WO2020012753A1 - Curable composition, structure and method for forming same - Google Patents

Abstract

The present invention provides: a curable composition which is excellent in terms of the formation of a highly accurate multilayer wiring line and the like; a method for easily forming a structure such as a highly accurate multilayer wiring line; and a structure which is obtained with use of this curable composition. The present invention is a curable composition which contains (A) a polymer component which contains a structural unit having a group represented by formula (1), a structural unit having an alkoxysilyl group and a structural unit having a cyclic ether group in a same polymer or in different polymers, (B) an acid generator and (C) a solvent. In formula (1), each of R1 and R2 independently represents a hydrogen atom or a fluorine atom; n represents an integer of 1-10, and in cases where n is 2 or more, the plurality of R1 moieties may be the same as or different from each other and the plurality of R2 moieties may be the same as or different from each other; and * represents a bonding position.

Description

Curable composition, structure, and method for forming the same

(4) The present invention relates to a curable composition, a structure, and a method for forming the same.

In recent years, portable information devices such as liquid crystal displays and mobile phones, and electronic devices such as digital cameras have been required to be smaller, thinner, and more sophisticated such as power conversion functions. To cope with this, a wiring board is used as a board mounted on an electronic device such as a semiconductor chip or a power semiconductor mounted on these electronic devices.

It is known that the wiring board includes a stacked structure, and functions to fix a plurality of electronic components in addition to a role as a conductive material (for example, Patent Document 1). In recent years, such laminated wiring materials have been particularly required to have higher precision in view of the demands for downsizing, thinning, and enhancing the functions such as the power conversion function of electronic devices as described above.

In addition, as a method for forming such a wiring substrate, a material for forming a conductive layer is brought into contact with a lyophilic surface region of an insulating film having a lyophobic surface region and a lyophilic surface region, and is laminated. There is known a method of forming a substrate by performing such a process (for example, Patent Document 2).

International Publication No. 2017-014065 WO 2017-018129

In the method for forming a wiring substrate disclosed in Patent Document 2, an insulating film having a lyophobic surface region and a lyophilic surface region is formed using a composition for forming an insulating film containing a polymer containing a fluorine atom. A step of applying a conductive ink to the liquid surface region to form a conductive layer. However, when a conventional insulating film forming material is used, it is difficult to form a sufficiently accurate laminated wiring.

The present invention has been made based on the above circumstances, and its object is to provide a curable composition excellent in forming a high-precision laminated wiring and the like, and a structure such as a high-precision laminated wiring. It is an object of the present invention to provide a method of easily forming a structure and a structure obtained by using the curable composition.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又はフッ素原子である。ｎは、１～１０の整数である。ｎが２以上である場合、複数のＲ^１は同一でも異なっていてもよく、複数のＲ^２は同一でも異なっていてもよい。＊は結合部位を表す。） The invention made to solve the above-mentioned problems comprises (A) a structural unit having a group represented by the following formula (1), a structural unit having an alkoxysilyl group, and a cyclic ether group in the same or different polymers. The curable composition contains a polymer component containing a structural unit having the formula (A), (B) an acid generator, and (C) a solvent.

(In the formula (1), ^{R 1} and ^{R 2} are each independently a is .n is hydrogen atom or a fluorine atom, an integer of 1 ~ 10 .n is 2 or more, multiple ^{R 1} is The same or different, and a plurality of R ² may be the same or different. * Represents a binding site.)

Another invention made to solve the above-mentioned problem includes (I) a step of forming a pattern having a liquid-repellent surface region and a lyophilic surface region on the substrate by using the curable composition; II) forming a coating film on the lyophilic surface region using the first conductive layer forming composition, (III) irradiating at least the lyophobic surface region with radiation, and (IV) A method for forming a structure, comprising a step of curing the pattern after the step (III).

発 明 Another invention made to solve the above-mentioned problem is a structure including a conductive film and a cured film formed from the curable composition.

According to the present invention, a curable composition excellent in forming a high-precision laminated wiring and the like, a method for easily forming a structure such as a high-precision laminated wiring, and a curable composition obtained using the curable composition Structure can be provided.

FIG. 1A is a first explanatory view of a method for forming a structure according to an embodiment of the present invention. FIG. 1B is a second explanatory view of the method for forming a structure according to one embodiment of the present invention. FIG. 1C is a third explanatory view of the structure forming method according to the embodiment of the present invention. FIG. 1D is a fourth explanatory view of the method for forming the structure according to the embodiment of the present invention. FIG. 1E is a fifth explanatory view of the method for forming the structure according to the embodiment of the present invention. FIG. 1F is a sixth explanatory view of the method for forming the structure according to the embodiment of the present invention. FIG. 1G is a seventh explanatory view of the method for forming the structure according to the embodiment of the present invention. FIG. 2 is an enlarged photograph showing an example of very good ink application assist performance. FIG. 3 is an enlarged photograph showing an example of the ink application assist performance which is slightly inferior to the example of FIG. 2 but is sufficient. FIG. 4 is an enlarged photograph showing an example in which a good laminate is formed.

Hereinafter, a curable composition, a method for forming a structure, and a structure according to an embodiment of the present invention will be described in detail.

<Curable composition>
The curable composition according to one embodiment of the present invention comprises (A) a structural unit having a group represented by the following formula (1), a structural unit having an alkoxysilyl group, and a cyclic compound in the same or different polymers. It contains a polymer component containing a structural unit having an ether group, (B) an acid generator, and (C) a solvent.

In the formula (1), R ¹ and R ² are each independently a hydrogen atom or a fluorine atom. n is an integer of 1 to 10. When n is 2 or more, a plurality of R ¹ may be the same or different, and a plurality of R ² may be the same or different. * Represents a binding site.

(4) The curable composition is suitable for forming a pattern suitable for applying a conductive ink. The pattern formed by the curable composition has high lyophobic and lyophilic contrast, and curing characteristics. Therefore, by using a pattern formed by the curable composition, a highly accurate structure such as a laminated wiring can be formed.

(4) The curable composition may further contain other components in addition to the components (A) to (C). Hereinafter, each component will be described in detail.

[(A) polymer component]
The component (A) is a polymer component containing a structural unit having a group represented by the above formula (1), a structural unit having an alkoxysilyl group, and a structural unit having a cyclic ether group in the same or different polymers. It is. As the component (A), one type or two or more types of polymers can be used, but it is preferable to use two or more types of polymers. By using two or more polymers, the content of the structural unit having the group represented by the above formula (1), the structural unit having the alkoxysilyl group, the structural unit having the cyclic ether group, and the content of other structural units Is easier to adjust. As a result, it becomes easy to form a highly accurate structure such as a laminated wiring. (A) The polymer constituting the polymer component is usually at least one of a structural unit having a group represented by the above formula (1), a structural unit having an alkoxysilyl group, and a structural unit having a cyclic ether group. Contains one structural unit.

The content of the above component (A) is preferably 85 to 99.5% by mass when the mass of the curable composition excluding the component (C) is 100% by mass, and 90% by mass. More preferably, it is ～ 98% by mass. In the case where two or more polymers are used as the component (A), the content of each polymer is defined as 100% by mass based on the total mass of the curable composition excluding the component (C). Is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more. Further, the content of each polymer may be 99.5% by mass or less, and may be 99% by mass, 98% by mass or 97% by mass or less.

[Structural unit having group represented by formula (1)]
The component (A) includes a structural unit having a group represented by the following formula (1).

In the formula (1), R ¹ and R ² are each independently a hydrogen atom or a fluorine atom. n is an integer of 1 to 10. When n is 2 or more, a plurality of R ¹ may be the same or different, and a plurality of R ² may be the same or different. * Represents a binding site.

When the component (A) contains a structural unit having a group represented by the above formula (1), the component (A) has high liquid repellency. Therefore, a pattern formed using the curable composition containing the above structural unit has high lyophobic and lyophilic contrast. As a result, a highly accurate laminated wiring and the like can be formed.

は As the lower limit of n in the above formula (1), 2 is preferable, and 4 is more preferable. As the upper limit of n, 7 may be preferable.

Here, as the group represented by the above formula (1), groups represented by the following formulas (2) and (3) are preferably mentioned, and the group represented by the following formula (2) is more preferable. preferable.

Ｘ In the formula (2), x is an integer of 0 to 2, and y is an integer of 1 to 8. In the formula (3), z is an integer of 1 to 5.

と し て As the lower limit of x in the above formula (2), 1 is preferable, and 2 is more preferable. As a minimum of y, 2 is preferred and 3 is more preferred. As the upper limit of y, 6 may be preferable.

Further, the binding site represented by * of the group represented by the above formula (1) is preferably linked to -O- or -CO-O-, and is preferably linked to -O-. More preferred. When the binding site represented by * is -O-, it is preferable that -O- forms a part of an acetal group. That is, the structural unit having a group represented by the above formula (1) preferably further has an acetal group linked to the group represented by the above formula (1). As described above, since the group represented by the above formula (1) is connected to the main chain side of the polymer via the acetal group, the acid of the acid generator (B) generated by irradiation of radiation or the like can be reduced. Acting on the acetal group, the group represented by the formula (1) is dissociated from the main chain of the polymer. As a result, the pattern formed by the curable composition can easily form a lyophobic and lyophilic contrast depending on whether or not radiation is applied.

The acetal group is usually a group represented by —O—CR ^a ₂ —O— (R ^a is each independently a hydrogen atom or a hydrocarbon group.) The hydrocarbon group represented by ^Ra is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. Further, the two R ^a, one is a hydrogen atom, it is preferred that the other hydrocarbon group (preferably an alkyl group of carbon number 1 to 3, more preferably a methyl group).

The structural unit having a group represented by the above formula (1) preferably contains an aromatic hydrocarbon group, and more preferably contains a phenylene group, a tolylene group, a mesitylene group, a naphthylene group, a biphenylene group or a combination thereof. More preferably, it contains a phenylene group. Particularly, in the structural unit having a group represented by the above formula (1), the aromatic hydrocarbon group is represented by the above formula (1) directly or via another group (for example, an acetal group). It is preferable that the group is bonded, and it is more preferable that the group represented by the formula (1) is bonded to these aromatic hydrocarbon groups via an acetal group. When the structural unit having the group represented by the formula (1) has such a structure, the polymer containing this structural unit has improved solubility in the solvent (C).

In the polymer containing the structural unit having the group represented by the formula (1), the content of the structural unit having the group represented by the formula (1) is 25% based on 100% by mass of the polymer. It is preferably from 95 to 95% by mass, more preferably from 35 to 90% by mass, even more preferably from 45 to 85% by mass. Within this range, the component (A) can be easily imparted with liquid repellency.

[Structural unit having alkoxysilyl group]
The component (A) includes a structural unit having an alkoxysilyl group. When the component (A) contains a structural unit having an alkoxysilyl group, high curing properties are imparted to the component (A). In addition, when the component (A) contains a structural unit having an alkoxysilyl group, a pattern and a cured film formed by the curable composition have high heat resistance and the like.

The alkoxysilyl group is preferably a group represented by —SiR ^b ₃ . R ^b is each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an aryl group, or an alkoxy group. However, at least one, preferably at least two, and more preferably all three of ^Rb are alkoxy groups. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably a methoxy group, an ethoxy group and a propoxy group, and further preferably a methoxy group. The number of alkoxysilyl groups contained in the structural unit having an alkoxysilyl group is usually 1 to 9, preferably 1 to 7, more preferably 1 to 5, and still more preferably 1.

構造 The structural unit having an alkoxysilyl group preferably contains an aromatic ring. Further, the silicon atom contained in the alkoxysilyl group is preferably bonded to a ring carbon atom of the aromatic ring. Here, examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.

置換 A substituent may be bonded to the ring carbon atom of the silicon-bonded aromatic ring contained in the alkoxysilyl group. Examples of the substituent include a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The substituent may be one kind or two or more kinds.

The content of the structural unit having an alkoxysilyl group in the polymer containing the structural unit having an alkoxysilyl group is preferably 1 to 60% by mass, and more preferably 5 to 50% by mass based on 100% by mass of the polymer. %, More preferably 10 to 40% by mass. When it is in this range, it becomes easy to impart curing properties to the component (A).

[Structural unit having cyclic ether group]
The component (A) includes a structural unit having a cyclic ether group. When the component (A) contains a structural unit having a cyclic ether group, the component (A) has high curing properties. In addition, when the component (A) contains a structural unit having a cyclic ether group, a pattern and a cured film formed by the curable composition have high heat resistance.

Examples of the cyclic ether group include an oxiranyl group (ethylene oxide group) which is a three-membered cyclic ether group, an oxetanyl group which is a four-membered cyclic ether group, and a tetramethylene oxide group which is a five-membered cyclic ether group ( Tetrahydrofuranyl group) and the like. Among these, an oxiranyl group and an oxetanyl group are preferred. The number of cyclic ether groups contained in the structural unit having a cyclic ether group is usually 1 to 9, preferably 1 to 7, more preferably 1 to 5, and still more preferably 1 to 3.

The content of the structural unit having a cyclic ether group in the polymer containing the structural unit having a cyclic ether group is preferably from 10 to 80% by mass, more preferably from 20 to 70% by mass, based on 100% by mass of the polymer. %, More preferably 30 to 60% by mass. When it is in this range, it becomes easy to impart curing properties to the component (A).

[Other structural units]
The component (A) may include structural units other than the structural unit having the group represented by the above formula (1), the structural unit having an alkoxysilyl group, and the structural unit having a cyclic ether group. Examples of the structural unit other than the above include a structural unit having a saturated hydrocarbon group having 8 to 30 carbon atoms, a structural unit having a hydroxyaryl group, and a structural unit derived from N-substituted maleimide.

When the component (A) has a structural unit having a saturated hydrocarbon group having 8 to 30 carbon atoms, the polymer containing the structural unit having the group represented by the formula (1) is dissolved in the solvent (C). It will be easier. As a result, high liquid repellency is imparted to the component (A). Therefore, the structural unit having a saturated hydrocarbon group having 8 to 30 carbon atoms is preferably included in the same polymer as the polymer including the structural unit having the group represented by the formula (1).

The saturated hydrocarbon group having 8 to 30 carbon atoms may be a linear, branched or cyclic saturated hydrocarbon group, but is preferably a linear one. Further, the number of carbon atoms is more preferably 10 or more and 30 or less, and further preferably 15 or more and 25 or less.

In the polymer containing a structural unit having a saturated hydrocarbon group having 8 to 30 carbon atoms, the content of the structural unit having a saturated hydrocarbon group having 8 to 30 carbon atoms is based on 100% by mass of the polymer. , Preferably from 1 to 20% by mass, more preferably from 3 to 18% by mass, even more preferably from 5 to 15% by mass. Within this range, the polymer containing the structural unit having the group represented by the above formula (1) is easily dissolved in the solvent (C), so that the component (A) has particularly high liquid repellency. .

When the component (A) contains a structural unit having a hydroxyaryl group, the polymer containing the structural unit having a group represented by the above formula (1) is easily dissolved in the solvent (C). As a result, high liquid repellency is imparted to the component (A). Therefore, the structural unit having a hydroxyaryl group is preferably included in the same polymer as the polymer including the structural unit having a group represented by the above formula (1). Examples of the hydroxyaryl group include a hydroxyphenyl group and a hydroxynaphthyl group, and a hydroxyphenyl group is preferred.

The content of the structural unit having a hydroxyaryl group in the polymer including the structural unit having a hydroxyaryl group is preferably 1 to 30% by mass, and more preferably 3 to 25% by mass based on 100% by mass of the polymer. %, More preferably 5 to 20% by mass. Within this range, the polymer containing the structural unit having the group represented by the above formula (1) is easily dissolved in the solvent (C), so that the component (A) has particularly high liquid repellency. .

場合 When the component (A) has a structural unit derived from an N-substituted maleimide, a high heat resistance is imparted to the pattern and the cured film formed by the curable composition. Examples of the N-substituted maleimide include N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl- Examples thereof include 3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N- (acridinyl) maleimide. Among these, N-phenylmaleimide or N-cyclohexylmaleimide is preferred, and N-phenylmaleimide is more preferred.

When the component (A) includes two or more polymers, the first polymer includes a structural unit having a group represented by the above formula (1), and the structural unit includes an alkoxysilyl group. It is preferable to contain a second polymer other than the first polymer. As described above, the first polymer including the structural unit having the group represented by the above formula (1) has a structure including a saturated hydrocarbon group having 8 to 30 carbon atoms and a structure including a hydroxyaryl group. It is preferable to further include one or both of the units. It is preferable that the second polymer including the structural unit having an alkoxysilyl group further includes a structural unit having a cyclic ether group. Each of the first polymer and the second polymer may further include another structural unit. The content of the first polymer with respect to 100 parts by mass of the second polymer can be, for example, 0.1 to 50 parts by mass, and preferably 0.3 to 30 parts by mass.

The component (A) includes, as other structural units, structural units derived from a (meth) acrylate having a hydrocarbon group having 1 to 7 carbon atoms, such as methyl (meth) acrylate and ethyl (meth) acrylate. And a structural unit having a carboxy group such as a structural unit derived from (meth) acrylic acid.

[Polymerization method of component (A)]

Among the components (A), as a method for obtaining a polymer containing at least a structural unit having a group represented by the above formula (1), a method using a polymer as a compound as a precursor, and a method as a compound as a precursor Two methods, a method using a monomer and a method using a monomer, will be exemplified.

(4) In the method using a polymer as the precursor compound, the precursor polymer contains a hydroxy group or a carboxy group in the molecule. A polymer of component (A) is obtained by reacting a compound represented by the following formula (4) (hereinafter, also referred to as “compound (4)”) or the like with a hydroxy group of the polymer to be a precursor. Can be.

In the formula (4), R ³ is a hydrogen atom or a methyl group. R ⁴ is independently a methylene group, an alkylene group having 2 to 12 carbon atoms, an alkenylene group having 2 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 13 carbon atoms, A to 12 substituted or unsubstituted alicyclic hydrocarbon group, or a group in which one or more hydrogen atoms of these groups are substituted with a fluorine atom; R ⁵ is a group represented by the above formula (1). M is an integer of 0 to 12. When m is 2 or more, a plurality of R ⁴ may be the same or different.

In the method of using a monomer as a precursor compound, the precursor monomer contains a hydroxy group or a carboxy group in the molecule. The compound (A) can be obtained by reacting the compound (4) or the like with a hydroxy group or a carboxy group of the monomer to be a precursor, and then polymerizing the obtained monomer.

Hereinafter, the above two methods will be described more specifically.

[Method of Using Polymer as Compound as Precursor]
In this method, a polymer having a hydroxy group or a carboxy group is obtained by polymerizing a monomer having a hydroxy group or a carboxy group. Thereafter, the compound (4) is reacted with a hydroxy group or a carboxy group of the polymer to be a precursor to obtain a polymer of the component (A).

As the above-mentioned monomer having a hydroxy group, (meth) acrylic acid ester is preferable, for example, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, -Hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxylethylphthalic acid, dipropylene glycol methacrylate, dipropylene glycol acrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate , Cyclohexane dimethanol monoacrylate, cyclohexane dimethanol monomethacrylate, ethyl α- (hydro (Methyl) acrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate, glycerin monomethacrylate, glycerin monoacrylate, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, poly (ethylene glycol-propylene glycol) monomethacrylate, poly (ethylene glycol-propylene glycol) ) Monoacrylate, polyethylene glycol-polypropylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol monoacrylate, poly (ethylene glycol-tetramethylene glycol) monomethacrylate, poly (ethylene glycol-tetramethylene glycol) monoacrylate, poly ( Propylene glycol-tetramethylene glycol) monomethacrylate, poly (propylene glycol-tetramethylene glycol) monoacrylate, propylene glycol polybutylene glycol monomethacrylate, propylene glycol polybutylene glycol monoacrylate, 4-hydroxyphenyl methacrylate, 4-hydroxyphenyl acrylate, etc. Can be mentioned. In addition, as commercially available products, the following Praxel FM1, Praxel FM1D, Praxel FM2D, Praxel FM3, Praxel FM3X, Praxel FM4, Praxel FM5, Praxel F A1, Plaxel FA1DDM, Plaxel FA2D, Plaxel FA10 made by Daicel Can be.

Examples of the monomer having a carboxy group include acrylic acid, methacrylic acid, 2-acryloyloxyethylsuccinic acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylphthalic acid, 2-methacryloyloxyethylphthalic acid, Acryloyloxyethyl tetrahydrophthalic acid, 2-methacryloyloxyethyl tetrahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxypropyl phthalic acid, 2-methacryloyloxypropyl phthalate Acid, 2-acryloyloxypropyltetrahydrophthalic acid, 2-methacryloyloxypropyltetrahydrophthalic acid, 2-acryloyloxypropylhexahydro Tal acid, 2-methacryloyloxy propyl hexahydrophthalic acid, and the like.

In order to introduce a structural unit having a cyclic ether group, the precursor can be obtained by reacting a monomer having a cyclic ether group with the precursor. Examples of the monomer having a cyclic ether group include glycidyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 3,4-epoxy Tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate and the like can be mentioned.

In order to introduce a structural unit having an alkoxysilyl group, it can be obtained by reacting a monomer having an alkoxysilyl group with the precursor. Examples of the monomer having an alkoxysilyl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acrylic acid. Roxypropyltrimethoxysilane, 4-trimethoxysilylstyrene and the like can be mentioned.

In order to introduce a structural unit having a saturated hydrocarbon group having 8 to 30 carbon atoms, the precursor can be obtained by reacting a monomer having a saturated hydrocarbon group having 8 to 30 carbon atoms with the precursor. Examples of the monomer having a saturated hydrocarbon group having 8 to 30 carbon atoms include 8-methylnonyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, and n- (meth) acrylate. Stearyl and the like.

The precursor may be reacted with another monomer. As other monomers, for example, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated aromatic compound, conjugated diene, unsaturated compound containing tetrahydrofuran skeleton, maleimide and other monomers are exemplified. Can be mentioned.

Examples of a solvent used for a polymerization reaction for synthesizing a polymer having a hydroxy group or a carboxy group, which is a precursor of the polymer of the component (A), include alcohol, glycol ether, ethylene glycol alkyl ether acetate, and diethylene glycol monoester. Examples thereof include alkyl ether, diethylene glycol dialkyl ether, dipropylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, and ester.

The weight average molecular weight (Mw) of the polymer having a hydroxy group or a carboxy group in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably from 1,000 to 30,000, more preferably from 5,000 to 20,000.

One example of a method of reacting the compound (4) with a polymer having a hydroxy group or a carboxy group to obtain a polymer of the component (A) is to add a vinyl ether group to the hydroxy group or the carboxy group as shown in the following formula. This can be done by causing

方法 As a method of obtaining the polymer of the component (A), for example, a method of forming an acetal group by a hydroxy group of a polymer having a hydroxy group and a vinyl ether group of the compound (4) or the like can be mentioned. Alternatively, an acetal such as a hemiacetal or a hemiacetal ester is formed by a carboxy group of the polymer having a carboxy group and a vinyl ether group such as the compound (4) to form an adduct.

For example, after dissolving a polymer having a hydroxy group or a carboxy group in an appropriate organic solvent, an equimolar or excess amount of the compound (4) or the like is added to the hydroxy or carboxy group of the polymer. The resulting reaction mixture is cooled from 0 ° C. to room temperature (25 ° C.). Thereafter, an acid (eg, oxalic acid solution) dissolved in the same solvent as the above-mentioned organic solvent is dropped as a catalyst, and after completion of the dropping, the mixture is stirred and reacted at room temperature for 1 to 24 hours. After completion of the reaction, the organic solvent is removed to obtain the desired polymer of the component (A).

[Method of Using Monomer as Precursor Compound]
In this method, the compound (A) is polymerized by reacting the compound (4) or the like with a hydroxy group or a carboxy group of a monomer having a hydroxy group or a carboxy group to obtain an adduct and polymerizing them. obtain. As a method for obtaining such a polymer of the component (A), a known method can be referred to. For example, as described in JP-A-2005-187609, an acetal bond is formed by the hydroxyl group of a monomer having a hydroxy group and the vinyl ether group of a vinyl ether compound, or the carboxy group of a monomer having a carboxy group is A hexacetal ester bond is formed by the vinyl ether group of compound (4) to form an adduct. Next, using the obtained monomer, a polymer of the component (A) can be obtained in the same manner as in the method for producing a polymer having a hydroxy group or a carboxy group described above. In the polymerization at this time, copolymerization may be performed by further using a monomer having a cyclic ether group, a monomer having an alkoxysilyl group, a monomer having a saturated hydrocarbon group having 8 to 30 carbon atoms, and the like.

The weight average molecular weight (Mw) in terms of polystyrene of the polymer of the component (A) obtained as described above as determined by gel permeation chromatography (GPC) is preferably from 1,000 to 50,000, more preferably from 5,000 to 30,000.

好 ま し い As a preferable example of the polymer of the component (A), a polymer having at least one selected from the group consisting of structural units represented by the following structural units can be given.

の う ち In addition, among the component (A), a polymer containing no structural unit having a group represented by the above formula (1) can be polymerized by a conventionally known method. For example, a polymer containing a structural unit having an alkoxysilyl group and a structural unit having a cyclic ether group can be obtained by copolymerizing the above-described monomer having an alkoxysilyl group and a monomer having a cyclic ether group. Can be.

[(B) acid generator]
(B) The acid generator is, for example, a compound that generates an acid at least by irradiation with radiation. When the curable composition contains the component (B), the curability of the curable composition can be improved. When the group represented by the above formula (1) in the component (A) is connected to the main chain side of the polymer via an acetal group, the acid generated from the component (B) by irradiation with radiation causes The group represented by the formula (1) can be dissociated from the main chain of the polymer.

(B) The acid generator includes, for example, an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonate compound, and a carboxylate compound. Such acid generators may be used alone or in combination of two or more.

Examples of the oxime sulfonate compound include, for example, (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)- (2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)- (2-methylphenyl) acetonitrile, 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile and the like.

As an example of the onium salt, examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, and sulfonimide compound.

Examples of the sulfonimide compound include, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (camphasulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyl) Oxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphasulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphasulfonyloxy) Phenyl maleimide, N- hydroxynaphthalimide - trifluoromethane sulfonate, N- hydroxynaphthalimide - nonafluorobutanesulfonate ester.

酸 As other acid generators, the acid generators described in JP-A-2011-215503 and WO2011 / 087-011A1 can be used.

The content of the acid generator (B) in the curable composition is 0.2 to 20% by mass when the mass of the curable composition excluding the component (C) is 100% by mass. %, More preferably 0.5 to 10% by mass, even more preferably 2 to 8% by mass. By setting the content of the acid generator (B) within the above range, the curability of the curable composition can be improved. In addition, when the group represented by the above formula (1) in the component (A) is connected to the main chain side of the polymer via an acetal group, the acid generated from the component (B) by irradiation with radiation. Thereby, the group represented by the above formula (1) is easily dissociated from the main chain of the polymer.

[(C) solvent]
The solvent (C) is not particularly limited as long as the solvent (A) and the component (B) are dissolved or dispersed uniformly. (C) As the solvent, for example, alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aliphatic hydrocarbons, Examples thereof include aromatic hydrocarbons, ketones, and esters. As such a solvent (C), one type may be used alone, or two or more types may be used.

(2) When two or more polymers are used as the component (A) as the solvent (C), it is preferable to use two or more solvents. (C) At least one of the solvents has a dispersion parameter (dD) of the Hansen solubility parameter of 10 or more and 17 or less and a square root of the sum of squares of the polarization term (dP) and the hydrogen bond term (dH) ((dP ＾ It is more preferable to use a (C ′) solvent having 2 + dH {2) {(1/2)) of 10 or less. (C ′) The solvent has a dispersion term (dD) of 12 to 16 and a square root of the sum of the squares of the polarization term (dP) and the hydrogen bond term (dH) ((dP ＾ 2 + dH ＾ 2) ＾ (1 / 2)) is more preferably 8 or less. (C ′) The square root ((dP ＾ 2 + dH ＾ 2) ＾ (1/2)) of the sum of the squares of the polarization term (dP) and the hydrogen bond term (dH) of the solvent is preferably 7 or less, more preferably 6 or less. . The square root of the sum of the squares of the polarization term (dP) and the hydrogen bond term (dH) ((dP （2 + dH 水 素 2) ＾ (１ ／)) may be 2 or more or 3 or more.

ハ ン By using a solvent (C ′) having a Hansen solubility parameter in the above range, two or more polymers can be easily dissolved or dispersed uniformly. As a result, by using the pattern formed by the curable composition, a highly accurate laminated wiring or the like can be formed. In order to enhance the above effects, the content of the (C ′) solvent in the (C) solvent is preferably 30% by mass or more, and more preferably 50% by mass or more. The (C) solvent may be substantially only the (C ′) solvent.

Examples of the solvent (C ′) having a Hansen solubility parameter in the above range include ethers such as isopentyl ether, dioctyl ether, and ethyl isopentyl ether; esters such as isobutyl n-octanoate, isoamyl hexanoate, octyl acetate, and hexyl acetate; Acetals such as hexanal diethyl acetal, glycols such as diethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ethyl acetate, and triethylene glycol dimethyl ether; ketones such as 2-heptanone and diisobutyl ketone; and NOVEC 7300 (3M) can be mentioned. . Among these, diethylene glycol methyl ethyl ether, octyl acetate, and hexyl acetate are particularly preferred.

Solvents other than the (C ′) solvent include propylene glycol monomethyl ether acetate, propylene glycol methyl ether, toluene and the like.

The content of the solvent (C) in the curable composition is preferably 50 to 95% by mass, more preferably 60 to 85% by mass, when the total mass of the curable composition is 100% by mass. By setting the content of the solvent (C) in the above range, the thickness of the obtained cured film can be easily adjusted. As a result, by using the pattern formed by the curable composition, a highly accurate laminated wiring or the like can be formed.

[Other ingredients]
The curable composition may contain other components other than the components (A) to (C). Examples of the other components include an acid diffusion inhibitor, a surfactant, a storage stabilizer, an adhesion aid, and a heat resistance improver.

The acid diffusion inhibitor is a component that prevents the diffusion of the acid generated from the acid generator (B). The acid diffusion controlling agent is not particularly limited as long as it exerts such an effect, and a photo-degradable base which is exposed to light and generates a weak acid can be used. The photodisintegrable base generates an acid in the exposed portion, while the unexposed portion exhibits a high acid-trapping function by an anion, thereby capturing (B) the acid from the acid generator, and the unexposed portion from the exposed portion. Inactivates the diffusing acid. That is, since the acid is deactivated only in the unexposed portions, the contrast of the elimination reaction of the group represented by the above formula (1) is improved, and as a result, the resolution can be further improved. As an example of the photodisintegrable base, there is an onium salt compound which is decomposed by exposure and loses acid diffusion controllability.

Other acid diffusion controllers include, for example, amine compounds, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds. Examples of the nitrogen-containing heterocyclic compound include imidazoles such as 2-phenylbenzimidazole; pyridines; and piperazines.

に お い て In the curable composition, one type of acid diffusion inhibitor may be used alone, or two or more types may be used in combination. In the curable composition, the content of the acid diffusion inhibitor is preferably from 0.001% by mass to 5% by mass, more preferably from 0.005% by mass to 3% by mass, based on 100% by mass of the acid generator (B). % Is more preferred. With the above range, the reactivity of the curable composition can be optimized. As a result, by using the pattern formed by the curable composition, a highly accurate laminated wiring or the like can be formed.

In the curable composition, when the mass obtained by removing the component (C) from the total mass of the curable composition was 100% by mass, the polymer component (A), the acid generator (B), and the acid diffusion control were used. The lower limit of the total content of the agent may be preferably 80% by mass, more preferably 90% by mass or 99% by mass. This total content may be substantially 100% by weight. With the above range, the reactivity of the curable composition can be optimized. As a result, by using the pattern formed by the curable composition, a highly accurate laminated wiring or the like can be formed.

<Method of forming structure>
The method for forming a structure according to an embodiment of the present invention includes: (I) a step of forming a pattern having a lyophobic surface region and a lyophilic surface region on a substrate using the curable composition; II) forming a coating film on the lyophilic surface region using the first conductive layer forming composition, (III) irradiating at least the lyophobic surface region with radiation, and (IV) A step of curing the pattern after the step (III). The formation method is generally performed in the order of the above (I) to (IV).

The method of forming the structure includes forming a coating film of the first conductive layer forming composition on a substrate having a lyophobic surface region and a lyophilic surface region. Is easy to form. Further, it becomes easy to further form a conductive layer on the pattern by the above (III) step and the like. In addition, the cured film in which the conductive layers are laminated can be formed by the above-mentioned step (III) or the like without the step of forming a via hole by laser irradiation or the like, which has been conventionally required. Hereinafter, each step will be described in detail with reference to FIGS. 1A to 1G as appropriate.

In the step (I), for example, (I-1) the curable composition is applied on the substrate 10 and then preferably heated (prebaked) on the substrate 10 so that the curable composition is applied on the substrate 10. Forming a coating film 11 formed by the above (FIG. 1A), and then (I-2) irradiating a part of the coating film 11 with radiation to connect the main chain side of the polymer via an acetal group. Step (FIG. 1B) of dissociating the group represented by the above formula (1), and then (I-3) developing the coating film 11 with a developing solution such as an aqueous alkaline solution to form the convex portion of the liquid repellent surface region 13. And a step (FIG. 1C) of forming an uneven pattern 12 having a concave portion of the lyophilic surface region 14. The uneven pattern 12 is an example of a pattern having a liquid-repellent surface area and a lyophilic surface area.

に お い て In the step (I), examples of the material of the substrate that can be used include glass, quartz, silicon, and resin. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyether sulfone, polycarbonate, polyimide, a ring-opened polymer of cyclic olefin (ROMP polymer), and a hydrogenated product thereof. Among these, for example, since it is preferable to use a substrate with wiring finally obtained by the method for forming the structure for an electronic circuit or the like, a resin substrate, glass, Substrates and semiconductor substrates are preferred. The surface of the substrate 10 is more lyophilic than the liquid-repellent surface region 13 of the uneven pattern 12. That is, the surface of the substrate 10 is a lyophilic surface region.

The method for applying the curable composition is not particularly limited, but may be an application method using a brush or brush, a dipping method, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar. An appropriate method such as a coating method, flexographic printing, offset printing, an ink jet method, and a dispensing method can be employed. Among these coating methods, a slit die coating method or a spin coating method is particularly preferable.

条件 The prebaking conditions vary depending on the composition of the curable composition to be used and the like, but are preferably from 60 ° C to 120 ° C for about 1 minute to 10 minutes.

As the radiation used for the irradiation, visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray and the like can be used. Among these radiations, radiations having a wavelength in the range of 190 nm to 450 nm are preferable, and radiations containing 365 nm ultraviolet rays are particularly preferable. The exposure amount is preferably a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (OA1 model 356, manufactured by OA1 Optical Associates Inc.), preferably from 10 mJ / cm ² to 1000 mJ / cm ² , more preferably 20 mJ / cm 2. ^{It is 2} to 500 mJ / cm ² .

基 By the irradiation of the radiation, the group represented by the above formula (1) of the polymer present in the coating film 11 is dissociated. As a result, the liquid repellency of the exposed portion of the coating film 11 decreases, and the lyophilic property increases. Therefore, the exposed portion of the coating film 11 flows by development using an alkaline aqueous solution or the like, and the surface of the substrate 10 is exposed. The surface of the protrusion that is not exposed and is not washed away becomes the lyophobic surface region 13, and the surface (recess) of the substrate 10 between the protrusions becomes the lyophilic surface region 14. Note that even if the exposed portion of the coating film 11 is not completely washed away and the surface of the substrate 10 is not exposed, the exposed portion of the coating film 11 has reduced lyophobicity and is a lyophilic surface region.

Examples of the developing solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, and methyldiethylamine. Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [ An aqueous solution of an alkali (basic compound) such as [4,3,0] -5-nonane is exemplified. Alternatively, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the alkali, or an aqueous alkali solution containing a small amount of various organic solvents capable of dissolving the composition may be used as the developer. Good. As the developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking immersion method, and a shower method can be adopted. The development time varies depending on the composition of the curable composition, but may be, for example, 30 seconds or more and 120 seconds or less.

(4) After the development, heating for drying the concavo-convex pattern 12 or the like may be performed. The heating conditions are, for example, about 60 to 120 ° C. and about 3 to 30 minutes.

In the step (II), for example, the lyophilic surface area 14 which is a concave part in the concave-convex pattern 12 having the lyophobic surface area 13 and the lyophilic surface area 14 formed in the above-mentioned step (I) A step of applying the first conductive layer forming composition to form the coating film 15 (FIGS. 1C and 1D).

と し て The first conductive layer forming composition is preferably a liquid ink having fluidity. In particular, from the viewpoints of conductivity and coatability, an ink in which at least one selected from the group consisting of metal particles and metal oxide particles is dispersed, and an ink containing a metal salt and a reducing agent are preferable.

The metal salt is reduced to a metal simple substance by reducing a metal ion contained in the metal salt by the reducing agent. Then, the conductive layer plays a role of expressing conductivity in a formed conductive layer such as a wiring. For example, when the metal salt is a copper salt, the copper ions contained in the copper salt are reduced by a reducing agent to become a single copper, and a conductive wiring is formed. As the metal salt, a copper salt and a silver salt are preferable. The above metal salts may be used alone or as a mixture of two or more.

In consideration of the solubility and dispersibility in a reducing agent or a solvent and the electrical resistance characteristics of the formed wiring, copper salts include copper acetate, copper propionate, copper isobutyrate, copper valerate, copper isovalerate, and formic acid. Copper carboxylate such as copper, copper formate tetrahydrate and copper glyoxylate are preferred.

For the purpose of reducing the metal ions contained in the metal salt into a simple metal, it is preferable to contain a reducing agent together with the above-mentioned metal salt. The reducing agent is not particularly limited as long as it has a reducing property for metal ions contained in the metal salt used.

Examples of the reducing agent include alkanethiols, amines, hydrazines, monoalcohols, diols, hydroxyamines, α-hydroxyketones, and carboxylic acids.

は As the first conductive layer forming composition, the compositions described in JP-A-2009-235964, JP-A-2011-12 2177, and JP-A-2011-241309 can be used.

The method for applying the first conductive layer forming composition includes a coating method using a brush or a brush, a dipping method, a spray method, a roll coating method, a spin coating method (spin coating method), and a slit die coating method. An appropriate method such as a bar coating method, flexographic printing, offset printing, an ink jet method, and a dispensing method can be adopted. Among these, the inkjet method is preferable from the viewpoint of easily forming a conductive layer at a predetermined position.

加熱 After applying the first conductive layer forming composition, heating for drying or curing the formed coating film 15 may be performed. The heating conditions are, for example, about 60 to 150 ° C. and about 3 to 20 minutes.

The step (III) includes, for example, irradiating at least the liquid-repellent surface region 13 with radiation to dissociate the group represented by the formula (1), thereby improving the wettability of the liquid-repellent surface region 13. The step of changing (FIG. 1E) is included. The irradiation of the radiation may be performed on the entire surface of the uneven pattern 12 and the coating film 15 of the first conductive layer forming composition.

(4) Due to the change in the wetting characteristics due to the irradiation of the radiation, the projections of the concavo-convex pattern 12, which have been the liquid-repellent surface area 13, have the lyophilic property. Due to such a change in the wettability, when the composition for forming a conductive layer is further applied using the above-mentioned convex portion as a bottom surface, the applicability of the composition is improved. As a result, it becomes easy to form a laminated film (layered structure).

As the radiation used for the irradiation, visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray and the like can be used. Among these radiations, radiations having a wavelength in the range of 190 nm to 450 nm are preferable, and radiations containing 365 nm ultraviolet rays are particularly preferable. The exposure amount is preferably a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (OA1 model 356, manufactured by OA1 Optical Associates Inc.), preferably 10 mJ / cm ² to 2000 mJ / cm ² , more preferably 20 mJ / cm 2. ² to 1500 mJ / cm ² .

In the step (IV), for example, the coating film 15 obtained by applying the first conductive layer forming composition and the concavo-convex pattern 12 (convex portion) after the irradiation of the radiation after the step (III) are used. A step of heating (post-baking) and curing. As a result, a structure 18 including the cured film 16 formed from the curable composition and the conductive layer 17 formed from the first conductive layer forming composition is obtained (FIG. 1F).

The coating film 15 obtained by applying the composition for forming a first conductive layer, and the concavo-convex pattern 12 (convex portion) after irradiation with radiation after the step (III) are heated to further laminate the upper portion thereof. Pattern roughness at the time of forming a film can be suppressed. Further, by performing the step (IV) by heating, the dissociated component containing the group represented by the above formula (1) is volatilized, and the lyophilic property of the surface of the cured film 16 can be further improved.

ポ ス ト The post-baking conditions vary depending on the curable composition used, the composition of the first conductive layer forming composition, and the like, but are preferably about 70 to 230 ° C for about 5 to 30 minutes.

Further, the method for forming the structure further includes (V) at least one of the pattern (cured film 16) after the step (IV) and the coating film (conductive layer 17) of the first conductive layer forming composition. The part may include a step of forming a coating film using the second conductive layer forming composition.

The step (V) includes, for example, a step of forming a pattern having a liquid-repellent surface region and a lyophilic surface region using a curable composition, as in the steps (I) to (II). And forming a coating film on the lyophilic surface region using the second conductive layer forming composition.

は The second conductive layer forming composition may be the same as the first conductive layer forming composition described above. By applying the same composition, a structure in which conductive layers are connected can be obtained, and a plurality of electronic components can be easily fixed with high accuracy. After a coating film is formed with the second conductive layer forming composition, the cured film 16 and the conductive layer 17 are obtained by performing a radiation irradiation step and a curing step similar to the above-mentioned steps (III) to (IV). A structure 21 in which the cured film 19 and the conductive layer 20 are further laminated on the film is obtained (FIG. 1G).

<Structure>
A structure according to one embodiment of the present invention is a structure including a conductive film and a cured film formed from the curable composition according to one embodiment of the present invention. As such a structure, the structure 18 in FIG. 1F and the structure 21 in FIG. 1G can be exemplified. The structure 18 includes the substrate 10 and a film having the cured film 16 and the conductive layer 17 laminated on the substrate 10. The structure 21 is a stacked structure including the substrate 10, a first film having the cured film 16 and the conductive layer 17, and a second film having the cured film 19 and the conductive layer 20 in this order. As in the structure 18, the cured film 16 and the conductive layer 17 may each be a single layer, or as in the structure 21, the cured films 16, 19 and the conductive layers 17, 20 may be stacked in two or more layers, respectively. It may be what has been done.

The structure is suitably used as a wiring structure, preferably a wiring structure having a laminated structure. In this case, the conductive layer in the structure constitutes a wiring or the like. The structure can be suitably used for a semiconductor element or an electronic circuit. The semiconductor element includes a power semiconductor. Further, the semiconductor element and the electronic circuit can be suitably used for an electronic device and the like. Examples of the electronic device include a liquid crystal display, a portable information device, a digital camera, an organic display, an organic EL lighting, a sensor, and a wearable device.

<Other embodiments>
The present invention is not limited to the above-described embodiment, and its configuration can be changed without changing the gist of the present invention. For example, the curable composition of the present invention may be used for forming a cured film by a method other than the method for forming a structure described above.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In addition, the measurement in an Example etc. was performed by the following method.
[GPC analysis]
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polymer of the component (A) were determined by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, trade name: HLC-8220) using tetrahydrofuran ( It was measured in terms of polystyrene under the condition of THF) solvent.
・ Measurement method: Gel permeation chromatography (GPC) method ・ Standard substance: polystyrene equivalent ・ Equipment: Tosoh Corporation, trade name: HLC-8220
-Column: Guard column HXL-H, TSK gel G7000HXL, two TSK gel GMHXL, and TSK gel G2000HXL manufactured by Tosoh Corporation-Solvent: Tetrahydrofuran-Sample concentration: 0.7% by mass
・ Injection volume: 70 μL
・ Flow rate: 1 mL / min
[NMR]
¹ H-NMR was measured with a nuclear magnetic resonance apparatus (AVANCE III AV400N manufactured by Bruker) at 25 ° C. and CDCl ₃ .

<Synthesis of component (A)>
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 44 parts by mass of 4-hydroxyphenyl methacrylate, 0.3 parts by mass of pyridinium-p-toluenesulfonate, and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-vinyloxyoctane (69 parts by mass) was added, and the mixture was heated at 80 ° C. under a nitrogen atmosphere. By reacting for 3 hours, a solution containing a fluorine-containing monomer was obtained.
Next, 135 parts by mass of propylene glycol monomethyl ether acetate, 11 parts by mass of methyl methacrylate, 19 parts by mass of stearyl methacrylate, 8 parts by mass of glycidyl methacrylate, and 18 parts by mass of 4-trimethoxysilyl styrene were charged into the obtained monomer solution. It is. After slightly stirring the mixture, 8 parts by mass of dimethyl 2,2′-azobis (2-methylpropionate) and 4 parts by mass of 2,4-diphenyl-4-methyl-1-pentene were charged, and the mixture was stirred under a nitrogen atmosphere. The temperature of the solution was raised to 80 ° C. with gentle stirring, and the polymerization was carried out while maintaining this temperature for 4 hours to obtain a solution containing the polymer (P-1) as a copolymer (solid). Separation concentration = 30.5% by mass, Mw = 25000, Mw / Mn = 2.2). The solid content concentration means the ratio of the mass of the copolymer to the total mass of the copolymer solution.
The obtained reaction solution was added dropwise to a large excess of methanol for reprecipitation purification. After drying, the polymer (A) (P-1) was obtained as a white solid copolymer. The obtained polymer (P-1) of the component (A) was analyzed using ¹ H-NMR, and it was confirmed that acetalization was in progress (chemical shift: 5.50 ppm, acetal group C-). H).

[Synthesis Example 2]
In a flask equipped with a condenser and a stirrer, 8 parts by mass of dimethyl 2,2'-azobis (2-methylpropionate), 4 parts by mass of 2,4-diphenyl-4-methyl-1-pentene, and propylene glycol 300 parts by mass of monomethyl ether acetate were charged. Subsequently, 70 parts by mass of 4-hydroxyphenyl methacrylate, 11 parts by mass of methyl methacrylate, and 19 parts by mass of stearyl methacrylate were charged, and the temperature of the solution was increased to 80 ° C. with gentle stirring under a nitrogen atmosphere. By carrying out polymerization for 4 hours, a solution containing a precursor which was a copolymer was obtained (solid content concentration = 24.3% by mass, Mw = 20,000, Mw / Mn = 2.5). The solid content concentration means the ratio of the mass of the copolymer to the total mass of the copolymer solution.
Next, 165 parts by mass of propylene glycol monomethyl ether acetate, 0.5 parts by mass of pyridinium-p-toluenesulfonate, and 3,3,4,4,5,5,6,6,7,7 , 8,8,8-Tridecafluoro-1-vinyloxyoctane (140 parts by mass) was added, and the mixture was reacted at 80 ° C. for 3 hours under a nitrogen atmosphere.
The obtained reaction solution was added dropwise to a large excess of methanol for reprecipitation purification, and after drying, a polymer (P-2) of the component (A) was obtained as a white solid copolymer. The obtained polymer (P-2) of the component (A) was analyzed using ¹ H-NMR, and it was confirmed that acetalization was in progress (chemical shift: 5.50 ppm, acetal group C-). H).

[Synthesis Examples 3 to 5]
Except for using each component having the kind and the compounding amount (parts by mass) shown in Table 1, it has the same molecular weight and molecular weight distribution as the polymer (P-2) by the same method as in Synthesis Example 2 (A The components (P-3) to (P-5) were obtained. In Table 1, 4-hydroxyphenyl methacrylate is abbreviated as HPMA, methyl methacrylate is abbreviated as MMA, stearyl methacrylate is abbreviated as StMA, 4-trimethoxysilylstyrene is abbreviated as TMST, and glycidyl methacrylate is abbreviated as GMA. In short, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-1-vinyloxyoctane is abbreviated as a fluorine compound, and propylene glycol monomethyl ether acetate is PGMEA. Dimethyl 2,2'-azobis (2-methylpropionate) is abbreviated as DAMP, 2,4-diphenyl-4-methyl-1-pentene is abbreviated as DMPN, and pyridinium-p-toluenesulfonate is PPTS. Is abbreviated.

 

 

[Synthesis Example 6]
A flask equipped with a condenser and a stirrer was charged with 10 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether. Subsequently, 25 parts by mass of 4-trimethoxysilylstyrene, 7 parts by mass of methacrylic acid, 10 parts by mass of glycidyl methacrylate, (3-ethyloxetane-3-yl) methyl methacrylate (“OXE-30” (manufactured by Osaka Organic Chemical Industry Co., Ltd.) )) 48 parts by mass and 10 parts by mass of N-phenylmaleimide were charged and purged with nitrogen. Thereafter, the temperature of the solution was raised to 70 ° C. with gentle stirring, and the temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (M-1) as the component (A). The solid concentration of this polymer solution was 34.1% by mass, the Mw of the polymer (M-1) as the component (A) was 14,000, and the molecular weight distribution (Mw / Mn) was 2.2. .
The resulting reaction solution was added dropwise to a large excess of a mixture of hexane / 2-propanol (1: 1 ratio) for reprecipitation purification. After drying, component (A) was obtained as a white solid copolymer. A polymer (M-1) was obtained.

[Synthesis Examples 7 and 8]
A molecular weight and a molecular weight distribution equivalent to that of the polymer (M-1) of the component (A) were obtained in the same manner as in Synthesis Example 6, except that the components and the amounts (parts by mass) shown in Table 2 were used. The polymers (M-2) to (M-3) of the component (A) having In Table 2, methacrylic acid is abbreviated as MA, glycidyl methacrylate is abbreviated as GMA, N-phenylmaleimide is abbreviated as CHMI, (3-ethyloxetane-3-yl) methyl methacrylate is abbreviated as EOXM, Trimethoxysilylstyrene is abbreviated as TMST, methyl methacrylate is abbreviated as MMA, diethylene glycol methyl ethyl ether is abbreviated as EDM, and 2,2′-azobis (2,4-dimethylvaleronitrile) is abbreviated as AIBN.

<Preparation of curable composition>
[Example 1]
100 parts by mass of the polymer (P-1) of the component (A) obtained in Synthesis Example 1 above, and 4 parts by mass of (B-1) N-hydroxynaphthalimide-nonafluorobutanesulfonic acid ester as an acid generator And 0.02 parts by mass of (D-1) 2-phenylbenzimidazole as an acid diffusion controller (quencher), and (C-1) propylene as a solvent so that the solid content concentration becomes 13% by mass. After adding glycol monomethyl ether acetate, the mixture was filtered through a Millipore filter having a pore size of 0.5 μm to prepare a curable composition (S-1).

[Example 2, Comparative Example 1]
Curable compositions (S-2) and (S-15) were obtained in the same manner as in Example 1 except that the components and the amounts (parts by mass) shown in Table 3 were used.

[Example 3]
2 parts by weight of the polymer (P-2) of the component (A) obtained in Synthesis Example 2 above, 100 parts by weight of the polymer (M-1) obtained in Synthesis Example 6, and (B) as an acid generator -1) A mixture of 4 parts by mass of N-hydroxynaphthalimide-nonafluorobutanesulfonic acid ester and 0.02 parts by mass of (D-1) 2-phenylbenzimidazole as an acid diffusion controller (quencher) was mixed. After adding (C-1) propylene glycol monomethyl ether acetate as a solvent so that the partial concentration becomes 13% by mass, the mixture is filtered through a millipore filter having a pore size of 0.5 μm to obtain a curable composition (S-3). Was prepared.

[Examples 4 to 14, Comparative Example 2]
The curable compositions (S-4) to (S-14), (S-) were prepared in the same manner as in Example 3 except that the components and the amounts (parts by mass) shown in Table 3 were used. 16) was obtained. In Table 3, C-1 is propylene glycol monomethyl ether acetate (dD is 15.6, (dP ＾ 2 + dH ＾ 2) ＾ (1/2) is 11.3), and C-2 is octyl acetate ( dD is 15.8, (dP ＾ 2 + dH ＾ 2) ＾ (１ ／) is 5.9), and C-3 is diethylene glycol methyl ethyl ether (dD is 15.8, (dP ＾ 2 + dH ＾ 2) ＾). (1/2) is 7.9), C-4 is propylene glycol methyl ether (dD is 15.6, (dP ＾ 2 + dH ＾ 2) ＾ (1/2) is 13.2), and C-4 is -5 is toluene (dD is 18, (dP ＾ 2 + dH ＾ 2) ＾ (＾) is 2.4).

<Evaluation method>
[Film evaluation]
The following evaluations were performed using the curable compositions prepared in Examples 1 to 14 and Comparative Examples 1 and 2. Table 4 shows the results.

[Contact angle (repellency conversion)]
The curable compositions prepared in Examples 1 to 14 and Comparative Examples 1 and 2 were each applied to a 9.5 cm square non-alkali glass substrate (EAGLE-XG, 0.7 mm thick, manufactured by Corning) using a spinner. . Thereafter, the film was prebaked on a hot plate at 70 ° C. for 4 minutes to form a coating film having a thickness of 2 μm. The obtained coating film was irradiated with radiation through a quartz mask (contact) using a high-pressure mercury lamp (exposure machine: MA-1400 manufactured by Dainippon Kaken Co., Ltd.) at an exposure amount of 300 mJ / cm ² . Thereafter, baking was performed at 70 ° C. for 5 minutes using a hot plate, so that the exposed portion became a lyophilic portion and the non-exposed portion became a lyophobic portion. (Liquid-repellent surface region) to form a film (hereinafter, may be referred to as a “lyophilic / repellent patterning film”). Using a contact angle meter (CA-X, manufactured by Kyowa Interface Science Co., Ltd.), the coating surface of the lyophilic portion corresponding to the exposed portion and the unexposed portion of the coating film corresponding to the lyophobic portion were formed on the formed lyophilic / repellent film. The contact angle of tetradecane on the surface was measured to confirm the repellency. In Table 4, the contact angle of tetradecane on the surface of the unexposed portion is indicated by “TD w / o UV”, and the difference between the contact angle of the tetradecane on the surface of the unexposed portion and the surface of the exposed portion is indicated by “Δ (difference)”. Was. Regarding the “TD w / o UV”, a case of 60 ° or more is particularly good, a case of 50 ° or more and less than 60 ° is good, a case of 40 ° or more and less than 50 ° is slightly good, and a case of less than 40 ° Was determined to be defective. Regarding “Δ (difference)”, a case of 50 ° or more is particularly good, a case of 40 ° or more and less than 50 ° is good, a case of 30 ° or more and less than 40 ° is slightly good, and The case was determined to be defective.

[Formation of liquid repellent template]
Each of the curable compositions prepared in Examples 1 to 14 and Comparative Examples 1 and 2 was applied to a 9.5 cm square non-alkali glass substrate (EAGLE-XG, 0.7 mm thick, manufactured by Corning Incorporated) using a spinner. After that, the coating was prebaked on a hot plate at 70 ° C. for 4 minutes to form a coating film having a thickness of 2.0 μm. The obtained coating film was irradiated with radiation using a high-pressure mercury lamp (exposure machine: MA-1400 manufactured by Dainippon Kaken Co., Ltd.) through a photomask (line & space = 50 μm / 450 μm) with an exposure amount of 300 mJ / cm ^2. went. Subsequently, the exposed portion was removed by immersing the substrate in a 2.38% tetraammonium hydroxide aqueous solution for 90 seconds. By removing the exposed portion, the unexposed portion corresponding to the lyophobic portion becomes a convex portion. Subsequently, the obtained pattern was dried and baked on a hot plate at 70 ° C. for 15 minutes to obtain a liquid-repellent template having a liquid-repellent convex portion (an uneven pattern).

[Ink coating assist performance using liquid repellent template]
In the vicinity of the concave portion of the lyophobic template prepared above, using an automatic minimum contact angle meter (MCA-2 manufactured by Kyowa Interface Science Co., Ltd.), 60 pL of tetradecane was dropped by a microcapillary, and after 5 seconds, the dropped portion was dropped from the dropping direction. Observed with a microscope. Here, FIG. 2 is an enlarged photograph showing an example of a very good ink application assisting performance, and FIG. 3 is an enlarged photograph showing a slightly inferior but sufficient example of the ink applying assisting performance as compared with the example of FIG. .

ＡAs shown in FIG. 2, when the line of the formed concave portion was not disturbed by tetradecane, it was evaluated as A. As shown in FIG. 3, a case where the line of the concave portion was partially disturbed by tetradecane was evaluated as B. In addition, when the line of the concave portion was greatly disturbed by tetradecane and the tetradecane spread over the entire surface irrespective of the line of the concave portion, it was evaluated as C.

[Appearance of coating film]
A film obtained by the same method as in the evaluation of [contact angle] was used, and a transparent film without unevenness or granularity was obtained, and was evaluated as A. Partial unevenness, granularity, and whitening were observed. The sample was evaluated as B when it was slightly good, and was evaluated as B when the whole surface was uneven, grainy, and whitened.

[Formation of laminated body]
Each of the curable compositions prepared in Examples 1 to 14 and Comparative Examples 1 and 2 was applied on a 9.5 cm square non-alkali glass substrate (EAGLE-XG, 0.7 mm thick, manufactured by Corning) using a spinner. After that, prebaking was performed on a hot plate at 70 ° C. for 4 minutes to form a coating film having a thickness of 2.0 μm.
The obtained coating film was irradiated with radiation using a high-pressure mercury lamp (exposure machine: MA-1400 manufactured by Dainippon Kaken Co., Ltd.) through a photomask (line & space = 50 μm / 450 μm) with an exposure amount of 300 mJ / cm ^2. went. Subsequently, the exposed portion was removed by immersing the substrate in a 2.38% tetraammonium hydroxide aqueous solution for 90 seconds. Subsequently, the substrate was dried and baked on a hot plate at 70 ° C. for 15 minutes to obtain a liquid-repellent template having a liquid-repellent convex portion (an uneven pattern).
When dry cure Ag (manufactured by Colloidal Inc.), which is a metal-containing composition, was applied by syringe to the vicinity of the concave portion of the formed lyophobic template, the template using the curable composition of Comparative Example 1 had a concave portion. In addition, it spread greatly, and a laminated body described later could not be formed. On the other hand, in the templates using the curable compositions of the other Examples and Comparative Examples, dry cured Ag does not remain on the convex portions of the liquid-repellent template, there is no erosion of the liquid-repellent template, and the liquid in the concave portions is further reduced. We confirmed that the wet spread. The lyophobic template coated with dry-cured Ag was prebaked on a hot plate at 70 ° C. for 2 minutes, and heated on a hot plate at 130 ° C. for 5 minutes to cure the dry-cured Ag.
Thereafter, using a high-pressure mercury lamp (exposure machine: MA-1400 manufactured by Dainippon Kaken Co., Ltd.), irradiation was performed at an exposure amount of 1000 mJ / cm ² , and the mixture was heated on a hot plate at 130 ° C. for 5 minutes to obtain a curable composition. Was cured.
Then, the curable compositions prepared in Examples 1 to 14 and Comparative Example 2 were applied again by a spinner, respectively, and then prebaked on a hot plate at 70 ° C. for 4 minutes to form a 2.0 μm thick coating film. Was formed to form a laminate having a total of 4.0 μm. Irradiation was performed through a photomask (line & space = 50 μm / 450 μm) using a high-pressure mercury lamp (exposure machine: MA-1400 manufactured by Dainippon Kaken Co., Ltd.) with an exposure amount of 300 mJ / cm ² . Subsequently, the exposed part was removed by immersing the substrate in a 2.38% tetraammonium hydroxide aqueous solution for 90 seconds. Subsequently, the substrate was dried and baked on a hot plate at 70 ° C. for 15 minutes to form a liquid-repellent template having liquid-repellent convex portions on the top of the laminate. Here, FIG. 4 is an enlarged photograph showing an example in which a good laminate (one example of a structure) is formed.

By laminating, without losing the boundary of the upper and lower layers, and the liquid-repellent template could be formed on the upper part of the laminate, A, when the metal-containing composition spread wet other than the concave portion of the template, and Those that could not form a laminate due to loss of the boundary were determined to be C.

As shown in Table 4, each of the curable compositions of Examples 1 to 14 has a large contrast between the liquid-repellent surface area and the lyophilic surface area, has excellent ink application assist performance, and has a good appearance. Can be formed. Further, each of the curable compositions of Examples 1 to 14 can form a good laminate. Thus, it can be seen that each of the curable compositions of Examples 1 to 14 is excellent in forming a highly accurate laminated wiring and the like.

硬化 The curable composition of the present invention is suitable for forming a pattern that becomes a mold suitable for applying a conductive ink. The pattern formed by the curable composition of the present invention has high lyophobic and lyophilic contrast and curing characteristics. Therefore, a structure such as a laminated wiring with high precision can be formed by a method for forming a structure using a pattern or the like formed using the curable composition or the like of the present invention.

DESCRIPTION OF SYMBOLS 10 Substrate 11 Coating film 12 Concavo-convex pattern 13 Liquid-repellent surface area 14 Liquid-philic surface area 15 Coating 16, 19 Cured film 17, 20 Conductive layer 18, 21 Structure

Claims (12)

(A) a polymer component containing a structural unit having a group represented by the following formula (1), a structural unit having an alkoxysilyl group, and a structural unit having a cyclic ether group in the same or different polymers;
A curable composition containing (B) an acid generator and (C) a solvent.

(In the formula (1), ^{R 1} and ^{R 2} are each independently a is .n is hydrogen atom or a fluorine atom, an integer of 1 ~ 10 .n is 2 or more, multiple ^{R 1} is The same or different, and a plurality of R ² may be the same or different. * Represents a binding site.) The curable composition according to claim 1, wherein the structural unit having the group represented by the formula (1) further has an acetal group linked to the group represented by the formula (1). The curable composition according to claim 1 or 2, wherein the polymer component (A) further includes a structural unit having a saturated hydrocarbon group having 8 to 30 carbon atoms. The curable composition according to any one of claims 1 to 3, wherein the cyclic ether group is an oxiranyl group, an oxetanyl group, or a combination thereof. The structural unit having a group represented by the formula (1) includes a phenylene group, a tolylene group, a mesitylene group, a naphthylene group, a biphenylene group, or a combination thereof. Curable composition. (6) The curable composition according to any one of (1) to (5), wherein the polymer component (A) contains two or more polymers. The content of each of the two or more polymers is 0.5% by mass or more when the mass of the curable composition excluding the solvent (C) is 100% by mass. 7. The curable composition according to 6. Other than the first polymer, wherein the two or more polymers include a structural unit having a group represented by the formula (1) and a structural unit having an alkoxysilyl group. The curable composition according to claim 6, further comprising a second polymer. The solvent (C) has a dispersion parameter (dD) of Hansen solubility parameter of 10 or more and 17 or less, and a square root of the sum of squares of a polarization term (dP) and a hydrogen bond term (dH) ((dP ＾ 2 + dH ＾ 2). The curable composition according to any one of claims 1 to 8, further comprising a solvent having (＾) (＾)) of 10 or less. (I) a step of forming a pattern having a lyophobic surface region and a lyophilic surface region on the substrate using the curable composition according to any one of claims 1 to 9;
(II) a step of forming a coating film on the lyophilic surface region using the first conductive layer forming composition;
(III) irradiating at least the liquid-repellent surface region with radiation, and (IV) curing the pattern after the (III) step.
A method for forming a structure comprising: (V) A step of forming a coating film using the second conductive layer forming composition on at least a part of the pattern after the step (IV) and the coating film of the first conductive layer forming composition. The method for forming a structure according to claim 10, further comprising: A structure comprising a cured film formed from the curable composition according to any one of claims 1 to 9, and a conductive layer.

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