structural unit (a2) represented by the following general formula (2), and an unsaturated double bond A photosensitive resin composition comprising a radically polymerizable compound [B].

（式中、Ｒ₁は水素原子またはメチル基、Ｒ₂は炭素数１〜４の直鎖又は分岐のアルキル基を表し、ｍは０〜４の整数である。）

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a linear or branched alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 4).

2. Furthermore, said 1 photosensitive resin composition containing radical photopolymerization initiator [C].
3. A radical containing a copolymerizable unsaturated double bond, wherein the polymer containing the structural unit (a1) represented by the general formula (1) and / or the structural unit (a2) represented by the general formula (2) 3. The photosensitive resin composition as described in 1 or 2 above, which is a copolymer with the polymerizable compound (a3).
4). A radically polymerizable compound (a3) having an unsaturated double bond capable of copolymerization is obtained from an aromatic vinyl compound, an unsaturated acid and its ester, an unsaturated acid anhydride, an unsaturated acid amide, a maleimide compound, and an olefinic compound. 3. The photosensitive resin composition according to 3 above, which is at least one compound selected.
5. The polymer containing the structural unit (a1) represented by the general formula (1) and / or the structural unit (a2) represented by the general formula (2) is an unsaturated epoxy compound, unsaturated oxetanyl compound, unsaturated The photosensitive resin composition according to any one of the above 1 to 4, which is a copolymer with at least one compound selected from an isocyanate compound and an unsaturated alcohol.
6). At least a part of the carboxyl group of the structural unit (a1) represented by the general formula (1) and / or the structural unit (a2) represented by the general formula (2) is an unsaturated epoxy compound, an unsaturated oxetanyl compound, The photosensitive resin composition according to any one of the above 1 to 4, which is modified by reacting with at least one compound selected from an unsaturated isocyanate compound and an unsaturated alcohol.
7). In the polymer [A], the structural unit (a1) represented by the general formula (1) and / or the structural unit (a2) represented by the general formula (2) and an unsaturated acid or an anhydride thereof are copolymerized. Modified by reacting at least part of the structural unit derived from the unsaturated acid with at least one compound selected from an unsaturated epoxy compound, an unsaturated oxetanyl compound, an unsaturated isocyanate compound, and an unsaturated alcohol. The photosensitive resin composition in any one of said 1-4 which is a thing.
8). At least a part of the radical polymerizable compound (a3) having an unsaturated double bond capable of copolymerization contains an unsaturated acid or an anhydride thereof, an unsaturated epoxy compound, an unsaturated oxetanyl compound, an unsaturated isocyanate compound and an unsaturated compound. 3. The photosensitive resin composition according to 3 above, which is a reaction product with at least one compound selected from saturated alcohols.
9. The radical polymerizable compound [B] having an unsaturated double bond is selected from monofunctional (meth) acrylic acid esters, polyfunctional (meth) acrylic acid esters, and amidated products of unsaturated carboxylic acids and polyvalent amine compounds. The photosensitive resin composition according to any one of 1 to 8 above, which is at least one kind of compound.

According to the present invention, a negative photosensitive resin composition having good alkali solubility and excellent developability can be obtained. With this photosensitive resin composition, transparency, heat resistance, and chemical resistance can be obtained. An excellent film can be formed.
Therefore, the photosensitive resin composition of the present invention is a photoresist material for forming integrated circuit elements, metal wirings, and plated objects, and protective films and planarization of electronic components such as display elements, integrated circuit elements, and solid-state imaging elements. Suitable for film, interlayer insulation film formation, microlens or microlens array formation, light diffusive reflection film for liquid crystal display elements, alignment control protrusions and spacers, color filter formation, optical waveguide formation, etc. .

  The polymer [A] contained as an essential component in the photosensitive resin composition of the present invention has a constitutional unit (a1) represented by the following general formula (1) and / or a constitution represented by the following general formula (2). It is a polymer containing the unit (a2), may be a polymer consisting only of the structural unit (a1), or may be a polymer consisting only of the structural unit (a2). The polymer [A] may be a copolymer comprising the structural unit (a1) and the structural unit (a2), and the polymer [A] may be composed of the structural unit (a1) and / or the structural unit. (a2) may be a copolymer with a radically polymerizable compound (a3) having a copolymerizable unsaturated double bond.

（式中、Ｒ₁は水素原子またはメチル基、Ｒ₂は炭素数１〜４の直鎖又は分岐のアルキル基を表し、ｍは０〜４の整数である。）

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a linear or branched alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 4).

  Here, specific examples of the monomer corresponding to the structural unit (a1) represented by the general formula (1) include 4-carboxyphenylacrylamide, 3-carboxyphenylacrylamide, 2-carboxyphenylacrylamide, 4-carboxy-3. -Methylphenylacrylamide, 4-carboxy-2-methylphenylacrylamide, 4-carboxy-2,3-dimethylphenylacrylamide, 4-carboxy-2,5-dimethylphenylacrylamide, 4-carboxy-2,6-dimethylphenylacrylamide 4-carboxy-3,5-dimethylphenylacrylamide, 4-carboxy-3-ethylphenylacrylamide, 4-carboxy-2-ethylphenylacrylamide, 4-carboxy-2,3-diethylphenylacrylic 4-carboxy-2,5-diethylphenylacrylamide, 4-carboxy-2,6-diethylphenylacrylamide, 4-carboxy-3,5-diethylphenylacrylamide, 4-carboxy-3-propylphenylacrylamide, 4- Carboxy-2-propylphenylacrylamide, 4-carboxy-2,3-dipropylphenylacrylamide, 4-carboxy-2,5-dipropylphenylacrylamide, 4-carboxy-2,6-dipropylphenylacrylamide, 4-carboxy -3,5-dipropylphenylacrylamide, 4-carboxy-3-butylphenylacrylamide, 4-carboxy-2-butylphenylacrylamide, 4-carboxy-2,3-dibutylphenylacrylamide, 4-carboxy-2,5-dibutylphenylacrylamide, 4-carboxy-2,6-dibutylphenylacrylamide, 4-carboxy-3,5-dibutylphenylacrylamide, 4-carboxyphenylmethacrylamide, 3-carboxyphenylmethacrylamide, 2-carboxyphenylmethacrylamide, 4-carboxy-3-methylphenylmethacrylamide, 4-carboxy-2-methylphenylmethacrylamide, 4-carboxy-2,3-dimethylphenylmethacrylamide, 4-carboxy-2,5- Dimethylphenyl methacrylamide, 4-carboxy-2,6-dimethylphenyl methacrylamide, 4-carboxy-3,5-dimethylphenyl methacrylamide, 4-carboxy-3-ethylphenyl methacrylate Amide, 4-carboxy-2-ethylphenylmethacrylamide, 4-carboxy-2,3-diethylphenylmethacrylamide, 4-carboxy-2,5-diethylphenylmethacrylamide, 4-carboxy-2,6-diethylphenylmethacrylate Amide, 4-carboxy-3,5-diethylphenylmethacrylamide, 4-carboxy-3-propylphenylmethacrylamide, 4-carboxy-2-propylphenylmethacrylamide, 4-carboxy-2,3-dipropylphenylmethacrylamide 4-carboxy-2,5-dipropylphenyl methacrylamide, 4-carboxy-2,6-dipropylphenyl methacrylamide, 4-carboxy-3,5-dipropylphenyl methacrylamide, 4-carboxy-3-buty Phenylmethacrylamide, 4-carboxy-2-butylphenylmethacrylamide, 4-carboxy-2,3-dibutylphenylmethacrylamide, 4-carboxy-2,5-dibutylphenylmethacrylamide, 4-carboxy-2,6-dibutyl Examples thereof include phenylmethacrylamide and 4-carboxy-3,5-dibutylphenylmethacrylamide.

  Specific examples of the monomer corresponding to the structural unit (a2) represented by the general formula (2) include 4-carboxyphenyl acrylate, 3-carboxyphenyl acrylate, 2-carboxyphenyl acrylate, 4-carboxy-3- Methylphenyl acrylate, 4-carboxy-2-methylphenyl acrylate, 4-carboxy-2,3-dimethylphenyl acrylate, 4-carboxy-2,5-dimethylphenyl acrylate, 4-carboxy-2,6-dimethylphenyl acrylate, 4-carboxy-3,5-dimethylphenyl acrylate, 4-carboxy-3-ethylphenyl acrylate, 4-carboxy-2-ethylphenyl acrylate, 4-carboxy-2,3-diethylphenyl acrylate, 4-carboxy-2 5-diethylphenyl acrylate, 4-carboxy-2,6-diethylphenyl acrylate, 4-carboxy-3,5-diethylphenyl acrylate, 4-carboxy-3-propylphenyl acrylate, 4-carboxy-2-propylphenyl acrylate, 4-carboxy-2,3-dipropylphenyl acrylate, 4-carboxy-2,5-dipropylphenyl acrylate, 4-carboxy-2,6-dipropylphenyl acrylate, 4-carboxy-3,5-dipropylphenyl Acrylate, 4-carboxy-3-butylphenyl acrylate, 4-carboxy-2-butylphenyl acrylate, 4-carboxy-2,3-dibutylphenyl acrylate, 4-carboxy-2,5-dibutylphenyl acrylate 4-carboxy-2,6-dibutylphenyl acrylate, 4-carboxy-3,5-dibutylphenyl acrylate, 4-carboxyphenyl methacrylate, 3-carboxyphenyl methacrylate, 2-carboxyphenyl methacrylate, 4-carboxy-3- Methylphenyl methacrylate, 4-carboxy-2-methylphenyl methacrylate, 4-carboxy-2,3-dimethylphenyl methacrylate, 4-carboxy-2,5-dimethylphenyl methacrylate, 4-carboxy-2,6-dimethylphenyl methacrylate, 4-carboxy-3,5-dimethylphenyl methacrylate, 4-carboxy-3-ethylphenyl methacrylate, 4-carboxy-2-ethylphenyl methacrylate, 4-carboxy- , 3-diethylphenyl methacrylate, 4-carboxy-2,5-diethylphenyl methacrylate, 4-carboxy-2,6-diethylphenyl methacrylate, 4-carboxy-3,5-diethylphenyl methacrylate, 4-carboxy-3-propyl Phenyl methacrylate, 4-carboxy-2-propylphenyl methacrylate, 4-carboxy-2,3-dipropylphenyl methacrylate, 4-carboxy-2,5-dipropylphenyl methacrylate, 4-carboxy-2,6-dipropylphenyl Methacrylate, 4-carboxy-3,5-dipropylphenyl methacrylate, 4-carboxy-3-butylphenyl methacrylate, 4-carboxy-2-butylphenyl methacrylate, 4-carboxy-2,3 Dibutyl phenyl methacrylate, 4-carboxy-2,5-di-butylphenyl methacrylate, 4-carboxy-2,6-di-butylphenyl methacrylate, 4-carboxy-3,5-di-butylphenyl methacrylate.

The polymer [A] can be obtained by polymerizing these monomers alone or in combination of two or more. Polymer [A] can also be made into a copolymer by combining these monomers together with compound (a3) having an unsaturated double bond in the copolymerizable molecule.
Examples of the compound (a3) having an unsaturated double bond capable of copolymerization include aromatic vinyl compounds, unsaturated acids and esters thereof, unsaturated acid anhydrides, unsaturated acid amides, maleimide compounds, and various olefinic compounds. Etc.

Examples of the aromatic vinyl compound include styrene derivatives such as styrene, vinyltoluene, hydroxystyrene, methoxystyrene, t-butoxystyrene, and alkenylphenols such as isopropenylphenol.
Examples of the unsaturated acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid. Examples of the ester include alkyl esters such as methyl ester, ethyl ester, and benzyl ester, and methoxymethyl ester. Examples thereof include alicyclic esters such as alkoxyalkyl esters, cyclohexyl esters and isobornyl esters, and aromatic esters such as phenyl esters and hydroxyphenyl esters.
Examples of the unsaturated acid anhydride include maleic anhydride.

Examples of the unsaturated acid amide include acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, 4-hydroxy-3,5-dimethylbenzylacrylamide, hydroxyphenylacrylamide, hydroxyphenylmethacrylamide and the like. .
Examples of the maleimide compound include N-cyclohexylmaleimide, N-phenylmaleimide, N-hydroxyphenylmaleimide and the like.
Examples of the olefin compound include allyl compounds, butene, butadiene, acrylonitrile, methacrylonitrile and the like.

The radically polymerizable compound (a3) having an unsaturated double bond that can be copolymerized is not limited to the above in order to improve developability and obtain the desired coating film properties. A radically polymerizable compound having a double bond can also be arbitrarily used.
Further, the polymer [A] can be made into a quaternary or higher copolymer by using a plurality of types of compounds (a3) having an unsaturated double bond capable of copolymerization.

  The polymer [A] includes a monomer corresponding to the structural unit (a1) and / or the structural unit (a2), a radical polymerizable compound (a3) having an unsaturated double bond that can be copolymerized if necessary, It can be obtained by polymerization using a radical polymerization initiator in an organic solvent. The organic solvent is not particularly limited as long as it dissolves the monomer corresponding to the structural unit (a1) or the structural unit (a2) and, if necessary, the radical polymerizable compound (a3) having an unsaturated double bond capable of copolymerization. Although propylene glycol monomethyl ether acetate and ethyl lactate which are generally used as solvents for photoresists are not preferred. In addition, since the monomers corresponding to the structural unit (a1) and the structural unit (a2) are relatively excellent in solubility in polar solvents, a method of dissolving the monomer in methanol or the like and replacing it with a photoresist solvent after polymerization is performed. You can also. As the radical polymerization initiator used for producing the polymer [A], generally used organic oxides and azo compounds can be used.

  The content of the structural unit (a1) and / or the structural unit (a2) in the polymer [A] is usually 10 to 70 mol%, preferably 100 mol% when the total amount of all monomer components to be polymerized is preferably 100 mol%. Is 20 to 60 mol%. By setting the content of the structural unit (a1) and / or the structural unit (a2) to 10 mol% or more, a suitable development speed can be obtained, and by setting the content of the structural unit (a2) to 70 mol% or less, the development speed is too high, resulting in poor development. There is no waking. Further, by adjusting the content of the structural unit (a1) and / or the structural unit (a2) of the polymer [A] within the above range, after developing, the substrate is subjected to etching treatment or plating treatment, and subsequently When it is necessary to strip the resist with a strong alkali or the like, no stripping failure occurs.

  When the photosensitive resin composition of the present invention is used for the purpose of etching and plating of a substrate, the polymer [A] is used in addition to the structural unit (a1) and / or the structural unit (a2), When the photosensitive resin composition of the present invention is used for the purpose of etching treatment and plating treatment of a substrate, in addition to the general formula (1) and / or (2), aromatic vinyl compounds such as styrene, various olefins It is preferable to copolymerize a system compound, a maleimide compound, an unsaturated acid amide, or the like. This improves resistance to the etching solution and the plating solution.

  Moreover, when using the photosensitive resin composition of this invention as permanent coatings, such as a protective film of an electronic component, a planarization film | membrane, an interlayer insulation film, of a structural unit (a1) and / or a structural unit (a2). Others, unsaturated epoxy compounds such as glycidyl methacrylate, allyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, unsaturated oxetanyl compounds, unsaturated isocyanate compounds such as 2-isocyanate ethyl acrylate, 2-isocyanate ethyl methacrylate, 2 It is preferable to copolymerize unsaturated alcohols such as hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 1,4-dimethanol cyclohexyl monoacrylate. This copolymer is subjected to a heat treatment after pattern formation to cause a crosslinking reaction with the carboxylic acid in the structural unit (a1) and / or the structural unit (a2), thereby further improving the physical properties of the coating film as a permanent coating film.

The photosensitive resin composition of the present invention can further improve the sensitivity and physical properties of the coating film by making the polymer [A] a polymer having an unsaturated double bond as described above.
As a method for introducing an unsaturated double bond, for example, the unsaturated epoxy compound, the unsaturated oxetanyl compound, or the unsaturated compound is added to the carboxylic acid moiety of the structural unit represented by the general formula (1) and / or (2). A method of reacting an isocyanate compound and an unsaturated alcohol, or a structural unit represented by the general formula (1) and / or (2) and an unsaturated acid such as acrylic acid or methacrylic acid, or an unsaturated acid such as maleic anhydride. Method of copolymerizing acid anhydride and reacting at least a part of structural units derived from the unsaturated acid with the unsaturated epoxy compound, unsaturated oxetanyl compound, unsaturated isocyanate compound, and unsaturated alcohol Etc. Further, at least a part of the radical polymerizable compound (a3) having an unsaturated double bond in the copolymerizable molecule is an unsaturated acid or an anhydride thereof, an unsaturated epoxy compound, an unsaturated oxetanyl compound, an unsaturated compound. An unsaturated double bond can also be introduced by using a reaction product of at least one compound selected from an isocyanate compound and an unsaturated alcohol.

  Next, the radical polymerizable compound [B] having an unsaturated double bond contained as an essential component in the photosensitive resin composition of the present invention may be a radical polymerizable compound having at least one unsaturated double bond. If there is no restriction | limiting in particular, according to the objective, it can select suitably. Examples thereof include unsaturated acid ester compounds, unsaturated acid amide compounds, and other unsaturated compounds.

  Examples of the unsaturated acid ester compound include monofunctional (meth) acrylic acid ester, polyfunctional (meth) acrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester, and the like. You may use individually or in combination of 2 or more types. Of these, monofunctional (meth) acrylic acid esters and polyfunctional (meth) acrylic acid esters are preferable.

Examples of the monofunctional (meth) acrylic acid ester include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl mono (meth) acrylate, and the like.
Examples of polyfunctional (meth) acrylic acid esters include polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and 1,3-butanediol di (meth) acrylate. , Tetramethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol poly (meth) acrylate, sorbitol (Meth) acrylate, sorbitol tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane Examples include tri (acryloyloxypropyl) ether and tri (acryloyloxyethyl) isocyanurate.

  Examples of unsaturated acid amide compounds include amidated products of unsaturated carboxylic acids and polyvalent amine compounds. Specific examples include methylene bis- (meth) acrylamide and 1,6-hexamethylene bis- (meth). Examples include acrylamide, diethylenetriamine tris (meth) acrylamide, and xylylene bis (meth) acrylamide.

As radically polymerizable compound [B] which has an unsaturated double bond, the said compound can be used individually by 1 type or in combination of 2 or more types.
The content of the radically polymerizable compound [B] having an unsaturated double bond in the photosensitive resin composition is preferably 30 to 80 parts by mass, more preferably 100 parts by mass of the polymer [A]. Is 40 to 70 parts by mass. By making the radically polymerizable compound [B] having an unsaturated double bond 30 parts by mass or more, the sensitivity at the time of exposure is improved, and by making it 80 parts by mass or less, the compatibility and storage of the photosensitive resin composition. Stability does not deteriorate.

  The radical photopolymerization initiator [C] contained as an essential component in the photosensitive resin composition of the present invention is not particularly limited as long as it generates radicals by light irradiation and initiates radical polymerization. For example, benzophenone 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-methoxycarbonylbenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzopheno 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, ethylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone 2,4-diethylthioxanthone, isopropylthioxanthone, fluorene, acridone and benzoin, 10-butyl-2-chloroacridone, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin phenyl ether Benzyldimethyl ketal, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bi Dicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, triarylimidazole dimer, 2,2′-bis (o-chlorophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-carboethoxyphenyl) biimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-bromophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'- Tetra (o, p-dichlorophenyl) biimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetrakis (3,4,5-trimethoxyphenyl) , 2′-biimidazole, 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenylpropan-1-one, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 4- (methylphenylthio) Examples include phenylphenylmethane, 1,4-dibenzoylbenzene, 2-benzoylnaphthalene, benzoylbiphenyl, benzoyldiphenyl ether, acrylated benzophenone, and dibenzoyl.

As these radical photopolymerization initiators [C], commercially available products having the following trade names may be used. Commercially available products include Irgacure 2959, 184, 500, 651, 369, 907, 819, 1800, 1700, Darocure 1173, Lucurin BDK, TPO, TPO-L, and Kayakure BDMK manufactured by Nippon Kayaku. , BMS, DETX-S, CTX, BP-100, 2-EAQ, Esacure KB1, EB3, KIP150, KIP100, TZT, Shinko Giken S-121, S-124, S-122, S- 112, S-113, Daicel UCB NK1300, NK1100, NK1200, BZO, Ebecryl P36, Shell Chemical Quantacure ITX, BMS, CTX, ABQ, QTX, Daito Chemix Dies Tocure OB, Kawaguchi Pharmaceutical's High Cure ABP, and the like.
The radical photopolymerization initiator [C] is used alone or in combination of two or more.

  The content of the photo radical polymerization initiator [C] in the photosensitive resin composition is preferably 10 to 40 parts by mass, more preferably 15 to 30 parts by mass with respect to 100 parts by mass of the polymer [A]. . By making content of radical photopolymerization initiator [C] 10 mass parts or more, the sensitivity at the time of exposure does not fall and the coating film bottom part does not cause poor curing. Moreover, by setting it as 40 mass parts or less, the compatibility of the photosensitive resin composition and the storage stability do not deteriorate.

  The photosensitive resin composition of this invention can be made to contain an organic solvent as needed. The organic solvent is not particularly limited as long as it dissolves the polymer [A], the radical polymerizable compound [B] having an unsaturated double bond, and the photo radical polymerization initiator [C]. Propylene glycol monomethyl ether acetate, ethyl lactate, and the like which are commonly used can be preferably used.

  The photosensitive resin composition of the present invention contains the polymer [A], a radical polymerizable compound [B] having an unsaturated double bond, and a photo radical polymerization initiator [C] as essential components. If necessary, thermal polymerization inhibitor, UV absorber, sensitizer, sensitization aid, filler, plasticizer, thickener, colorant, organic solvent, dispersant, antifoaming agent, surfactant, A compound capable of undergoing a crosslinking reaction with the polymer [A] such as an adhesion aid, a heat-sensitive acid generating compound, and an epoxy resin can be contained.

  Next, it shows about the formation method of the coating film using the photosensitive resin composition of this invention. First, the photosensitive resin composition of the present invention dissolved in an organic solvent is applied on a glass substrate, a silicon wafer, and a substrate on which various metals are formed, and dried to form a coating film of the photosensitive resin composition. Form. The method for applying the composition solution is not particularly limited, and examples thereof include appropriate methods such as a spray method, a roll coating method, a spin coating method, a bar coating method, and a slit coating method. The drying conditions vary depending on the type of each component, the use ratio, and the like, but are, for example, 60 to 110 ° C. and about 30 seconds to 30 minutes.

  Next, after irradiating light through the mask which has a predetermined pattern to the formed coating film, it patterns by developing with a developing solution. Examples of the light used at this time include g-line (wavelength 436 nm), i-line (wavelength 365 nm), KrF excimer laser, ArF excimer laser, X-ray, electron beam, and the like. A high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, an excimer laser generator, etc. can be mentioned. Examples of the developer used in the development processing include sodium hydroxide, potassium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -undec-7-ene, 1,5-diazabicyclo An aqueous solution of an alkali (basic compound) such as [4,3,0] -none-5-ene 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 alkaline aqueous solution described above, or various organic solvents that dissolve the photosensitive resin composition of the present invention can be used as a developing solution. Can do. Furthermore, as a developing method, 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 varies depending on the composition of the photosensitive resin composition, but can be, for example, 30 to 120 seconds.

Next, it is preferable to perform a rinsing process by, for example, washing with running water on the patterned thin film. Furthermore, in order to improve the performance of the coating film as a resist, it is preferable to irradiate the entire surface with light.
When this photosensitive resin composition is used for etching a substrate or for plating, these treatments are performed, and then the resist is removed with a strong basic stripping solution or organic solvent.
Further, when this photosensitive resin composition is used for a patterned permanent coating, it can be subjected to a curing treatment by a heat treatment (post-bake treatment) using a hot plate, oven or the like. 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.

  In this way, the target integrated circuit element, metal wiring, photoresist material for forming the plated structure, and the protective film, planarizing film, and interlayer of electronic components such as display elements, integrated circuit elements, and solid-state imaging elements Patterns corresponding to various applications such as insulation film formation, microlens or microlens array formation, light diffusion reflection film for liquid crystal display elements, alignment control protrusions and spacers, color filter formation, optical waveguide formation, etc. A thin film can be formed on the surface of a substrate, and the formed coating film becomes a coating film excellent in transparency, heat resistance, and chemical resistance.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.
In addition, the measurement of the mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer [A] obtained in the following synthesis examples and comparative synthesis examples, and the photosensitivity obtained in the following examples and comparative examples. The performance evaluation of the functional resin composition was performed as follows.

(1) Measurement of mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of polymer [A] Measured under gel permeation chromatography (GPC) under the following conditions, a polymer in terms of polystyrene The mass average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of [A] were calculated.
Column: Shodex KF-801 + KF-802 + KF-802 + KF-803
Column temperature: 40 ° C
Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Shodex RI-101)
Flow rate: 1 ml / min

(2) Performance evaluation of photosensitive resin composition [Developability]
The solution of the photosensitive resin composition was applied on a glass substrate so as to have a film thickness of 3 μm and dried in an oven at 80 ° C. for 30 minutes. The dried coating film was irradiated with 1000 mJ / cm ² ultraviolet light with a super high pressure mercury lamp through a pattern mask, immersed in an aqueous solution of 2.38% tetramethylammonium hydroxide for 1 minute, and rinsed with pure water. went. The case where the pattern was transferred was marked with ◯, the unevenness was not perfect, but the transferred pattern was marked with Δ, and the pattern was not transferred with x.

[chemical resistance]
The solution of the photosensitive resin composition was applied on a glass substrate so as to have a film thickness of 3 μm and dried in an oven at 80 ° C. for 30 minutes. The entire surface of the dried coating film was exposed without using a pattern mask. One drop of 98 mass% concentrated sulfuric acid was dropped on the coating film cured by ultraviolet rays, and rinsed with pure water after 1 minute. The state of the coating film at that time was visually observed. The case where no change occurred in the coating film was evaluated as ◯, and the case where the coating film surface was eroded was evaluated as X.

[transparency]
The solution of the photosensitive resin composition was applied on a glass substrate so as to have a film thickness of 3 μm and dried in an oven at 80 ° C. for 30 minutes. The entire surface of the dried coating film was exposed without using a pattern mask, and was cured by heating in an oven at 200 ° C. for 30 minutes. About the obtained board | substrate with a cured coating film, the minimum transmittance | permeability of the light with a wavelength of 400-800 nm was measured using the glass substrate as the blank using the spectrophotometer. A sample having a minimum transmittance of 98% or more was rated as “◯”, and a sample having a minimum transmittance of less than 98% was evaluated as “×”.

[Heat-resistant]
The photosensitive resin composition was heat-cured at 200 ° C. for 30 minutes by the above method, and then heat-treated again at 230 ° C. for 2 hours, and the film thickness was measured. After heat curing at 200 ° C. for 30 minutes, the change in film thickness after reheating at 230 ° C. for 2 hours was calculated as the film thickness reduction rate. The film thickness reduction rate after reheating was less than 3%, and the film thickness reduction rate was 3% or more.

Synthesis Example 1 [Production of Copolymer [A-1]]
In a flask equipped with a reflux condenser and a stirrer, 56.8 parts by mass of p-carboxyphenylmethacrylamide, 43.2 parts by mass of styrene, 150 parts by mass of ethyl lactate, 150 parts by mass of methanol, dimethyl 2,2′-azobis (2 -Methylpropionate) After charging 12.0 parts by mass and purging with nitrogen, the liquid temperature was raised to 70 ° C. while stirring, and the reaction was carried out at 70 ° C. for 28 hours. The disappearance of the monomer was confirmed by gel permeation chromatography, methanol and ethyl lactate were removed by distillation under reduced pressure at 120 ° C., the solid content concentration was adjusted to 30% by mass with ethyl lactate, and a copolymer represented by the following formula [ A polymer solution containing A-1] was obtained. The resulting copolymer [A-1] had a polystyrene-reduced mass average molecular weight (Mw) of 10,600 and a molecular weight distribution (Mw / Mn) of 4.0.

Synthesis Example 2 [Production of copolymer [A-2]]
In a flask equipped with a reflux condenser and a stirrer, 56.9 parts by mass of p-carboxyphenyl methacrylate, 43.1 parts by mass of styrene, 150 parts by mass of ethyl lactate, 150 parts by mass of methanol, dimethyl 2,2′-azobis (2- 12.0 parts by weight of methyl propionate) were charged and reacted in the same manner as in Synthesis Example 1 to obtain a polymer solution containing a copolymer [A-2] represented by the following formula. The resulting copolymer [A-2] had a polystyrene-reduced mass average molecular weight (Mw) of 10,500 and a molecular weight distribution (Mw / Mn) of 3.9.

Synthesis Example 3 [Production of copolymer [A-3]]
In a flask equipped with a reflux condenser and a stirrer, 82.1 parts by mass of p-carboxyphenylmethacrylamide, 17.9 parts by mass of styrene, 150 parts by mass of ethyl lactate, 150 parts by mass of methanol, dimethyl 2,2′-azobis (2 -Methylpropionate) 12.0 parts by mass were charged and reacted in the same manner as in Synthesis Example 1. Subsequently, 12.2 parts by mass of glycidyl methacrylate, 1.0 part by mass of triethylamine, and 0.02 part by mass of hydroquinone were added and reacted at 80 ° C. for 4 hours to obtain a copolymer [A-3] represented by the following formula. A solution containing was obtained.
The copolymer [A-3] had a polystyrene-reduced mass average molecular weight (Mw) of 13,000 and a molecular weight distribution (Mw / Mn) of 4.3.

Synthesis Example 4 [Production of Copolymer [A-4]]
In a flask equipped with a reflux condenser and a stirrer, 67.9 parts by weight of p-carboxyphenylmethacrylamide, 11.4 parts by weight of methacrylic acid, 20.7 parts by weight of styrene, 150 parts by weight of ethyl lactate, 150 parts by weight of methanol, dimethyl 1,2 parts by weight of 2,2′-azobis (2-methylpropionate) was charged, and the reaction was carried out in the same manner as in Synthesis Example 1. Subsequently, 14.1 parts by weight of glycidyl methacrylate, 1.0 part by weight of triethylamine, and 0.02 part by weight of hydroquinone were added and reacted at 80 ° C. for 4 hours to give a copolymer having an unsaturated double bond in the molecule [A -4] was obtained.
The polystyrene equivalent weight average molecular weight (Mw) of the copolymer [A-4] was 9,800, and the molecular weight distribution (Mw / Mn) was 3.7.

Synthesis Example 5 [Production of Copolymer [A-5]]
In a flask equipped with a reflux condenser and a stirrer, 55.5 parts by mass of p-carboxyphenyl methacrylate, 38.3 parts by mass of glycidyl methacrylate, 6.2 parts by mass of styrene, 150 parts by mass of ethyl lactate, 150 parts by mass of methanol, dimethyl 2 , 2′-azobis (2-methylpropionate) 12.0 parts by mass, reacted in the same manner as in Synthesis Example 1, and a polymer solution containing a copolymer [A-5] represented by the following formula Got.
The copolymer [A-5] had a polystyrene-reduced mass average molecular weight (Mw) of 13,000 and a molecular weight distribution (Mw / Mn) of 4.3.

Comparative Synthesis Example 1 [Production of Copolymer [A-6]]
In a flask equipped with a reflux condenser and a stirrer, 53.3 parts by mass of p-hydroxyphenyl methacrylate, 46.7 parts by mass of styrene, 150 parts by mass of ethyl lactate, 150 parts by mass of methanol, dimethyl 2,2′-azobis (2- 12.0 parts by weight of methyl propionate) were charged and reacted in the same manner as in Synthesis Example 1 to obtain a polymer solution containing a copolymer [A-6] represented by the following formula.
The copolymer [A-6] had a polystyrene-reduced mass average molecular weight (Mw) of 9,200 and a molecular weight distribution (Mw / Mn) of 3.6.

Comparative Synthesis Example 2 [Production of Copolymer [A-7]]
In a flask equipped with a reflux condenser and a stirrer, 79.9 parts by mass of p-hydroxyphenylmethacrylamide, 20.1 parts by mass of styrene, 150 parts by mass of ethyl lactate, 150 parts by mass of methanol, dimethyl 2,2′-azobis (2 -Methylpropionate) 12.0 parts by mass were charged and reacted in the same manner as in Synthesis Example 1. Subsequently, 13.7 parts by mass of glycidyl methacrylate, 1.0 part by mass of triethylamine, and 0.02 part by mass of hydroquinone were added and reacted at 80 ° C. for 4 hours to obtain a copolymer [A-7] represented by the following formula. A polymer solution containing was obtained.
The copolymer [A-7] had a polystyrene equivalent weight average molecular weight (Mw) of 10,800 and a molecular weight distribution (Mw / Mn) of 3.9.

Example 1
100 parts by mass of the copolymer [A-1] (solid content concentration: 30% by mass) obtained in Synthesis Example 1 as the polymer [A], and the radical polymerizable compound [B] having an unsaturated double bond as the polymer [A]. 17.0 parts by mass of methylolpropane triacrylate, 7.0 parts by mass of Irgacure 907 (manufactured by Ciba Specialty Chemicals) as a radical photopolymerization initiator [C], and 146 parts by mass of ethyl lactate as a solvent were mixed and dissolved. The solution was filtered through a 2 μm membrane filter to prepare a solution of the photosensitive resin composition. The performance evaluation results of the photosensitive resin composition are shown in Table 1.

Examples 2-5, Comparative Examples 1-2
Photosensitive resin as in Example 1 except that the copolymers [A-2] to [A-7] obtained in Synthesis Examples 2 to 5 and Comparative Synthesis Examples 1 and 2 were used as the polymer [A]. A solution of the composition was prepared. The performance evaluation results of the photosensitive resin composition are shown in Table 1.

Claims (5)

Unsaturated epoxy compound is a copolymer of at least one compound selected unsaturated oxetanyl compounds and unsaturated isocyanate compound or al the following general formula (1) include structural units represented by (a1) and / or Photosensitivity comprising a polymer [A] containing a structural unit (a2) represented by the following general formula (2) and a radical polymerizable compound [B] having an unsaturated double bond Resin composition.

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a linear or branched alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 4). The polymer [A] containing the structural unit (a1) represented by the following general formula (1) and / or the structural unit (a2) represented by the following general formula (2), and an unsaturated double bond contains a radical polymerizable compound [B], at least the carboxyl group of the general formula (1) include structural units represented by (a1) and / or the general formula (2) structural units represented by (a2) A photosensitive resin composition characterized in that a part thereof is modified by reacting with at least one compound selected from an unsaturated epoxy compound, an unsaturated oxetanyl compound, an unsaturated isocyanate compound, and an unsaturated alcohol object.

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a linear or branched alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 4). The polymer [A] containing the structural unit (a1) represented by the following general formula (1) and / or the structural unit (a2) represented by the following general formula (2), and an unsaturated double bond contains a radical polymerizable compound [B], said polymer [a] is the general formula (1) include structural units represented by (a1) and / or structural units represented by general formula (2) (a2) and an unsaturated acid or an anhydride thereof are copolymerized, and at least a part of a structural unit derived from the unsaturated acid, an unsaturated epoxy compound, an unsaturated oxetanyl compound, an unsaturated isocyanate compound, and an unsaturated alcohol A photosensitive resin composition, which is modified by reacting with at least one compound selected from the group consisting of:

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a linear or branched alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 4). The polymer [A] containing the structural unit (a1) represented by the following general formula (1) and / or the structural unit (a2) represented by the following general formula (2), and an unsaturated double bond contains a radical polymerizable compound [B], said polymer [a] is, Ri copolymer der the copolymerizable unsaturated double bond radical polymerizable compound having (a3), the radical polymerization Reaction of at least part of the functional compound (a3) with an unsaturated acid or an anhydride thereof and at least one compound selected from an unsaturated epoxy compound, an unsaturated oxetanyl compound, an unsaturated isocyanate compound, and an unsaturated alcohol A photosensitive resin composition characterized by being a product.

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a linear or branched alkyl group having 1 to 4 carbon atoms, and m is an integer of 0 to 4). The radical polymerizable compound [B] having an unsaturated double bond is selected from monofunctional (meth) acrylic acid esters, polyfunctional (meth) acrylic acid esters, and amidated products of unsaturated carboxylic acids and polyvalent amine compounds. The photosensitive resin composition according to any one of claims 1 to 4 , which is at least one kind of compound.