JP7294804B2 - Curable resin composition, cured product, and method for producing patterned substrate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a curable resin composition, a cured product using the same, and a method for producing a patterned substrate, and more particularly to a curable resin composition used as a resist for photolithography.

2. Description of the Related Art In recent years, due to the miniaturization of electronic devices and the development of technology, large-scale integrated circuits (LSIs) are becoming more highly integrated and multi-layered. In order to obtain such LSIs and various precision parts, photolithography technology is often used as a precision microfabrication technology. In this technique, a fine pattern or the like can be formed on an object using chemical etching, electrolytic etching, or the like. For example, as a technique related to photolithography, a method for forming a hole pattern using a resin film containing an alkali-soluble resin and a photopolymerization initiator is disclosed (see, for example, Patent Document 1 below).

JP 2015-135470 A

In the photolithography technique as described above, for example, a photosensitive layer (etching resist) such as the resin film described in Patent Document 1 is exposed and developed for patterning, so that the surface of the object is insoluble in the etchant. A resist pattern is formed and then etched. When a resist pattern is formed using a negative photocurable resin composition, the exposed portion of the photosensitive layer is cured (insoluble) by the crosslinking reaction of the monomer or the like. After forming the resist pattern, in the case of chemical etching, the object is etched using an etchant to form a fine conductor pattern or the like on the surface of the object.

Materials for forming the photosensitive layer include, for example, film-like dry film resists and liquid resists. Although not completely dependent on these aspects, for example, in the case of a dry film resist, an aqueous Na ₂ CO ₃ solution is used as a developer when developing a photosensitive layer, or as a stripper when stripping a resist pattern. An aqueous NaOH solution can be used. Moreover, in the liquid resist, a TMAH (tetramethylammonium hydroxide) aqueous solution can be used as a developer, and a TMAH/DMSO (dimethylsulfoxide) aqueous solution can be used as a remover.

Here, when the resist pattern is peeled off after the etching process, the mechanism of resist pattern peeling differs depending on the material used.
For example, "swelling stripping", which is relatively used for dry film resists, uses an alkaline solution or the like as a stripping solution to chlorinate and hydrophilize the polymer that makes up the resist pattern with a strong base, allowing water to permeate the polymer. As a result, the polymer swells and the resist pattern is peeled off from the object. In swelling peeling, a peeling liquid such as an alkaline aqueous solution, which is relatively easy to handle and environmentally friendly, can be used. However, when the resist pattern is peeled off from the object by swelling peeling, the resist pattern is broken into small pieces. The peeled resist pattern may remain as a peeling residue in the fine structure of the object, and such a peeling residue causes drive failure of precision equipment. In particular, as the pattern becomes finer and finer, the stripped residue becomes more likely to remain in the structure of the object.

On the other hand, "dissolution stripping", which is relatively used for liquid resists, strips the resist pattern from the object by dissolving the polymer forming the resist pattern in stripping solution. Therefore, the dissolution stripping does not easily cause the problem of the resist pattern becoming small pieces, and the generation of stripping residue can be suppressed. However, conventional liquid resists (curable resin compositions for resists) require the use of TMAH/DMSO or the like as a stripping solution used for dissolution and stripping, and the stripping solution is difficult to handle and tends to have an adverse effect on the environment. .

In order to solve the above-described problems, the present invention provides a curable resin composition, a cured product, and a patterning composition that can provide a cured product that exhibits excellent etching resistance and excellent solubility in a stripping solution such as an alkaline aqueous solution. It aims at providing the manufacturing method of a board|substrate.

（式（１）中、Ｘは、炭素数３～６であり、直鎖状、分岐状若しくは環状の、飽和又は不飽和炭化水素基を示し、Ｙは、－ＮＨ－、－Ｏ－又は－Ｓ－を示し、Ｚは、（メタ）アクリロイル基、－ＯＨ又は－Ｈを示し、ｎは１～５の整数を示す。式（１）中、複数のＹ及びＺはそれぞれ同一でもよいし異なっていてもよい。但し、複数のＺにおいて、全（メタ）アクリロイル基の数は、１～４である。）
＜２＞ 前記式（１）における複数のＺにおいて、全（メタ）アクリロイル基の数が、１～２である前記＜１＞に記載の硬化性樹脂組成物。
＜３＞ 前記式（１）における複数のＺの少なくとも一つが、－ＯＨである前記＜１＞又は＜２＞に記載の硬化性樹脂組成物。
＜４＞ 前記式（１）におけるＸが環状の飽和又は不飽和炭化水素基である前記＜１＞～＜３＞のいずれかに記載の硬化性樹脂組成物。
＜５＞ 全固形分に対する前記式（１）で表されるモノマー（Ａ）の含有量が１０～６０質量％である前記＜１＞～＜４＞のいずれかに記載の硬化性樹脂組成物。
＜６＞ さらに溶剤を含む前記＜１＞～＜５＞のいずれかに記載の硬化性樹脂組成物。
＜７＞ 前記アルキル（メタ）アクリレートポリマー（Ｂ）のガラス転移温度（Ｔｇ）が７０～１５０℃である前記＜１＞～＜６＞のいずれかに記載の硬化性樹脂組成物。
＜８＞ 前記＜１＞～＜７＞のいずれかに記載の硬化性樹脂組成物を硬化させた硬化物。
＜９＞ ３％水酸化ナトリウム（４０℃）への溶解する時間が０．０１ｍ²及び膜厚１５μｍ当たり２０分間以下である前記＜８＞に記載の硬化物。
＜１０＞ 前記＜１＞～＜７＞のいずれかに記載の硬化性樹脂組成物を用いて製造されるパターニング基板の製造方法であって、
基板上に前記硬化性樹脂組成物を含む感光層を付与する感光層形成工程と、
前記硬化性樹脂組成物を含む感光層を露光する露光工程と、
前記露光工程にて露光した前記感光層を現像する現像工程と、
前記現像工程にて前記感光層を現像した前記基板にエッチング処理を施すエッチング工程と、
前記エッチング工程が施された前記基板から前記感光層を除去する除去工程と、
を含むパターニング基板の製造方法。
＜１１＞前記除去工程は、水酸化ナトリウム水溶液によって前記感光層を除去する前記＜１０＞に記載のパターニング基板の製造方法。 <1> a monomer (A) represented by the following formula (1);
an alkyl (meth)acrylate polymer (B) containing (meth)acryloyl acid as a structural unit;
A curable resin composition comprising:

(In formula (1), X represents a linear, branched or cyclic, saturated or unsaturated hydrocarbon group having 3 to 6 carbon atoms, and Y represents -NH-, -O- or - S—, Z represents a (meth)acryloyl group, —OH or —H, and n represents an integer of 1 to 5. In formula (1), a plurality of Y and Z may be the same or different. However, in multiple Zs, the number of all (meth)acryloyl groups is 1 to 4.)
<2> The curable resin composition according to <1> above, wherein the number of all (meth)acryloyl groups in the plurality of Zs in formula (1) is 1 to 2.
<3> The curable resin composition according to <1> or <2>, wherein at least one of the plurality of Zs in formula (1) is —OH.
<4> The curable resin composition according to any one of <1> to <3>, wherein X in formula (1) is a cyclic saturated or unsaturated hydrocarbon group.
<5> The curable resin composition according to any one of <1> to <4>, wherein the content of the monomer (A) represented by the formula (1) with respect to the total solid content is 10 to 60% by mass. .
<6> The curable resin composition according to any one of <1> to <5>, further comprising a solvent.
<7> The curable resin composition according to any one of <1> to <6>, wherein the alkyl (meth)acrylate polymer (B) has a glass transition temperature (Tg) of 70 to 150°C.
<8> A cured product obtained by curing the curable resin composition according to any one of <1> to <7>.
<9> The cured product according to <8> above, wherein the time taken to dissolve in 3% sodium hydroxide (40° C.) is 20 minutes or less per 0.01 m ² and film thickness of 15 μm.
<10> A method for producing a patterned substrate using the curable resin composition according to any one of <1> to <7>,
A photosensitive layer forming step of providing a photosensitive layer containing the curable resin composition on a substrate;
An exposure step of exposing a photosensitive layer containing the curable resin composition;
a developing step of developing the photosensitive layer exposed in the exposing step;
an etching step of etching the substrate on which the photosensitive layer has been developed in the developing step;
a removing step of removing the photosensitive layer from the substrate subjected to the etching step;
A method of manufacturing a patterned substrate, comprising:
<11> The method for manufacturing a patterned substrate according to <10>, wherein the removing step removes the photosensitive layer with an aqueous sodium hydroxide solution.

The present invention provides a curable resin composition, a cured product, and a method for producing a patterned substrate that can provide a cured product exhibiting excellent etching resistance and excellent solubility in a stripping solution such as an alkaline aqueous solution. be able to.

EMBODIMENT OF THE INVENTION Hereinafter, the form (henceforth "this embodiment") for implementing this invention is demonstrated in detail. However, the present invention is not limited to this, and various modifications are possible without departing from the scope of the invention.

<<Curable resin composition>>
The curable resin composition of the present embodiment (hereinafter sometimes simply referred to as “resin composition”) comprises a monomer (A) represented by the following formula (1) and (meth)acryloyl acid as structural units and an alkyl (meth)acrylate polymer (B) containing as

（式（１）中、Ｘは、炭素数３～６であり、直鎖状、分岐状若しくは環状の、飽和又は不飽和炭化水素基を示し、Ｙは、－ＮＨ－、－Ｏ－又は－Ｓ－を示し、Ｚは、（メタ）アクリロイル基、－ＯＨ又は－Ｈを示し、ｎは１～５の整数を示す。式（１）中、複数のＹ及びＺはそれぞれ同一でもよいし異なっていてもよい。但し、複数のＺにおいて、全（メタ）アクリロイル基の数は、１～４である。）

(In formula (1), X represents a linear, branched or cyclic, saturated or unsaturated hydrocarbon group having 3 to 6 carbon atoms, and Y represents -NH-, -O- or - S—, Z represents a (meth)acryloyl group, —OH or —H, and n represents an integer of 1 to 5. In formula (1), a plurality of Y and Z may be the same or different. However, in multiple Zs, the number of all (meth)acryloyl groups is 1 to 4.)

The resin composition of the present embodiment is used as a photosensitive layer (etching resist) when etching an object to be etched having a copper film of a copper-clad laminate, an oxide film of a semiconductor substrate, or the like to form a conductor pattern, an oxide film pattern, or the like. can be used as The photosensitive layer can be formed by coating the resin composition of the present embodiment on the surface of the object to be etched. Although not particularly limited, the resin composition of the present embodiment can be made into a negative photocurable resin composition, for example, by including a photopolymerization initiator or the like. When the photosensitive layer is formed using a negative photocurable resin composition, the exposed portion can be cured by irradiating the photosensitive layer with radiation such as light and exposing it (by exposing it to light) (hereinafter referred to as , the cured product obtained by curing the resin composition of the present embodiment may be referred to as “the cured product of the present embodiment” or simply “cured product”). At this time, the non-cured portion (non-exposed portion) of the photosensitive layer is soluble in the developer, but the cured portion (exposed portion) is insoluble in the developer. For this reason, after exposing the photosensitive layer to light in a pattern using a mask or the like, the uncured portion is developed (removed) using a developer, so that the surface of the object to be etched is exposed. A resist pattern formed from the cured product of the embodiment can be formed.
After forming the resist pattern, the object to be etched is etched using an etchant to remove the copper film and oxide film, thereby forming a conductor pattern, an oxide film pattern, and the like. After that, the resist pattern is removed from the surface of the object to be etched using a stripping solution. The curable resin composition of the present embodiment is not limited to a resist composition for chemical etching using an etchant, and can also be used as a resist composition for electrolytic etching.

A cured product using the resin composition of the present embodiment has excellent etching resistance and solubility in a stripping solution such as an alkaline aqueous solution.
Here, "etching resistance" means the resistance of the resist pattern to an etchant such as an aqueous solution of ferric chloride. For example, when a resist pattern is formed on an object to be etched using the resin composition of the present embodiment and a conductor pattern or the like is formed by etching, the surface has no unevenness and a linear pattern (for example, the conductor pattern rectangular in cross-section).
The term "solubility in a stripping solution such as an alkaline aqueous solution" means the solubility of the resist pattern (hardened product) in the stripping solution when the resist pattern is stripped. That is, the resist pattern obtained by curing the resin composition of the present embodiment has excellent resistance to the etchant, and also has excellent solubility in the stripping solution when stripping the resist pattern. Since the resist pattern residue in the stripping solution is small when the solubility in the stripping solution is high, the occurrence of problems caused by the residue can be suppressed. Moreover, the resist pattern obtained by curing the resin composition of the present embodiment can exhibit excellent solubility even in a low-concentration alkaline stripping solution such as an aqueous sodium hydroxide solution (3%). Therefore, since the resist pattern can be dissolved in a relatively short time, it is possible to suppress the etching target from being damaged by the stripping solution.

Furthermore, the photosensitive layer using the resin composition of the present _embodiment is excellent in developing speed with a developer such as an aqueous _K2CO3 solution.

（式（１）中、Ｘは、炭素数３～６であり、直鎖状、分岐状若しくは環状の、飽和又は不飽和炭化水素基を示し、Ｙは、－ＮＨ－、－Ｏ－又は－Ｓ－を示し、Ｚは、（メタ）アクリロイル基、－ＯＨ又は－Ｈを示し、ｎは１～５の整数を示す。式（１）中、複数のＹ及びＺはそれぞれ同一でもよいし異なっていてもよい。但し、複数のＺにおいて、全（メタ）アクリロイル基の数は、１～４である。） (Monomer (A) Represented by Formula (1))
The monomer (A) used in the resin composition of this embodiment is represented by the following formula (1).

(In formula (1), X represents a linear, branched or cyclic, saturated or unsaturated hydrocarbon group having 3 to 6 carbon atoms, and Y represents -NH-, -O- or - S—, Z represents a (meth)acryloyl group, —OH or —H, and n represents an integer of 1 to 5. In formula (1), a plurality of Y and Z may be the same or different. However, in multiple Zs, the number of all (meth)acryloyl groups is 1 to 4.)

In formula (1), X has 3 to 6 carbon atoms and represents a linear, branched or cyclic, saturated or unsaturated hydrocarbon group. Although not particularly limited, X is preferably a cyclic saturated or unsaturated hydrocarbon group, more preferably a cyclic saturated hydrocarbon group.
Examples of X include a methylene group, an ethylene group, a propylene group, an n-butylene group, a t-butylene group, a cyclohexylene group, a phenylene group, and the like. is more preferred.

In formula (1), Y represents -NH-, -O- or -S-. In formula (1), a plurality of Y's may be the same or different. The monomer (A) preferably contains at least an oxygen atom as Y.

In formula (1), Z represents a (meth)acryloyl group, -OH or -H. In formula (1), a plurality of Y's may be the same or different. However, in the formula (1), in a plurality of Z, the total number of (meth)acryloyl groups is 1 to 4, and from the viewpoint of etching resistance, solubility in a stripping solution such as an alkaline aqueous solution, and developability, 1 ~2 is preferred. Further, in the monomer (A), although not particularly limited, from the viewpoint of solubility in a stripping solution such as an alkaline aqueous solution, it is preferable that at least one of the plurality of Z is —OH (hydroxyl group), and the monomer (A) is It is more preferable to have 1 to 4 hydroxyl groups, and particularly preferably to have 1 to 2 hydroxyl groups.
In the formula (1) n represents an integer of 1-5. From the standpoint of developability, n is preferably 1 to 3, more preferably 1 to 2. In addition, several n may be the same and may differ.

Examples of the monomer (A) include the following compounds.

The molecular weight of the monomer (A) is not particularly limited, but is preferably 300 to 1,000, more preferably 300 to 800, particularly preferably 400 to 700, from the viewpoint of development speed. The molecular weight of monomer (A) can be measured using, for example, gel permeation chromatography (GPC).

The content of the monomer (A) is not particularly limited, but is preferably 10 to 60% by mass, preferably 20 to 50% by mass, based on the total solid content from the viewpoint of further increasing the solubility in a stripping solution such as an alkaline aqueous solution. % is more preferred, and 20 to 40% by mass is particularly preferred. The term "total solids" used throughout this specification means all components other than the solvent in the resin composition.
Further, when other monomers are used in combination with the monomer (A), the total amount of the monomers is not particularly limited, but from the viewpoint of solubility in a stripping solution such as an alkaline aqueous solution, the total solid content is 10 to 60. % by mass is preferable, 20 to 50% by mass is more preferable, and 20 to 40% by mass is particularly preferable.
Furthermore, the ratio (x/y) of all monomers (x) to all polymers (y) in the composition is not particularly limited, but from the viewpoint of patterning properties, it is preferably 20/80 to 80/20. /70 to 60/40 is more preferred, and 40/60 to 60/40 is particularly preferred.

(Alkyl (meth)acrylate polymer (B))
In the present embodiment, the alkyl (meth)acrylate polymer (B) (hereinafter sometimes simply referred to as “polymer (B)”) is an alkali-soluble resin containing (meth)acryloyl acid as a structural unit.
Examples of monomers that can serve as structural units of the polymer (B) include alkyl (meth)acrylates and alicyclic (meth)acrylates. Polymer (B) can be obtained by polymerizing these monomers.
Examples of alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, hydroxyethyl ( meth)acrylate, hydroxypropyl (meth)acrylate, ethoxyethyl (meth)acrylate, and the like.
Alicyclic (meth)acrylates include, for example, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and the like.
Further, the polymer (B) may contain (meth)acryloyl acid as a structural unit, and may be a homopolymer or a copolymer. When the polymer (B) is a copolymer, the polymer (B) may contain structural units derived from other monomers copolymerizable with the alkyl (meth)acrylate. Other monomers include, for example, (meth)acrylates, styrene, maleimide derivatives and the like. When the polymer (B) is a copolymer containing structural units derived from other polymers, the proportion of structural units derived from alkyl (meth)acrylate in the entire polymer (B) is not particularly limited, From the viewpoint of development speed, it is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.

Examples of combinations of monomers constituting the polymer (B) include, but are not particularly limited to, the following.
- (meth) acrylate [(meth) acrylic acid];
methyl (meth) acrylate [methyl (meth) acrylate];
Combination of butyl acrylate [butyl (meth) acrylate] and; (meth) acrylate [(meth) acrylic acid] and;
benzyl (meth) acrylate [benzyl (meth) acrylate;
Butyl acrylate [with butyl (meth)acrylate:

The glass transition temperature (Tg) of the polymer (B) is not particularly limited, but from the viewpoint of improving tackiness and developability, it is preferably 60 to 150°C, more preferably 60 to 130°C, and 70 to 130°C. Especially preferred.
Although the weight average molecular weight of the polymer (B) is not particularly limited, it is preferably 5,000 to 80,000, more preferably 8,000 to 50,000, more preferably 10,000 to 30, from the viewpoint of etching resistance. 000 is particularly preferred.
Molecular weight measurement of the polymer (B) is performed, for example, by gel permeation chromatography (GPC (manufactured by Tosoh Corporation, product number: GPC-8320, column: manufactured by Tosoh Corporation, product number: TSKgel-G5000H, solvent: tetrahydrofuran, flow rate : 1.0 mL/min)).

The acid value of the polymer (B) is preferably 10 to 200 in terms of solid content from the viewpoint of suppressing the occurrence of defects such as the occurrence of poor development in alkali development and the erosion of the surface of the exposed portion by the developer. Preferably, 20-120 is more preferable, and 30-60 is particularly preferable. Methods for adjusting the acid value include a method of adding an acid anhydride to a hydroxyl group, and a method of copolymerizing a carboxylic acid-containing acrylate in the case of an acrylic resin.

The content of the polymer (B) in the resin composition of the present embodiment is not particularly limited, and can be appropriately determined based on the relationship with the monomer (A) described above. 30 to 70% by mass is preferable, 40 to 60% by mass is more preferable, and 40 to 50% by mass is particularly preferable, based on the total solid content in the composition.

(Photoinitiator)
The resin composition in this embodiment can contain a photopolymerization initiator. Although not particularly limited, as the photopolymerization initiator in the present embodiment, one having an absorption wavelength in the i-line (365 nm) can be preferably used.

Examples of photopolymerization initiators include, but are not limited to, acetophenone, 2,2′-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p- Acetophenones such as tert-butylacetophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-( α-aminoketones such as 4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one [Irgacure 907] Photopolymerization initiators, 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H -carbazol-3-yl]-1-(O-acetyloxime), 1-[9-ethyl-6-benzoyl-9. H. -carbazol-3-yl]-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9. H. -carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9. H. -carbazol-3-yl]-ethan-1-one oxime-O-benzoate, ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9. H. -carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9. H. -carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9. H. -carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl }-9. H. -Carbazol-3-yl]-1-(O-acetyloxime) and other oxime ester photopolymerization initiators, benzophenone, 2-chlorobenzophenone, p,p'-bisdimethylaminobenzophenone and other benzophenones; benzyl, Benzoin ethers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropyl sulfur compounds such as thioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone and 2,3-diphenylanthraquinone; 2,4-trichloromethyl-(4′-methoxyphenyl)- 6-triazine, 2,4-trichloromethyl-(4′-methoxynaphthyl)-6-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4′-methoxy triazines such as styryl)-6-triazine; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2,4,6-trimethylbenzoyl-diphenyl phosphine oxide [Irgacure TPO]; Thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole are included. One of these photopolymerization initiators may be used alone, or two or more thereof may be used in combination.

The content of the photopolymerization initiator in the resin composition of the present embodiment is not particularly limited. 0% by mass is preferred, 0.5 to 7.5% by mass is more preferred, and 1.0 to 5.0% by mass is particularly preferred.

(others)
The resin composition of the present embodiment may contain, for example, a photopolymerization initiation aid, fine particles of 100 nm or less, and the like, as long as the effects of the resin composition of the present embodiment are not impaired.

The photopolymerization initiation aid is a compound that does not function as a photopolymerization initiator by itself, but increases the ability of the photopolymerization initiator when used in combination with the photopolymerization initiator. Examples of photopolymerization initiation aids include tertiary amines such as triethanolamine, which are effective when used in combination with benzophenone.

Addition of fine particles of 100 nm or less can improve the elastic recovery rate of the cured product of the resin composition of the present embodiment. Fine particles of 100 nm or less are not particularly limited, but examples thereof include Al ₂ O ₃ , TiO ₂ , Fe ₂ O ₃ , ZnO, CeO ₂ , Y ₂ O ₃ , Mn ₃ O ₄ and SiO ₂ . Also, the shape of the fine particles is not particularly limited, but examples include spherical, spherical, and polyhedral shapes.

(Preparation of resin composition)
In addition to the above-described monomer (A) and polymer (B), the resin composition of the present embodiment includes a photopolymerization initiator and the like, and if necessary, a solvent, a leveling agent, a chain transfer agent, a polymerization inhibitor, and a viscosity adjuster. It can be prepared by adding agents and the like and mixing.

-solvent-
As the solvent, a known solvent used in photosensitive resin compositions can be appropriately selected and used. Examples of solvents include, but are not limited to, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate (PGMEA ), esters such as propylene glycol monoethyl ether acetate and methyl-3-methoxypropionate, and ethers such as polyoxyethylene lauryl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether and diethylene glycol methyl ethyl ether. , aromatic hydrocarbons such as benzene, toluene and xylene, and amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

<<Method for manufacturing patterned substrate>>
The patterned substrate manufacturing method of the present embodiment is a method of manufacturing a patterned substrate manufactured using the resin composition of the present embodiment,
A photosensitive layer forming step of providing a photosensitive layer containing the curable resin composition on a substrate;
An exposure step of exposing a photosensitive layer containing the curable resin composition;
a developing step of developing the photosensitive layer exposed in the exposing step;
an etching step of etching the substrate on which the photosensitive layer has been developed in the developing step;
a removing step of removing the photosensitive layer from the substrate subjected to the etching step;
including.

In the method for manufacturing a patterned substrate of the embodiment, exposure, development, and etching are performed by photolithography as described above, so that, for example, a conductor pattern of a copper film is provided on a copper-clad laminate, or an oxidation is performed on a semiconductor substrate. Substrates with patterned films can be manufactured.

-Photosensitive layer forming process-
The photosensitive layer forming step is a step of applying a photosensitive layer (etching resist) containing a curable resin composition on the substrate. A method for applying the curable resin composition is not particularly limited, and a known method such as coating can be appropriately employed. Although the layer thickness of the photosensitive layer is not particularly limited, it is preferably 1 to 30 μm, more preferably 5 to 20 μm, particularly preferably 10 to 20 μm, from the viewpoint of etching resistance. The photosensitive layer may be subjected to a heating (post-baking) treatment after forming a layer by coating or the like. The substrate can be appropriately changed according to the desired purpose, and examples thereof include, but are not limited to, a copper-clad laminate, a semiconductor substrate provided with an oxide film, and the like.

-Exposure process-
The exposure step is a step of exposing the photosensitive layer containing the curable resin composition. Exposure is generally through a mask having the desired pattern. As described above, when the resin composition of the present embodiment is a negative photocurable resin composition, the monomer (A) in the exposed area is cured by a cross-linking reaction and rendered insoluble in the developer. The light source used in the exposure step varies depending on the type of photopolymerization initiator used, and includes, for example, an ultra-high pressure mercury lamp, a xenon lamp, and an LED.

- Development process -
The development step is a step of developing the photosensitive layer exposed in the exposure step. When the resin composition of the present embodiment is a negative photocurable resin composition, when the exposed photosensitive layer is developed, the unexposed area is removed by the developer, and the exposed area made of the cured product of the resin composition is removed. A formed etching pattern is formed.

The developer used in the development process is not particularly limited, but examples include alkaline aqueous solutions ( _e.g. , _K2CO3 aqueous solution (0.3%)), tetramethylammonium hydroxide (TMAH), and environmental and workability. From the viewpoint of safety, an alkaline aqueous solution is preferred.

The development time in the development step is not particularly limited, but since the resin composition of the present embodiment has an excellent development speed with a developer, for example, a K ₂ CO ₃ aqueous solution (0.3%) or the like can be used as the developer. is used, the non-exposed portion of the photosensitive layer can be dissolved (removed) preferably within 60 seconds, more preferably within 40 seconds.

- Etching process -
The etching step is a step of etching the substrate on which the photosensitive layer has been developed in the developing step. In this step, a conductive pattern, an oxide film pattern, and the like can be formed by etching the substrate on which the photosensitive layer is developed in the developing step, that is, the substrate on which the etching pattern is formed. In addition, since the cured product (resist pattern) using the resin composition of the present embodiment has excellent etching resistance, it is possible to suppress the penetration of the etchant during the etching process and form a linear conductor pattern. Although the thickness of the resist pattern generally maintains the thickness of the photosensitive layer, it may become thinner than the thickness of the photosensitive layer due to curing shrinkage or the like. Therefore, the thickness of the photosensitive layer is preferably 1 to 30 μm, more preferably 5 to 20 μm, particularly preferably 10 to 20 μm. It can also be 15 μm.

The etchant used in the etching step is not particularly limited, but a known etchant such as an aqueous ferric chloride solution (40%) can be appropriately selected according to the object to be etched. Examples of such an etchant include ferric chloride aqueous solution (4%), phosphoric acid, nitric acid, hydrochloric acid, and the like. A ferric aqueous solution is preferred.

-Removal process-
The removal step is a step of removing the photosensitive layer from the substrate that has undergone the etching step. This step is a step of removing the etching pattern after etching the photosensitive layer, ie, the substrate on which the etching pattern is formed, from the substrate subjected to the etching step.

The stripping solution used in the removal step is not particularly limited, but examples include alkaline aqueous solutions (e.g., sodium hydroxide aqueous solution (3%), potassium hydroxide aqueous solution (3%)) and other known stripping solutions. An alkaline aqueous solution is preferable from the viewpoint of the property and work safety.

The resin composition of this embodiment has high solubility in the stripping solution. “Solubility in stripping solution” means that the resin composition of the present embodiment is coated on a 10 cm×10 cm (0.01 m ² ) square glass substrate with a spin coater and dried to form a coating film having a dry film thickness of 15 μm. The cured layer was cured by irradiating 100 mJ/cm ² of light from an ultra-high pressure mercury lamp to the resulting coating film and immersed in an aqueous sodium hydroxide solution (3%; 40°C) to completely remove the coating film from the aqueous sodium hydroxide solution. Means the time until it dissolves in The solubility of the cured product (resist pattern) using the resin composition of the present embodiment in the stripping solution (that is, the time to dissolve in 3% sodium hydroxide (40 ° C.) per 0.01 m ² and 15 μm film thickness) is , preferably 20 minutes or less, more preferably 15 minutes or less, particularly preferably 10 minutes or less. In addition, the time for the cured product to dissolve in 3% sodium hydroxide (40°C) per 0.01 m ² and film thickness of 1 µm is preferably 5 minutes or less, more preferably 4 minutes or less, and still more preferably 3 minutes. It is particularly preferably 2 minutes or less, most preferably 1 minute or less.

The apparatus, method, and the like used for manufacturing the patterned substrate by the patterned substrate manufacturing method of the present embodiment are not particularly limited, and can be manufactured by a known patterned substrate manufacturing apparatus or the method described later. That is, the method for manufacturing the patterned substrate described above can be performed using an apparatus and method capable of performing the patterning method including each of the steps described above.

Although aspects of the present invention have been described above using the embodiments, the present invention is not limited to the above embodiments. Hereinafter, the present invention will be specifically described using examples.

[Production Example 1]
(Production of acrylic resin (P-1))
20.0 g of methacrylic acid, 60.5 g of methyl methacrylate, and 11.9 g of butyl acrylate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. Then, after the gas phase in the system was replaced with nitrogen, 7.6 g of 2,2'-azobis(isobutyronitrile) was added and heated to 80°C. The mixture was reacted at the same temperature for 8 hours to obtain a 40% solution of the desired polymer (P-1).
The solid content-equivalent acid value of the obtained polymer (P-1) was 141.1. Moreover, the weight average molecular weight (Mw) by gel permeation chromatography (GPC) was 18,700. The weight average molecular weight (Mw) is determined by GPC (manufactured by Tosoh Corporation, product number: GPC-8320, column: manufactured by Tosoh Corporation, product number: TSKgel-G5000H, solvent: tetrahydrofuran, flow rate: 1.0 mL/min)]. was measured in terms of polystyrene.

[Production Example 2]
(Production of acrylic resin (P-2))
20.0 g of methacrylic acid, 106.6 g of benzyl methacrylate, and 11.9 g of butyl acrylate were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. Then, after the gas phase in the system was replaced with nitrogen, 7.6 g of 2,2'-azobis(isobutyronitrile) was added and heated to 80°C. The mixture was reacted at the same temperature for 8 hours to obtain a 40% solution of the desired polymer (P-2).
The acid value of the obtained polymer (P-2) in terms of solid content was 94.1. Moreover, the weight average molecular weight (Mw) by GPC was 20,500. The weight average molecular weight (Mw) was measured by the same means as in Production Example 1.

[Production Example 3]
(Production of bifunctional monomer (M-1))
20.0 g of diglycidyl 1,2-cyclohexanedicarboxylate, 8.8 g of acrylic acid, 0.1 g of triphenylphosphine, and propylene glycol were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. 7.2 g of monomethyl ether acetate was charged. Then, the system was heated to 100° C. after replacing the gas phase with air. A reaction was carried out at the same temperature for 12 hours to obtain an 80% solution of the desired bifunctional monomer (M-1).

[Production Example 4]
(Production of tetrafunctional monomer (M-3))
20.0 g of diglycidyl 1,2-cyclohexanedicarboxylate, 19.7 g of methacrylic anhydride, 0.3 g of tetrabutylammonium bromide, propylene glycol were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. 10.0 g of monomethyl ether acetate was charged. Then, after replacing the gas phase in the system with air, the system was heated to 70° C. and reacted at the same temperature for 12 hours to obtain an 80% solution of the desired tetrafunctional monomer (M-3).

[Example 1]
(Preparation of photocurable resin composition)
Polymer (P-1) 35.2 g, bifunctional acrylate (M-1) 17.6 g, photoinitiator (I-1) (Irgacure 907, manufactured by BASF) 1.2 g, photoinitiator (I -2) 0.6 g of (Irgacure TPO, manufactured by BASF) and 44.9 g of propylene glycol monomethyl ether acetate (PGMEA) were mixed under light shielding to prepare a photocurable resin composition (etching resist composition).

(Method for producing resist pattern)
A 1.6 mm thick copper clad laminate laminated with 35 μm rolled copper foil was used as a substrate. After the photocurable resin composition of Example 1 prepared on the substrate was uniformly coated with a spin coater, it was dried on a hot plate at 90° C. for 2 minutes to form a photosensitive layer (photosensitive layer forming step). The resulting photosensitive layer was irradiated with 100 mJ/cm ² of light from an extra-high pressure mercury lamp through a mask having 200 μm line-and-space openings (illuminance: 20 mW in terms of i-line) (exposure step). The distance (exposure gap) between the mask and the substrate was 50 μm. After that, alkali development was carried out using a 0.3% K ₂ CO ₃ aqueous solution (development step). After that, it was washed with water and dried at 90° C. for 2 minutes to form a resist pattern with a film thickness of 15 μm.

The copper-clad laminate with the resist pattern was immersed in an aqueous ferric chloride solution (40%) for 30 minutes to etch the copper foil (etching step). After that, the resist pattern was stripped with an aqueous solution of sodium hydroxide (3%) at 40° C. for 20 minutes to remove the resist pattern (removal step) to form a conductor pattern.

(Etching resistance)
The resulting conductor patterns were observed under a microscope and ranked according to the following criteria.
[Evaluation criteria for etching resistance]
A: The conductor pattern was linearly formed, and no penetration of the etchant was observed.
B: Although the conductor pattern was linearly formed, penetration of the etchant was observed.
C: The conductor pattern was not formed linearly, and unevenness was observed on the pattern surface.

(Solubility in stripping solution such as alkaline aqueous solution)
The photocurable resin composition was applied on a 10 cm×10 cm square glass substrate by a spin coater and dried to form a coating film having a dry film thickness of 15 μm. The resulting coating film was irradiated with 100 mJ/cm ² of light from an ultra-high pressure mercury lamp to form a cured layer. The resulting cured layer was immersed in a stripping solution (aqueous sodium hydroxide solution (3%)) together with the substrate, and allowed to stand at 40° C. for 20 minutes. The stripping solution was then observed under a microscope and ranked according to the following criteria.
[Solubility evaluation]
A: The cured layer on the substrate was completely dissolved, and no insoluble matter was found in the stripping solution.
B: The cured layer on the substrate was dissolved, but a small amount of insoluble matter was observed in the stripping solution.
C: The cured layer was peeled off from the substrate, but a large amount of insoluble matter was found in the peeling liquid.

[Development speed]
The photocurable resin composition was applied on a 10 cm×10 cm square glass substrate with a spin coater and dried to form a coating film (photosensitive layer) with a dry film thickness of 15 μm. The obtained coating film was heated on a hot plate at 90° C. for 2 minutes. After heating, the coating film was alkali-developed using a K ₂ CO ₃ aqueous solution (0.3%), and the developing time until the resist residue disappeared from the substrate was measured and ranked according to the following criteria.
[Evaluation Criteria for Developability]
A: Development time was within 40 seconds.
B: Development time was more than 40 seconds and less than 60 seconds.
C: The development time was more than 60 seconds and within 80 seconds.

[Examples 2 to 6 and Comparative Example]
Photocurable resin compositions of other Examples and Comparative Examples were prepared in the same manner as in Example 1, except that each component was used according to the table below. Moreover, a resist pattern was prepared in the same manner as in Example 1, and the same evaluation was performed. The results are shown in the table below.

表１の記載からわかるように、本発明におけるモノマー（Ａ）に該当するＭ－１及びＭ－３を用いた実施例は現像性、耐エッチング性及びアルカリ水溶液等の剥離液に対する溶解性はいずれも十分な効果を示していた。一方、Ｍ－１及びＭ－３を用いていない比較例は、いずれも剥離液中に多量の不溶物が認められ、アルカリ水溶液等の剥離液に対する溶解性が劣っていた。

As can be seen from the description in Table 1, the examples using M-1 and M-3, which correspond to the monomer (A) in the present invention, have good developability, etching resistance, and solubility in stripping solutions such as alkaline aqueous solutions. was also quite effective. On the other hand, in the comparative examples in which M-1 and M-3 were not used, a large amount of insoluble matter was observed in the stripping solution, and the solubility in the stripping solution such as an alkaline aqueous solution was poor.

Claims (9)

a monomer (A) represented by the following formula (1);
an alkyl (meth)acrylate polymer (B) containing (meth)acryloyl acid as a structural unit and having an acid value of 10 to 200 in terms of acid solid content and a weight average molecular weight of 5,000 to 50,000; ,
A curable resin composition containing 10 to 60% by mass of the monomer (A) represented by the formula (1) with respect to the total solid content.

(In formula (1), X represents a cyclic saturated hydrocarbon group having 3 to 6 carbon atoms, Y represents -NH-, -O- or -S-, and Z is (meta) represents an acryloyl group, —OH or —H, and n represents an integer of 1 to 5. In formula (1), multiple Y and Z may be the same or different, provided that multiple Z , The total number of (meth)acryloyl groups is 2 to 4.) 2. The curable resin composition according to claim 1, wherein the total number of (meth)acryloyl groups in the plurality of Zs in formula (1) is two. 3. The curable resin composition according to claim 1, wherein at least one of the plurality of Zs in formula (1) is -OH. The curable resin composition according to any one of claims 1 to 3 , further comprising a solvent. The curable resin composition according to any one of claims 1 to 4, wherein the alkyl (meth)acrylate polymer (B) has a glass transition temperature (Tg) of 70 to 150°C. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 5 . 7. The cured product according to claim 6 , wherein the time for dissolving in 3% sodium hydroxide (40° C.) is 20 minutes or less per 0.01 m ² and film thickness of 15 μm. A method for producing a patterned substrate produced using the curable resin composition according to any one of claims 1 to 5 ,
A photosensitive layer forming step of providing a photosensitive layer containing the curable resin composition on a substrate;
An exposure step of exposing a photosensitive layer containing the curable resin composition;
a developing step of developing the photosensitive layer exposed in the exposing step;
an etching step of etching the substrate on which the photosensitive layer has been developed in the developing step;
a removing step of removing the photosensitive layer from the substrate subjected to the etching step;
A method of manufacturing a patterned substrate, comprising: 9. The method of manufacturing a patterned substrate according to claim 8 , wherein the removing step removes the photosensitive layer with an aqueous sodium hydroxide solution.