Curable composition

Abstract

Provided is a polysiloxane-containing curable composition capable of forming a resin layer in which a curing reaction can sufficiently proceed even after development. An embodiment of the present invention is a curable composition comprising: a first component that is a polysiloxane having an epoxy group; and a second component that is a compound including a carbonyl group, a first group bonded to the carbonyl group and capable of generating a base liberated from the carbonyl group upon heating, and a second group containing an ethylenic double bond.

Description

curable composition

[0001] This invention relates to a curable composition.

[0002] Photolithography has traditionally been used for microfabrication in the manufacturing of semiconductor devices. Photolithography is a method in which a layer made of a photosensitive composition is formed on a substrate such as a silicon wafer or a copper-clad laminate, and after irradiation (exposure) with light in a predetermined pattern, either the unexposed or exposed areas are dissolved and removed with a developer to form a pattern.

[0003] Resin materials used in semiconductor devices and photolithography require high insulation performance, chemical stability, and adhesion to metals. Polysiloxane is one such material that can be used in photolithography and meets these requirements.

[0004] For example, Patent Document 1 discloses a photosensitive resin composition containing a polysiloxane compound having a specific structure and a photoradical generator, which can be formed into fine patterns by photolithography.

[0005] Japanese Patent Publication No. 2011-186069

[0006] It has been found that when a resin layer formed with a curable composition containing a polysiloxane compound according to the prior art is developed, the curing of the resulting cured product may not proceed sufficiently due to the elution of the curing agent into the solvent during development, and a pattern with the desired performance may not be obtained.

[0007] Therefore, the object of the present invention is to provide a polysiloxane-containing curable composition that can form a resin layer in which the curing reaction can proceed sufficiently even after development.

[0008] The inventors have discovered that the above problems can be solved by a curable composition formulated in combination with a specific polysiloxane and a specific compound, and have completed the present invention. That is, the present invention is as follows.

[0009] One embodiment of the present invention is a curable composition. The curable composition includes a first component and a second component. The first component is a polysiloxane having an epoxy group. The second component is a compound including a carbonyl group, a group bonded to the carbonyl group, a first group that generates a base released from the carbonyl group by heating, and a second group including an ethylenic double bond.

[0010] The second group preferably includes a (meth)acryloyl group. The second component is preferably a compound represented by the following general formula (A). (In general formula (A), R １ is the first group, R ２ is a divalent linking group, n1 is 1 or 2, and n2 is 1 or 2.) In general formula (A), R １ is preferably a group represented by the following general formula (1)-11, general formula (1)-12, general formula (1)-13, or general formula (1)-14. In the formula, R １１ , R １２ , R １３ , R ２１ , R ２２ , R ２３ , R ２４ , R ３１ , R ３２ , R ３３ , R ４１ , R ４２ , R ４３ and R ４４ each independently represent a hydrogen atom or a hydrocarbon group. When two or more of R １１ , R １２ and R １３ are hydrocarbon groups, two or more of the hydrocarbon groups may be bonded to each other to form a ring. When two or more of R ２１ , R ２２ , R ２３ and R ２４ are hydrocarbon groups, two or more of the hydrocarbon groups may be bonded to each other to form a ring. When two or more of R ３１ , R ３２ and R ３３If two or more of them are hydrocarbon groups, the two or more hydrocarbon groups may be bonded to each other to form a ring, R ４１ , R ４２ , R ４３ and R ４４ If two or more of these are hydrocarbon groups, the two or more hydrocarbon groups may be bonded to each other to form a ring. * represents a bond that connects to the carbon atom of the carbonyl group. The first component preferably has a functional group containing an unsaturated carbon bond. The curable composition preferably further contains a photoradical generator. The first component preferably contains a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II). In the formula, R Ａ R represents a hydrogen atom, hydroxyl group, alkoxy group, or hydrocarbon group. Ｂ This represents a functional group containing an epoxy group. In the formula, R Ｃ R represents a hydrogen atom, hydroxyl group, alkoxy group, or hydrocarbon group. Ｄ This represents a functional group containing an unsaturated double bond.

[0011] The present invention provides a polysiloxane-containing curable composition capable of forming a resin layer in which the curing reaction can proceed sufficiently even after development.

[0012] Figure 1 is a scatter plot showing the decrease in epoxy groups in the evaluation sample according to the example, which changes depending on whether or not development is performed and the heating time. Figure 2 is a scatter plot showing the decrease in epoxy groups in the comparative sample, which changes depending on whether or not development is performed and the heating time.

[0013] If isomers exist for the compound described, all possible isomers are available for use in this disclosure unless otherwise specified.

[0014] In this disclosure, unless otherwise specified, "unsaturated carbon bond" refers to an ethylenically or acetylenely occurring multiple carbon-carbon bond (double or triple bond).

[0015] In this disclosure, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polymers were determined by gel permeation chromatography (GPC). In the GPC, a Shodex K-805L column was used, with a column temperature of 40°C, a flow rate of 1 mL / min, chloroform as the eluent, and polystyrene as the standard substance.

[0016] Where the upper and lower limits of a numerical range are described separately in this disclosure, all combinations of each lower limit and each upper limit shall be substantially described to the extent that they are not inconsistent.

[0017] The components of the curable composition will be described below, followed by a description of the method of use and applications of the curable composition.

[0018] <<<<<Components of the Curable Composition>>>> The curable composition of this disclosure comprises a polysiloxane having a specific structure (component 1) and a compound having a specific structure (component 2). The curable composition of this disclosure preferably contains a photoradical generator. The curable composition of this disclosure may also contain other components. Each component is described below.

[0019] <<

[0020] Polysiloxanes having epoxy groups preferably include those containing the structural unit represented by formula (I), which will be described later.

[0021] The polysiloxanes relating to this disclosure preferably have functional groups containing unsaturated carbon bonds. The inclusion of unsaturated carbon bonds in the polysiloxane makes it photocurable. Such polysiloxanes allow for two curing reactions: an epoxy reaction and a photocuring reaction, enabling the curable composition to be patterned by photolithography. Furthermore, using such polysiloxanes facilitates the formation of cured products with excellent properties such as low dielectric strength.

[0022] Specific examples of polysiloxanes having functional groups containing epoxy groups and unsaturated carbon bonds include those containing the structural unit shown in formula (I) and the structural unit shown in formula (II) below.

[0023] In the formula, R Ａ R represents a hydrogen atom, a hydroxyl group, an alkoxy group (preferably with 1 to 10, 1 to 5, or 1 to 3 carbon atoms), or a hydrocarbon group (preferably with 1 to 10, 1 to 5, or 1 to 3 carbon atoms). Ｂ This represents a functional group containing an epoxy group.

[0024] R in equation (I) Ｂ In this case, the epoxy group is preferably located at the end of the side chain. More specifically, R Ｂ It is preferable that the functional group is represented by the following formula (I-1), and more preferably by the following formula (I-2).

[0025]

[0026] In the formula, R ｂ１ This represents a hydrocarbon group that may contain a single bond or a heteroatom (for example, a halogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom) (preferably with 1 to 20, 1 to 10, or 1 to 5 carbon atoms).

[0027] In the formula, R ｂ２ R represents a hydrocarbon group (preferably with 1 to 10, 1 to 5, or 2 to 5 carbon atoms), ｂ３ This represents a hydrocarbon group (preferably with 1 to 10, 1 to 5, or 1 to 3 carbon atoms).

[0028] In the formula, R Ｃ R represents a hydrogen atom, a hydroxyl group, an alkoxy group (preferably with 1 to 10, 1 to 5, or 1 to 3 carbon atoms), or a hydrocarbon group (preferably with 1 to 10, 1 to 5, or 1 to 3 carbon atoms). Ｄ This represents a functional group containing an unsaturated double bond.

[0029] R in equation (II)Ｄ In this case, the unsaturated carbon bond is preferably located at the end of the side chain. More specifically, R Ｄ It is preferable that the functional group is represented by the following formula (II-1), and more preferably by the functional group represented by the following formula (II-2).

[0030] In the formula, R ｄ１ R represents a hydrocarbon group which may contain a single bond or a heteroatom (for example, a halogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom) (preferably with 1 to 10, 1 to 5, or 2 to 4 carbon atoms), ｄ２ This represents a hydrogen atom or a hydrocarbon group (preferably with 1 to 5 or 1 to 2 carbon atoms).

[0031] In the formula, R ｄ３ R represents a hydrocarbon group (preferably with 1 to 10, 1 to 5, or 2 to 4 carbon atoms), ｄ２ represents a hydrogen atom or a methyl group.

[0032] Polysiloxanes having structural units represented by formulas (I) and (II) have structures extended by siloxane bonds between structural units represented by formula (I) and structural units represented by formula (II), siloxane bonds between structural units represented by formula (I) and structural units represented by formula (II), etc. Polysiloxanes may be in the form of block copolymers in which structural units represented by formula (I) and structural units represented by formula (II) are arranged according to a predetermined rule, or they may be in the form of random copolymers in which structural units represented by formula (I) and structural units represented by formula (II) are arranged randomly.

[0033] The polysiloxanes relating to this disclosure may contain structures other than the structural unit represented by formula (I) and the structural unit represented by formula (II). The content of the structural unit represented by formula (I) in the polysiloxane, or the total content of the structural unit represented by formula (I) and the structural unit represented by formula (II) in the polysiloxane, is preferably 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, or 99% by mass or more. When the polysiloxane contains both the structural unit represented by formula (I) and the structural unit represented by formula (II), the ratio (y / x) of the number of repeating units y of the structural unit represented by formula (II) to the number of repeating units x of the structural unit represented by formula (I) is preferably 0.05 / 0.95 to 0.70 / 0.30, or 0.10 / 0.90 to 0.60 / 0.40.

[0034] In other words, the preferred polysiloxane relating to this disclosure has the structure represented by the following formula (III).

[0035]

[0036] R Ａ , R Ｂ , R Ｃ , and R Ｄ As previously stated, x and y can be any value depending on the weight-average molecular weight of the polysiloxane. The ratio of y to x (y / x) is preferably 0.05 / 0.95 to 0.70 / 0.30, or 0.10 / 0.90 to 0.60 / 0.40. Note that formula (III) does not refer only to block copolymers, but also includes random copolymers.

[0037] Polysiloxanes may have a network structure. For example, in a part of a polysiloxane having structural units represented by formulas (I) and (II), the R of formula (I) Ａ The part and / or R of formula (II) Ｃ The portion may have a network structure in which parts are substituted with siloxane bonds and bonded to other structural units.

[0038] The weight-average molecular weight of the polysiloxane is preferably 2,000 or more, or 10,000 or more, and more preferably 50,000 or less, 35,000 or less, or 25,000 or less. Furthermore, the polydispersity index (weight-average molecular weight / number-average molecular weight) of the polysiloxane is preferably 1.5 to 5.0, and more preferably 1.5 to 2.0.

[0039] <<Method for Producing Polysiloxanes>> <Raw Materials / Monomers> Polysiloxanes having epoxy groups can be produced, for example, by polymerizing a monomer containing a silane component (A) represented by the following formula (I-A). Polysiloxanes having functional groups containing epoxy groups and unsaturated double bonds can be produced, for example, by polymerizing a monomer containing a silane component (A) represented by the following formula (I-A) and a silane component (B) represented by the following formula (II-A).

[0040]

[0041] In the formula, R １０１ R represents a hydrogen atom, a hydroxyl group, an alkoxy group (with carbon atoms, for example, 1 to 10, 1 to 5, or 1 to 3), or a hydrocarbon group (with carbon atoms, for example, 1 to 10, 1 to 5, or 1 to 3). １０２ , R １０３ Each of these independently represents a hydroxyl group or an alkoxy group, R Ｂ represents a functional group containing an epoxy group, and R in formula (I) Ｂ It is similar to that.

[0042]

[0043] In the formula, R ２０１ R represents a hydrogen atom, a hydroxyl group, an alkoxy group (with carbon atoms, for example, 1 to 10, 1 to 5, or 1 to 3), or a hydrocarbon group (with carbon atoms, for example, 1 to 10, 1 to 5, or 1 to 3). ２０２ , R ２０３ Each of these independently represents a hydroxyl group or an alkoxy group, R Ｄ R represents a functional group containing an unsaturated double bond, and in formula (II), R Ｄ It is similar to that.

[0044] Methods for synthesizing polysiloxanes using these monomers can be conventionally known methods. For example, a synthetic composition can be prepared containing each silane component (or a mixture of each silane component and a partial hydrolysate of each silane component), and water as needed. Polysiloxanes can then be synthesized by condensing each silane component in the presence of a catalyst and heating as needed. Alternatively, the catalyst may be removed (e.g., by neutralization) or the polysiloxane may be distilled as needed. By using silane component (A) shown in formula (I-A) as a raw material, a preferred polysiloxane having a repeating structure consisting of structural units containing epoxy groups can be obtained. Furthermore, by using silane component (A) shown in formula (I-A) and silane component (B) shown in formula (II-A) as raw materials, a preferred polysiloxane having a repeating structure consisting of structural units containing epoxy groups and structural units having functional groups containing unsaturated double bonds can be obtained. In this process, the ratio (y / x) of structural units in the resulting polysiloxane can be adjusted by changing the molar ratio of silane component (A) and silane component (B).

[0045] The catalyst is not particularly limited, and organic acids (e.g., formic acid, acetic acid, oxalic acid, maleic acid, citric acid, etc.) or inorganic acids (e.g., hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, etc.) can be used.

[0046] The synthesis composition may, if necessary, contain an organic solvent.

[0047] Polysiloxanes having epoxy groups may be produced by modifying the side chains of polysiloxane with functional groups containing epoxy groups. Alternatively, polysiloxanes having functional groups containing unsaturated double bonds may be produced by modifying the side chains of polysiloxane with functional groups containing unsaturated double bonds.

[0048] <<<Second Component>>> The second component is a compound comprising: [1] a carbonyl group (hereinafter sometimes referred to as a specific carbonyl group); [2] a group bonded to the specific carbonyl group, which generates a base that is released from the specific carbonyl group upon heating; and [3] a second group containing an ethylenic double bond.

[0049] The second component may be a compound having a carboxylic acid amide bond formed by the bonding of a nitrogen atom contained in the first group to a carbon atom of a specific carbonyl group. Preferably, the second component has the property that the bond between the carbon atom of the specific carbonyl group present in its structure and the nitrogen atom contained in the first group is broken by heating or the like, and the nitrogen atom that was bonded to the carbon atom of the specific carbonyl group is bonded to a hydrogen atom to produce a basic compound (in this disclosure, also simply referred to as "base") in which this bond is broken.

[0050] The second component may contain one specific carbonyl group and one first group, or it may contain two specific carbonyl groups and two first groups. If the second component contains two first groups, the first groups may be the same or different.

[0051] The second component may contain one second group or two second groups. If the second component contains two second groups, the second groups may be the same or different.

[0052] In the second component, it is preferable that the specific carbonyl group and the second group are bonded via a ring structure, and more preferably that they are bonded via a benzene ring. When the specific carbonyl group and the second group are bonded to a benzene ring, the bonded position is preferably the meta or para position.

[0053] The specific structures of the first group, the second group, and the second component will be described in detail below.

[0054] <First group> The first group is bonded to a carbonyl group and generates a base that is released from the carbonyl group upon heating (a group that is released from the carbonyl group upon heating and constitutes a base), and is not particularly limited.

[0055] The first group is preferably a group represented by the following general formulas (1)-11, (1)-12, (1)-13, or (1)-14.

[0056] In the formula, R １１ , R １２ , R １３ , R２１ , R ２２ , R ２３ , R ２４ , R ３１ , R ３２ , R ３３ , R ４１ , R ４２ , R ４３ and R ４４ each independently represents a hydrogen atom or a hydrocarbon group. When two or more of R １１ , R １２ and R １３ are hydrocarbon groups, the two or more hydrocarbon groups may be bonded to each other to form a ring. When two or more of R ２１ , R ２２ , R ２３ and R ２４ are hydrocarbon groups, the two or more hydrocarbon groups may be bonded to each other to form a ring. When two or more of R ３１ , R ３２ and R ３３ are hydrocarbon groups, the two or more hydrocarbon groups may be bonded to each other to form a ring. When two or more of R ４１ , R ４２ , R ４３ and R ４４ are hydrocarbon groups, the two or more hydrocarbon groups may be bonded to each other to form a ring. * represents a bond that binds to the carbon atom of a specific carbonyl group.

[0057] When the first group is a group represented by general formula (1)-11, general formula (1)-12, general formula (1)-13 or general formula (1)-14, the nitrogen atom contained in these groups and the carbon atom of the carbonyl group are bonded to form a carboxylic acid amide bond.

[0058] A compound having a group represented by general formula (1)-11, general formula (1)-12, general formula (1)-13 or general formula (1)-14 has a base conversion action of expressing a base by the action of a base and a base growth action of reacting with a hydroxyl group or the like to generate a base, as described later.

[0059] R １１ , R １２ and R １３ (hereinafter, "R１１ ~R １３ The terms (sometimes abbreviated as ") may all be the same, may all be different, or may only partially be the same. Similarly, in general formula (1)-12, R ２１ , R ２２ , R ２３ and R ２４ (Hereinafter referred to as “R ２１ ~R ２４ The terms (sometimes abbreviated as ") may all be the same, may all be different, or may only partially be the same. Similarly, in general formula (1)-13, R ３１ , R ３２ and R ３３ (Hereinafter referred to as “R ３１ ~R ３３ The elements (sometimes abbreviated as ") may all be the same, may all be different, or may only partially be the same. Similarly, in general formula (1)-14, R ４１ , R ４２ , R ４３ and R ４４ (Hereinafter referred to as “R ４１ ~R ４４ (Sometimes abbreviated as ") may all be the same, all be different, or only partially the same.

[0060] R １１ ~R １３ , R ２１ ~R ２４ , R ３１ ~R ３３ , and R ４１ ~R ４４ The hydrocarbon group in this expression may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group (aryl group). It may be an aliphatic hydrocarbon group in which one or more hydrogen atoms are substituted with an aromatic hydrocarbon group, or it may be a polycyclic hydrocarbon group formed by the fusion of a cyclic aliphatic hydrocarbon group and an aromatic hydrocarbon group.

[0061] The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group (alkyl group) or an unsaturated aliphatic hydrocarbon group.

[0062] The alkyl group may be linear, branched, or cyclic, and if cyclic, it may be monocyclic or polycyclic. Preferably, the alkyl group has 1 to 20 carbon atoms.

[0063] Linear or branched alkyl groups preferably have 1 to 20 carbon atoms. Examples of linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, and 3-methyl Examples include hexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group.

[0064] The cyclic alkyl group preferably has 3 to 20 carbon atoms. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl, and tricyclodecyl groups. Furthermore, examples include those in which one or more hydrogen atoms of these cyclic alkyl groups are substituted with linear, branched, or cyclic alkyl groups. Here, examples of linear, branched, and cyclic alkyl groups that substitute for hydrogen atoms include those listed above as examples of alkyl groups.

[0065] Furthermore, the unsaturated aliphatic hydrocarbon group may be linear, branched, or cyclic. In the case of a cyclic unsaturated aliphatic hydrocarbon group, it may be monocyclic or polycyclic, and the number of carbon atoms in the unsaturated aliphatic hydrocarbon group is preferably 2 to 20. An example of an unsaturated aliphatic hydrocarbon group is a group in which one or more single bonds (C-C) between carbon atoms in the alkyl group are replaced by unsaturated double bonds (C=C) or triple bonds (C≡C). In the unsaturated aliphatic hydrocarbon group, there may be only one unsaturated bond, or there may be two or more, and if there are two or more, these unsaturated bonds may be only double bonds, only triple bonds, or a mixture of double and triple bonds. In the unsaturated aliphatic hydrocarbon group, the position of the unsaturated bond is not particularly limited.

[0066] Preferred unsaturated aliphatic hydrocarbon groups include, for example, linear or branched alkenyl and alkynyl groups, which correspond to groups with one unsaturated bond, and cyclic cycloalkenyl and cycloalkynyl groups. Examples of the alkenyl groups include ethenyl (vinyl) groups, 2-propenyl (allyl) groups, and cyclohexenyl groups.

[0067] The aryl group may be monocyclic or polycyclic, and preferably has 6 to 20 carbon atoms. Examples of such aryl groups include phenyl, 1-naphthyl, 2-naphthyl, o-tolyl, m-tolyl, p-tolyl, and xylyl (dimethylphenyl) groups. These aryl groups may also be substituted with one or more hydrogen atoms of other aryl groups, alkyl groups, etc. The aryl groups having these substituents preferably have 6 to 20 carbon atoms, including the substituents.

[0068] In general formula (1)-11, R １１ , R １２ and R １３If two or more of these are hydrocarbon groups, these hydrocarbon groups may bond to each other and form a ring together with the carbon atoms to which these hydrocarbon groups are bonded (carbon atoms that make up the imidazole skeleton). Here, "two or more hydrocarbon groups bond to each other" means R １１ ~R １３ When only two or all (three) of these are hydrocarbon groups, and only two of these hydrocarbon groups are bonded to each other, R １１ ~R １３ All three of these are hydrocarbon groups, and there are cases where all of these hydrocarbon groups are bonded to each other. In either case, these hydrocarbon groups are bonded to each other by carbon atoms.

[0069] When two or more hydrocarbon groups are bonded to each other, the position of the carbon atom to which they bond (bonding position) is not particularly limited. For example, if the hydrocarbon groups to be bonded are linear or branched, the bonding position may be the terminal carbon atom of the hydrocarbon group, or it may be the so-called root carbon atom directly bonded to the carbon atom constituting the imidazole skeleton of the hydrocarbon group, or it may be a carbon atom in an intermediate position between these terminal and root positions. On the other hand, if the hydrocarbon groups to be bonded are cyclic, or have both a linear and cyclic structure, the bonding position may be the root carbon atom, or it may be any other carbon atom.

[0070] R １１ ~R １３ When two of the hydrocarbon groups are bonded to each other, the resulting ring may be monocyclic or polycyclic. The group represented by general formula (1)-11 has a fused ring structure consisting of an imidazole skeleton and a ring formed by the bonding of these hydrocarbon groups.

[0071] In general formula (1)-12, R ２１ , R ２２ , R ２３ and R ２４If two or more of these are hydrocarbon groups, these hydrocarbon groups may bond to each other and form a ring with the nitrogen atom to which these hydrocarbon groups are bonded and the carbon atom bonded to this nitrogen atom (the same carbon atom to which all three nitrogen atoms are bonded). Here, "two or more hydrocarbon groups bond to each other" means R as described above. １１ ~R １３ This means the same as when any of the hydrocarbon groups are bonded to each other. For example, to bond in this way, R ２１ ~R ２４ When only two, three, or all (four) of these are hydrocarbon groups, and only two or three of these hydrocarbon groups are bonded to each other, R ２１ ~R ２４ All of these (four types) are hydrocarbon groups, and there are cases where all of these hydrocarbon groups are bonded to each other, and the way in which hydrocarbon groups are bonded to each other is also R １１ ~R １３ This is the same as the case described above.

[0072] In general formula (1)-13, R ３１ , R ３２ and R ３３ If two or more of these are hydrocarbon groups, these hydrocarbon groups may bond to each other and form a ring with the nitrogen atom or carbon atom to which these hydrocarbon groups are bonded, together with the carbon atom bonded to this nitrogen atom, or the nitrogen atom bonded to the carbon atom. Here, "two or more hydrocarbon groups bonded to each other" means R as described above. １１ ~R １３ This means the same as when any of the hydrocarbon groups are bonded to each other. For example, to bond in this way, R ３１ ~R ３３ When only two or all (three) of these are hydrocarbon groups, and only two of these hydrocarbon groups are bonded to each other, R ３１ ~R ３３ All of these (3 types) are hydrocarbon groups, and there are cases where all of these hydrocarbon groups are bonded to each other, and the way in which hydrocarbon groups are bonded to each other is also R １１ ~R １３ This is the same as the case described above.

[0073] In general formula (1)-14, R ４１ , R ４２ , R ４３ and R ４４ If two or more of these are hydrocarbon groups, these hydrocarbon groups may bond to each other and form a ring with the nitrogen atom to which these hydrocarbon groups are bonded and the carbon atom bonded to this nitrogen atom (the same carbon atom to which all three nitrogen atoms are bonded). Here, "two or more hydrocarbon groups bond to each other" means R as described above. １１ ~R １３ This means the same as when any of the hydrocarbon groups are bonded to each other. For example, to bond in this way, R ４１ ~R ４４ When only two, three, or all (four) of these are hydrocarbon groups, and only two or three of these hydrocarbon groups are bonded to each other, R ４１ ~R ４４ All of these (four types) are hydrocarbon groups, and there are cases where all of these hydrocarbon groups are bonded to each other, and the way in which hydrocarbon groups are bonded to each other is also R １１ ~R １３ This is the same as the case described above.

[0074] <Second group> The second group contains an ethylenic double bond, preferably a (meth)acryloyl group, and more preferably an acryloyl group.

[0075] The second group may contain structures other than an ethylenic double bond, and may contain a divalent linking group. Examples of divalent linking groups include an oxygen atom, an alkylene group, a carbonyl group, an ester group, an arylene group (excluding arylene groups that bond to a specific carbonyl group), or a combination of two or more of these.

[0076] The divalent linking group in the second group is preferably an ester group or a divalent linking group containing an ester group.

[0077] The ester group is preferably *1-C(=O)-O-*2 (where *1 is the bond position with the ethylenic double bond, and *2 is the bond position with a specific carbonyl group or a linking group between specific carbonyl groups).

[0078] The divalent linking group containing an ester group is [1]*1-C(=O)-O-alkylene group A-*2, [2]*1-C(=O)-O-(RO) ｎ - *2, or [3] *1 - C(=O) - O - alkylene group A - O - C(=O) - *2 (*1 and *2 are as described above. In [1] and [3], the number of carbon atoms in alkylene group A is, for example, 1 to 10, 1 to 5, or 1 to 3. In [2], R is an alkylene group (the number of carbon atoms is, for example, 2 to 4, or 2 to 3), and n is an integer of 1 or more (for example, 1 to 15, 1 to 10, or 1 to 5). The second group is [R Ｘ -CH=CR Ｙ -C(=O)-OR Ｚ It is preferable that the group is represented as -*. Ｘ R is hydrogen or an alkyl group (with, for example, 1 to 5 or 1 to 3 carbon atoms), and hydrogen is preferred. Ｙ R is either a hydrogen atom or a methyl group. Ｚ The first group is a divalent linking group, preferably an alkylene group (with, for example, 1 to 10 or 1 to 5 carbon atoms). * indicates the bonding position. The second group bonds to the benzene ring, for example, at the position of *.

[0079] <Specific structure of the second component> The second component is preferably a compound represented by the following general formula (A).

[0080]

[0081] In general formula (A), R １ is the first base (in other words, R １ The carbonyl group bonded to it is a specific carbonyl group. ２ is a divalent linking group. n1 is 1 or 2. n2 is 1 or 2. n1 + n2 may be 2 to 4, or 2 or 3. When n1 is 2, the substituents consisting of the first group and a specific carbonyl group may be the same or different. When n2 is 2, R ２ The substituents consisting of the acryloyl group may be the same or different. In general formula (A), R ２Furthermore, substituents consisting of acryloyl groups can be treated as a second group.

[0082] In general formula (A), R １ Preferably, the group is represented by the general formula (1)-11, general formula (1)-12, general formula (1)-13, or general formula (1)-14 mentioned above. As the groups represented by general formula (1)-11, general formula (1)-12, general formula (1)-13, or general formula (1)-14 have been described above, their explanation will be omitted here.

[0083] In general formula (A), R ２ It is preferable that the linking group is an oxygen atom or a divalent linking group containing an oxygen atom. Examples of divalent linking groups containing an oxygen atom include *3-O-alkylene group A-*4, *3-O-(RO) ｎ Examples include groups represented by -*4, or *3-O-alkylene group A-O-C(=O)-*4. *3 is the bonding site to the carbonyl group, and *4 is the bonding site to the benzene ring. The alkylene groups A, R, and n are the same as those described for the second group.

[0084] In general formula (A), when n1 and n2 are 1, the compound represented by general formula (A) may also be the compound represented by the following general formula (B).

[0085]

[0086] R in general formula (B) １ and R ２ R in general formula (A) １ and R ２ It is similar to that.

[0087] The second component may consist of only one type or two or more types.

[0088] By forming a resin layer using a curable composition comprising a first component (polysiloxane having epoxy groups) and a second component containing an ethylenically double bond, when the resin layer is exposed, intermolecular reactions of the ethylenically double bond of the second component proceed, causing the second component to polymerize and reducing its solubility in the solvent (developer). Therefore, when the resin layer is developed after exposure, elution of the second component from the resin layer into the solvent (developer) becomes less likely (the content of the second component in the resin layer is easily maintained). Therefore, when the resin layer is heated after development, a cured product is easily formed in which the curing reaction of the epoxy groups of the polysiloxane due to the base released from the second component, and the curing reaction from the remainder of the second component after the base is released, have proceeded sufficiently. As described above, by using the curable composition according to this disclosure, the elution of the second component during development is suppressed, and the curing reaction during heating after development can proceed sufficiently, so it is considered that a cured product with excellent patternability can be easily formed.

[0089] Furthermore, if the first component has a functional group containing an unsaturated carbon bond, a reaction proceeds between the first and second components when the resin layer is exposed to light. This results in polymerization of the second component, reducing its solubility in the solvent, and can also contribute to improving the lithographic properties of the curable composition.

[0090] In particular, by using a second component having a group represented by the aforementioned general formulas (1)-11, (1)-12, (1)-13, or (1)-14, a base conversion effect is achieved in which a base is expressed by the action of a base, as well as a base proliferation effect that generates a base by reacting with hydroxyl groups, etc. For details on the base conversion and base proliferation effects related to these structures, please refer to the content described in International Publication No. 2020 / 045458. When a second component having base conversion and base proliferation effects is used, hydroxyl groups derived from the reaction product of the base and the epoxy group, or hydroxyl groups derived from the polysiloxane, act on the second component, resulting in the generation of a base from the second component and a reaction between the remainder of the second component and the hydroxyl groups. In this way, the curing reaction originating from the epoxy group proceeds, and the increase in the number of hydroxyl groups contained in the resulting polysiloxane cured product is suppressed, resulting in a cured product with excellent low dielectric properties, etc.

[0091] The content of the second component in the curable composition is preferably 1.0 part by mass or more, 5.0 parts by mass or more, 10.0 parts by mass or more, or 15.0 parts by mass or more, and also preferably 150.0 parts by mass or less, 100.0 parts by mass or less, 80.0 parts by mass or less, or 50.0 parts by mass or less, based on the content of the first component in the curable composition being 100 parts by mass or more. From another viewpoint, the content of the second component in the curable composition is preferably 1.0% by mass or more, 5.0% by mass or more, 8.0% by mass or more, or 120.0% by mass or more, and also preferably 60.0% by mass or less, 50.0% by mass or less, 40.0% by mass or less, or 30.0% by mass or less, based on the total amount of the curable composition.

[0092] <<<Photoradical Generator>>> A photoradical generator is a compound that generates radicals upon light irradiation (exposure). The generated radicals radically polymerize the ethylenic double bond of the second component and the unsaturated double bond of the polysiloxane, thereby improving the curability (developer resistance, etc.) of the exposed area.

[0093] As the photoradical generator, known and conventional photoradical generators can be used. Examples include benzoin ethers, acetophenones, α-ketols, aromatic sulfonyl chlorides, photoactive oximes, benzoin, benzyl, benzophenones, ketals, thioxanthones, and acylphosphine oxides.

[0094] Examples of benzoin ether-based photoradical generators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, and anisoine.

[0095] Examples of acetophenone-based photoradical generators include 1-hydroxycyclohexyl phenyl ketone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and methoxyacetophenone.

[0096] Examples of α-ketol-based photoradical generators include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropan-1-one.

[0097] Examples of aromatic sulfonyl chloride-based photoradical generators include 2-naphthalene sulfonyl chloride. Examples of photoactive oxime-based photoradical generators include 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-oxime.

[0098] Examples of benzoin-based photoradical generators include benzoin.

[0099] Examples of benzyl-based photoradical generators include benzyl.

[0100] Examples of benzophenone photoradical generators include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexylphenyl ketone.

[0101] Examples of ketal-based photoradical generators include benzyldimethyl ketal.

[0102] Examples of thioxanthone-based photoradical generators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.

[0103] Examples of acylphosphine oxide-based photoradical generators include bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylpropan-1-yl)phosphine oxide, and bis(2,6-dimethyl (Xybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylprop Pan-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2 - Phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-Trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethitoxybenzoyl-2,4,6-trimeth Examples include benzoyl-n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, tri(2-methylbenzoyl)phosphine oxide, etc.

[0104] These photoradical generators may be used individually or in combination of two or more types.

[0105] The amount of photoradical generator in the curable composition is preferably 0.1 to 15.0 parts by mass, and more preferably 1.0 to 10.0 parts by mass, when the first component in the curable composition is 100 parts by mass.

[0106] <<<Other Components>>> The curable composition of this disclosure may contain other components. Other components may include, for example, inorganic fillers such as silica, peroxides such as α,α'-bis(t-butylperoxy-m-isopropyl)benzene, resins and polymer components such as maleimide resins and styrene elastomers, sensitizers, adhesion aids, surfactants, leveling agents, plasticizers, adhesives, colorants, fibers, silane coupling agents, flame retardants, cellulose nanofibers, dispersants, thermosetting catalysts, thickeners, defoamers, antioxidants, rust inhibitors, adhesion enhancers, organic solvents, etc. These components may be blended in appropriate amounts depending on the application.

[0107] <<

[0108] First, in step 1, a curable composition is applied to the substrate and dried to form a resin layer, or a dry film is laminated onto the substrate to transfer a resin layer made of the curable composition. As for the method of applying the curable composition to the substrate, conventional methods used for applying curable compositions, such as application using a spin coater, bar coater, blade coater, curtain coater, screen printing machine, spray application using a spray coater, and inkjet methods can be used.

[0109] Methods for drying the coating include forced-air drying, heating with an oven or hot plate, and vacuum drying. While the drying conditions are not particularly limited, natural drying, forced-air drying, or heating can be performed at 60-130°C for 1-30 minutes.

[0110] There are no particular restrictions on the substrate; it can be widely applied to semiconductor substrates such as silicon wafers, wiring boards, and substrates made of various resins and metals.

[0111] Next, in step 2, the resin layer formed on the substrate is irradiated (exposed) with light either through a photomask having a pattern or directly in a patterned manner. In the method of laminating a dry film, the film material is peeled off before exposure. If the film material is light-transmitting, the film material may be left on the resin layer during exposure, and then the film material may be peeled off. For exposure, light with a wavelength that can activate the photoradical generator is used. Specifically, light with a maximum absorption wavelength in the range of 350 to 410 nm is preferred. As the exposure apparatus, contact aligners, mirror projections, steppers, laser direct exposure apparatuses, etc., can be used.

[0112] Next, in step 3, the resin layer is treated with a developer. This removes the unexposed portions of the resin layer, allowing a patterned film to be formed. After development, the resin layer may be washed with a rinsing solution if necessary.

[0113] For development, any method can be selected from conventionally known photoresist development methods, such as the rotary spray method, the paddle method, or the immersion method with ultrasonic treatment.

[0114] The developer can be a solvent that dissolves polysiloxane, the main component of the curable composition, and it is preferable to use an organic solvent to prevent corrosion of circuits, etc. For example, solvents such as chloroform, methylene chloride, toluene, N-methyl-2-pyrrolidone (NMP), tetrahydrofuran (THF), cyclohexanone, propylene glycol monomethyl ether acetate (PMA), diethylene glycol monoethyl ether acetate (CA), methyl ethyl ketone, and ethyl acetate can be used. The developer may be used alone or as a mixture of two or more types.

[0115] Furthermore, the developing solution may contain solvents other than the organic solvents mentioned above, from the viewpoint of adjusting the development speed, and may also contain appropriate amounts of surfactants, etc., as needed.

[0116] Examples of rinsing solutions include distilled water, methanol, ethanol, and isopropyl alcohol.

[0117] Furthermore, if necessary, the pattern film may be heated in step 4. The heating temperature is not particularly limited, but for example, it may be heated at 100 to 220°C for 30 to 120 minutes. Air may be used as the atmosphere (gas) at this time, or an inert gas such as nitrogen or argon may be used.

[0118] <<<<<Applications>>>>> The curable composition according to this disclosure can be used for a variety of applications. In particular, since the cured product obtained using the curable composition according to this disclosure can undergo a sufficient curing reaction even after development, it is preferably used as a material for electronic components. More specifically, the cured product obtained using the curable composition according to this disclosure is preferably used as an insulating material in electronic components such as high-capacity, high-speed communication systems represented by fifth-generation communication systems (5G) and millimeter-wave radar for automotive ADAS (Advanced Driver-Assistance Systems).

[0119] The curable composition will be specifically described below with reference to examples, but the present invention is not limited to the following.

[0120] <<<Curable Composition>>> <<Raw Materials>> <First Component: Polysiloxane> 3-Glycidyloxypropyltrimethoxysilane (GPTS) and 3-(trimethoxysilyl)propyl acrylate (APTS), represented by the following formula, were used as monomers.

[0121]

[0122] The molar ratio of GPTS to APTS is made equal, and a partial hydrolysis and condensation reaction is carried out under anhydrous methanol using hydrochloric acid as a catalyst, resulting in GPTS represented by the following formula. ０．５ - APTS ０．５ I obtained it.

[0123]

[0124] The obtained GPTS ０．５ - APTS ０．５ The number-average molecular weight was 4,358, the weight-average molecular weight was 10,742, and the polydispersity index (weight-average molecular weight / number-average molecular weight) was 2.5.

[0125] <Second Component> As shown in the following reaction equation, 4-hydroxybenzoic acid and acryloyl chloride were reacted to synthesize 4-acryloyloxybenzoic acid. 4-hydroxybenzoic acid (b-OH, 14 g, 0.10 mol), triethylamine (TEA, 20 mL), and dried tetrahydrofuran (THF, 140 mL) were added to a flask. Next, acryloyl chloride (a-cl, 10 mL) was added to the flask and stirred overnight at room temperature. After the reaction was complete, the reaction product was washed with dichloromethane, hydrochloric acid, and saturated sodium chloride aqueous solution. The washed reaction product was then further washed with tetrahydrofuran, hydrochloric acid, and saturated sodium chloride aqueous solution. Finally, it was washed with hot water to obtain 4-acryloyloxybenzoic acid (b-A).

[0126] Next, 4-acryloyl benzoyl chloride was synthesized by reacting 4-acryloyloxybenzoic acid (b-A) with thionyl chloride, as shown in the following reaction equation. Compound (A-1) was obtained by reacting the obtained 4-acryloyl benzoyl chloride with 2-ethyl-4-methylimidazole. 4-acryloyloxybenzoic acid (b-A, 8.2 g, 0.43 mol) and thionyl chloride (10 mL) were added to the flask. The mixture in the flask was then stirred at 75°C for 3 hours. After stirring, the solvent was removed by distillation under reduced pressure. Then, dichloromethane, triethylamine (15 mL) and 2-ethyl-4-methylimidazole (2E4MZ, 4.4 g, 40 mmol) were added to the flask and stirred overnight at room temperature. After the reaction was complete, the reactants were washed with water and saturated sodium chloride aqueous solution. Purification was performed by silica gel column chromatography using a mixed solvent of acetone / hexane (3 / 7 by volume) as the mobile phase. The fraction containing the target substance was collected and concentrated to obtain the target compound (A-1) as a yellow viscous liquid (yield 5.7 g, yield 47%). The obtained compound (A-1) １ The results of the H-NMR analysis are shown in Table 1.

[0127]

[0128] <Comparative Compound> Compound A-2 was used as a comparative compound.

[0129] <Photoradical Generator> As the photoradical generator, IRGACURE OXE 05, a photoradical generator manufactured by BASF Japan, was used.

[0130] <<<Preparation of curable composition>>> <<Evaluation test 1: Evaluation of curing agent elution>> <Preparation of evaluation sample> GPTS ０．５ - APTS ０．５ (88 mg) was dissolved in chloroform (0.41 g), and a predetermined amount of compound A-1 and a photoradical initiator (5.0 mg) were added. The amount of compound A-1 added was changed to 10 mg, 20 mg, 30 mg, 50 mg, or 80 mg to prepare varnishes of multiple curable compositions. Using a spin coater, each varnish of the curable composition was applied to a silicon wafer at 3000 rpm for 60 seconds, and dried on a hot plate at 60°C for 3 minutes to form a resin layer consisting of each curable composition. Subsequently, the silicon wafer with the resin layer formed was cut into a 2.5 × 15 cm shape to obtain test specimens. The resin layer of the test specimen was subjected to an irradiation at a wavelength of 365 nm and an irradiance of 50 mW / cm². ２ The LED light was measured as an integrated luminous intensity of 200 mJ / cm². ２ The light was applied in such a manner. After light irradiation, the test specimen was immersed in propylene glycol monomethyl ether acetate (PEGMA) for 20 seconds for development. Subsequently, the resin layer of the test sample was heat-cured using a hot plate at 160°C for a predetermined time (0-60 minutes). In this way, evaluation sample 1 (developing sample) was obtained. In addition, the resin layer of the test specimen was irradiated with a wavelength of 365 nm and an irradiance of 50 mW / cm². ２ The LED light was measured as an integrated luminous intensity of 200 mJ / cm². ２ The light was applied in such a manner. After light irradiation, the test specimen was heated on a hot plate at 160°C for a predetermined time (0-60 minutes) to heat-cur the resin layer of the test sample. In this way, evaluation sample 2 (No Development sample) was obtained.

[0131] <Preparation of comparison samples> GPTS ０．５ - APTS ０．５(80 mg) was dissolved in chloroform (0.37 g), and compound A-2 (9.0 mg) and a photoradical initiator (5.1 mg) were added. Using a spin coater, the varnish of each curable composition was applied to a silicon wafer at 3000 rpm for 60 seconds, and dried on a hot plate at 60°C for 3 minutes to form a resin layer consisting of each curable composition. Subsequently, the silicon wafer with the resin layer formed was cut into a 2.5 × 15 cm shape to obtain test specimens. The resin layer of the test specimen was exposed to light at a wavelength of 365 nm and an illuminance of 5 mW / cm². ２ The LED light was measured as an integrated luminous intensity of 200 mJ / cm². ２ The light was applied in such a manner. After light irradiation, the test specimen was immersed in propylene glycol monomethyl ether acetate (PEGMA) for 20 seconds for development. Subsequently, the resin layer of the test sample was heat-cured using a hot plate at 170°C for a predetermined time (0-1500 seconds). Comparative sample 1 (developing sample) was obtained in this manner. In addition, the resin layer of the test specimen was irradiated with a wavelength of 365 nm and an irradiance of 5 mW / cm². ２ The LED light was measured as an integrated luminous intensity of 200 mJ / cm². ２ The specimens were irradiated in such a manner. After light irradiation, the specimens were heated on a hot plate at 170°C for a predetermined time (0-1500 seconds) to heat-cur the resin layer of the test sample. In this way, comparative sample 2 (No Development sample) was obtained.

[0132] <Evaluation> For each of evaluation samples 1 and 2, and comparative samples 1 and 2, the decrease in epoxy groups in the cured films prepared by varying the heating time was confirmed by FT-IR. More specifically, FT-IR measurements were performed on evaluation samples 1 and 2, which were prepared by varying the heating time, and the measured spectra were recorded at 2940 cm⁻¹. －１ 913 cm when normalized based on the peak. －１ Absorption peak height (913 cm) －１ The normalized peak height was calculated. Figure 1 shows the results for evaluation sample 1 (developing sample) and evaluation sample 2 (no developing sample) when compound A-1 was added at a dose of 30 mg, with the X axis representing heating time (minutes) and the Y axis representing 913 cm.－１ Figure 2 shows a scatter plot with normalized peak heights, superimposed on each other. Figure 2 also shows the results for Evaluation Sample 2 (Developing Sample) and Evaluation Sample 2 (No Development Sample), with the X-axis representing heating time (seconds) and the Y-axis representing 913 cm. －１ A scatter plot with normalized peak height was created and superimposed, and this figure is shown. From Figure 1, regardless of whether development was performed or the heating time, the peak height was 913 cm. －１ It is understood that the normalized peak height changes are similar (showing similar behavior with respect to the decrease in epoxy groups). Similar trends were also observed for samples with compound A-1 added at amounts of 10 mg, 20 mg, 50 mg, and 80 mg. On the other hand, as shown in Figure 2, when compound A-2 was used, the heating time varied depending on whether development was performed, resulting in a difference of 913 cm⁻¹. －１ The normalized peak height changes differ. Based on the above, it is considered that by using a specified polysiloxane in combination with compound A-1, unlike when compound A-2 is used, the effect of curing agent elution due to development is suppressed due to polymerization of compound A-1, and the curing reaction of the epoxy groups of the polysiloxane proceeds sufficiently.

[0133] <<Evaluation Test 2: Developerability Evaluation>> GPTS ０．５ - APTS ０．５ (160 mg) was dissolved in chloroform (0.84 g), and compound A-1 (43 mg) and a photoradical initiator (10 mg) were added to prepare a curable composition varnish. The curable composition varnish was applied to a silicon wafer using a spin coater to a cured film thickness of 3.3 μm, and dried on a hot plate at 60°C for 3 minutes to form a resin layer made of the curable composition. Subsequently, the silicon wafer with the resin layer formed was cut into a 2.5 × 15 cm shape to obtain test specimens. The resin layer of the test specimen was subjected to irradiation at a wavelength of 365 nm and an irradiance of 5 mW / cm². ２ The LED light was measured as an integrated luminous intensity of 20 mJ / cm². ２The light was applied in such a manner. After light irradiation, the test specimen was immersed in propylene glycol monomethyl ether acetate (PEGMA) for 20 seconds for development. Subsequently, the resin layer of the test sample was heat-cured using a hot plate at 160°C for 60 minutes. Cross-sectional observation of the pattern of the resin layer after heat curing confirmed that a pattern with a film thickness of approximately 3.3 μm and a line / space of 10 μm / 10 μm could be formed. From the above, it is understood that by using a specified polysiloxane in combination with compound A-1, it is possible to form a cured product with excellent developability.

[0134] According to the curable composition of the present invention, the curing reaction can proceed sufficiently even after development. Therefore, the curable composition of the present invention can be preferably used for various applications, such as materials for electronic components. Cross-reference of related applications

[0135] This application claims priority pursuant to Japanese Patent Application No. 2024-157027, filed with the Japan Patent Office on 10 September 2024, all of which disclosures are incorporated herein by reference in their entirety.

Claims

1. A curable composition comprising: a first component which is a polysiloxane having an epoxy group; and a second component which is a compound comprising a carbonyl group, a first group bonded to the carbonyl group which generates a base that is released from the carbonyl group upon heating, and a second group which contains an ethylenic double bond.

2. The curable composition according to claim 1, wherein the second group comprises a (meth)acryloyl group.

3. The curable composition according to claim 1, wherein the second component is a compound represented by the following general formula (A). (In general formula (A), R １ is the first base, R ２ (This is a divalent linking group, where n1 is 1 or 2, and n2 is 1 or 2.) 4. In the general formula (A), R １ is a group represented by the following general formula (1)-11, general formula (1)-12, general formula (1)-13 or general formula (1)-14, The curable composition according to claim 3. In the formula, R １１ , R １２ , R １３ , R ２１ , R ２２ , R ２３ , R ２４ , R ３１ , R ３２ , R ３３ , R ４１ , R ４２ , R ４３ and R ４４ each independently represents a hydrogen atom or a hydrocarbon group. When two or more of R １１ , R １２ and R １３ are hydrocarbon groups, two or more hydrocarbon groups may be bonded to each other to form a ring. When two or more of R ２１ , R ２２ , R ２３ and R ２４ are hydrocarbon groups, two or more hydrocarbon groups may be bonded to each other to form a ring. When two or more of R ３１ , R ３２ and R ３３ are hydrocarbon groups, two or more hydrocarbon groups may be bonded to each other to form a ring. When two or more of R ４１ , R ４２ , R ４３ and R ４４ are hydrocarbon groups, two or more hydrocarbon groups may be bonded to each other to form a ring. * represents a bond that binds to the carbon atom of the carbonyl group.

5. The curable composition according to claim 1, wherein the first component has a functional group containing an unsaturated carbon bond.

6. The curable composition according to claim 1, further comprising a photoradical generator.

7. The curable composition according to claim 5, wherein the first component comprises a structural unit represented by the following formula (I) and a structural unit represented by the following formula (II). In the formula, R Ａ R represents a hydrogen atom, hydroxyl group, alkoxy group, or hydrocarbon group. Ｂ This represents a functional group containing an epoxy group. In the formula, R Ｃ R represents a hydrogen atom, hydroxyl group, alkoxy group, or hydrocarbon group. Ｄ This represents a functional group containing an unsaturated double bond.

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